JPS61261365A - Photo-curable coating composition - Google Patents
Photo-curable coating compositionInfo
- Publication number
- JPS61261365A JPS61261365A JP10176585A JP10176585A JPS61261365A JP S61261365 A JPS61261365 A JP S61261365A JP 10176585 A JP10176585 A JP 10176585A JP 10176585 A JP10176585 A JP 10176585A JP S61261365 A JPS61261365 A JP S61261365A
- Authority
- JP
- Japan
- Prior art keywords
- group
- epoxy
- weight
- parts
- epoxycycloalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐摩耗性に優れた被覆組成物に関する。さら
に詳しくは、優れた耐摩耗性が要求される被塗物の表面
に塗布し、紫外線を短時間照射することにより、透明ま
たは半透明の被膜を形成させて被塗料物を保護する被覆
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coating composition with excellent wear resistance. More specifically, it is a coating composition that protects the object by forming a transparent or translucent film by applying it to the surface of the object that requires excellent abrasion resistance and irradiating it with ultraviolet light for a short period of time. Regarding.
近年、プラスチック製品はますますその用途を拡大しつ
つあり、自動車、電子機器、事務機器といった産業分野
において、成形の容易さあるいは重量の軽減化といった
利点のためその使用が増大しつつある。プラスチック成
形物の最大の難点の一つに、金属やガラスに比べてその
表面が傷つきやすいことがある。特にポリメチルメタク
リレー） （ＰＭＭＡ）やポリカーボネート（ｐｃ）に
代表される有機ガラスにおいては、その表面が損傷され
ることによって透明性を失うことは致命的であり、その
表面を何らかの方法で保護することが要請される。In recent years, plastic products have been increasingly used in industrial fields such as automobiles, electronic equipment, and office equipment due to their advantages such as ease of molding and reduced weight. One of the biggest drawbacks of plastic molded products is that their surfaces are more easily scratched than metal or glass. In particular, for organic glasses such as polymethyl methacrylate (PMMA) and polycarbonate (PC), loss of transparency due to damage to the surface is fatal, so it is necessary to protect the surface in some way. This is required.
このようなプラスチック成形物の表面の損傷の防止を目
的として、既に多くの組成物や方法が提案されているが
、それらは大別して三つのグループに分けられる。Many compositions and methods have already been proposed for the purpose of preventing damage to the surface of such plastic molded products, but these can be roughly divided into three groups.
その一つは、熱硬化性のシリコン樹脂等をプラスチック
に塗布し、加熱により架橋させて硬度の高い塗膜を得る
ものである。この硬化塗膜は硬度は極めて高く耐摩耗性
は優れるが、可撓性が乏しく脆いという欠点がある。ま
た加熱による硬化は速度が遅く、またシリコン樹脂が高
価である等の欠点もある。One of them is to apply a thermosetting silicone resin or the like to plastic and crosslink it by heating to obtain a highly hard coating film. Although this cured coating film has extremely high hardness and excellent abrasion resistance, it has the disadvantage of poor flexibility and brittleness. Further, curing by heating is slow and silicone resins are expensive.
第二のグループは、多官能のアクリロイル基を有するプ
レポリマーおよび多官能もしくは単官能の反応性溶剤に
光開始剤を組み合せた組成物で、これは塗布後紫外線を
照射してアクリロイル基の重合反応により硬化させて被
膜を形成させるものである。この場合には反応そのもの
は数秒〜数十秒で終了し、加熱が不要であり、プラスチ
ックの塗装には適合した方法であるが、形成された被膜
が純有機物であるため硬度が不十分で耐摩耗性が十分と
はいい難い。The second group consists of compositions in which a photoinitiator is combined with a prepolymer having a polyfunctional acryloyl group and a polyfunctional or monofunctional reactive solvent. It is cured to form a film. In this case, the reaction itself completes in a few seconds to several tens of seconds, and no heating is required, making it suitable for painting plastics.However, since the film formed is a pure organic material, it is insufficiently hard and resistant. It is difficult to say that the abrasion resistance is sufficient.
第三のグループは、上記した二つの方法のいわば折衷案
であり、光反応性の７クリロイル基を有するプレポリマ
ーまたはモノマーの中にシリカやアルミナのような無機
物を分散させ、硬化プロセスとしては光硬化反応を利用
し、硬化塗膜の硬度は無３機フィラーの性質を反映させ
て高硬度にしようとするものである。この際、有機マト
リックス中へのフィラーの分散を容易にするために、フ
ィラーの表面を有機物で処理する方法が採用されている
。この方法についての先行技術としては、例えば公表公
報間５７−５００９１１１４号、公表公報間５８−５０
０２５１号、特開昭５７−７４３８９号が挙げられる。The third group is a compromise between the two methods described above, in which an inorganic material such as silica or alumina is dispersed in a prepolymer or monomer containing photoreactive 7-acryloyl groups, and the curing process is performed using light. By utilizing the curing reaction, the hardness of the cured coating film is made to reflect the properties of the inorganic filler to achieve high hardness. At this time, in order to facilitate the dispersion of the filler into the organic matrix, a method is adopted in which the surface of the filler is treated with an organic substance. Prior art regarding this method includes, for example, Publication No. 57-50091114 and Publication No. 58-50.
No. 0251 and JP-A-57-74389.
この方法によれば硬度の高い塗膜が得られるが、光硬化
反応はアクリロイル基の重合反応によるものであり、従
って重合による体積収縮率が大きく被塗物への密着性が
十分ではなかった。またこの反応はラジカル反応である
ため酸素の存在する空気中で反応を実施すると表面の硬
化速度が遅いという欠点があった。According to this method, a coating film with high hardness can be obtained, but the photocuring reaction is based on a polymerization reaction of acryloyl groups, and therefore, the volume shrinkage due to polymerization is large and the adhesion to the object to be coated is not sufficient. Furthermore, since this reaction is a radical reaction, there is a drawback that the surface hardening speed is slow when the reaction is carried out in air where oxygen is present.
本発明の目的は、上述したような欠点を克服する耐摩耗
性の優れた被覆組成物を提供することにある。The object of the present invention is to provide a coating composition with excellent wear resistance that overcomes the above-mentioned drawbacks.
本発明の紫外線硬化性被覆用組成物は、下記成分（Ａ）
、 （Ｂ）および（Ｃ）、
（Ａ）多官能エポキシオリゴマー１００重量部、ＣＢ）
一般式 （ＲＯ）３−ｎＳｉＲ１Ｒ２１・・・［Ｉ ］
［Ｉ式中、ｎは０または１、Ｒはメチル、エチルまたは
プロピル基、Ｒ１はエポキシアルキル、エポキシシクロ
アルキル、グリシドキシより選ばれる炭素数１〜２０の
エポキシ基含有有機残基、Ｒ２はアルキルシクロアルキ
ル、アミノアルキル、アルキルアミン、アルコキシ、ア
ルコキシアルキル、エポキシアルキル、エポキシシクロ
アルキル、アルケニル、クリシドキ、メタクリロキシア
ルキルおよびγ−メルカプトプロピル基からなる群より
選ばれた炭素数１〜２０の有機残基］で表わされる化合
物を加水分解したものでその表面を処理された微粉状の
無機充填剤５〜１００重量部
（Ｃ）紫外線の照射によりエポキシ基を反応させ得る光
開始剤０．１〜１０重量部、
を必須成分として含有するものである。The ultraviolet curable coating composition of the present invention comprises the following component (A):
, (B) and (C), (A) 100 parts by weight of polyfunctional epoxy oligomer, CB)
General formula (RO)3-nSiR1R21...[I]
[In formula I, n is 0 or 1, R is a methyl, ethyl or propyl group, R1 is an epoxy group-containing organic residue with 1 to 20 carbon atoms selected from epoxyalkyl, epoxycycloalkyl, and glycidoxy, and R2 is alkylcyclo An organic residue having 1 to 20 carbon atoms selected from the group consisting of alkyl, aminoalkyl, alkylamine, alkoxy, alkoxyalkyl, epoxyalkyl, epoxycycloalkyl, alkenyl, methacryloxyalkyl, and γ-mercaptopropyl group] 5 to 100 parts by weight of a finely powdered inorganic filler whose surface has been treated with a hydrolyzed compound represented by (C) 0.1 to 10 parts by weight of a photoinitiator capable of reacting epoxy groups by irradiation with ultraviolet light. , contains as essential ingredients.
すなわち１本発明の紫外線硬化性被覆用組成物は、エポ
キシ樹脂またはエポキシ基を含む七ツマ−を有機マトリ
ックスとして用い、エポキシ基を有するシランカップリ
ング剤によりその表面を処理されてグラフト化され、従
ってその表面にエポキシ基を有するシリカやアルミナ等
の無機充填剤を有機マトリックス中に分散させたもので
、これに光反応開始剤として、紫外線の照射によりそれ
自身が分解等の反応を生じ、エポキシ環が開環反応を起
し得るようなある種の酸を生成する化合物を組合わせた
ものである。Namely, the ultraviolet curable coating composition of the present invention uses an epoxy resin or an epoxy group-containing hexamer as an organic matrix, and its surface is treated with a silane coupling agent having an epoxy group to form a graft. An inorganic filler such as silica or alumina that has an epoxy group on its surface is dispersed in an organic matrix, and when used as a photoreaction initiator, it causes reactions such as decomposition when irradiated with ultraviolet rays, and the epoxy ring It is a combination of compounds that produce certain acids that can undergo a ring-opening reaction.
この組成物は、紫外線を照射することによって光開始剤
が分解しである種の酸を生成してエポキシ化合物が開環
反応して硬化し、その際エポキシ基を有するシランカッ
プリング剤で処理されたシリカやアルミナ等もその表面
の官能基が反応してマトリックス中に組み込まれるため
強固な被膜が形成される。また、硬化反応がエポキシ基
の開環反応なので体積収縮率が小さく、しかも開環反応
により水酸基が生成する。これらの理由により、この硬
化組成物を塗膜とした場合には被塗物への密着性が優れ
ている。更に有機マトリックスとして用いるエポキシ樹
脂は、各種の特性を有するものが工業的に生産されてい
るので、その選択によりフレキシビリティ−に優れた塗
膜を得ることもできる。When this composition is irradiated with ultraviolet light, the photoinitiator decomposes and generates a certain type of acid, and the epoxy compound undergoes a ring-opening reaction and cures. At that time, it is treated with a silane coupling agent having an epoxy group. The functional groups on the surface of silica, alumina, etc. react and are incorporated into the matrix, forming a strong film. Further, since the curing reaction is a ring-opening reaction of epoxy groups, the volumetric shrinkage rate is small, and moreover, hydroxyl groups are generated by the ring-opening reaction. For these reasons, when this cured composition is used as a coating film, it has excellent adhesion to the object to be coated. Furthermore, since the epoxy resin used as the organic matrix is industrially produced with various properties, a coating film with excellent flexibility can be obtained by selecting the epoxy resin.
このような理由から、本発明により、紫外線照射によっ
て硬化し、優れた耐摩耗性を示し、かつ被塗物への密着
性が改良された被覆組成物が提供される。For these reasons, the present invention provides a coating composition that is cured by ultraviolet irradiation, exhibits excellent abrasion resistance, and has improved adhesion to objects to be coated.
本発明に用いられる多官能エポキシオリゴマーとは、い
わゆるエポキシ樹脂が広く使用され得る。より具体的に
は、下式に示すような各種のエポキシ樹脂が挙げられる
。As the polyfunctional epoxy oligomer used in the present invention, so-called epoxy resins can be widely used. More specifically, various epoxy resins as shown in the following formulas may be mentioned.
グリシジルエーテル型
ビスフェノールＡジグリシジルエーテルビスフェノール
ＡジβメチルグリシジルエーテルビスフェノールＦジグ
リシジルエーテルテトラヒドロキシフェニルメタンテト
ラグリシジルエーテルレゾルシノールジグリシジルエー
テル
ブロム化ビスレエノールＡジグリシジルエーテル（Ｂｒ
の代りにＣＩのものもある）
ノボラックグリシジルエーテル
ポリアルキレングリコールジグリシジルエーテル水素添
加ビスフェノールＡグリシジルエーテルＨ３０
ビスフェノールＡアルキレンオキサイド付加物のジグリ
シジルエーテル
エポキシウレタン樹脂
グ
リセリントリグリシジルエーテルペ
ンタエリスリトールジグリシジルエーテルｐ−オキシ安
息香酸グリシジルエーテル番エステルシジルエステル
ハ
（ＣＨ２）、−ｃｏｏｅｄ２−ＣＨ−ＣＨ２しＨ
、１
（ＣＨ２）５ ＣＨ３
ダイマー酸ジグリシジルエステル
ダニ２２止１１ｚ屋
グリシジルアニリン テトラグリシジルアミノジフェニ
ルメタントリグシジルイソシアヌレート
エポキシ化ポリブタジェン
エポキシ化大豆油
胆」麓王ゴ土之樹脂
レート
アジペート
ホキサイド サイドペンチル）エー
テル
上式においてＲ１、Ｒ２、Ｒ３およびＲ４はそれぞれ独
立して水素または炭素数１〜６のアルキル基を表わし、
Ａ、ｍ、およびｎはそれぞれ独立して０〜２０の整数を
表わす。Glycidyl ether type Bisphenol A diglycidyl ether Bisphenol A diβ-methylglycidyl ether Bisphenol F diglycidyl ether Tetrahydroxyphenylmethane Tetraglycidyl ether Resorcinol diglycidyl ether Brominated bisthreenol A diglycidyl ether (Br
) Novolak glycidyl ether polyalkylene glycol diglycidyl ether hydrogenated bisphenol A glycidyl ether H30 bisphenol A alkylene oxide adduct diglycidyl ether epoxy urethane resin glycerin triglycidyl ether pentaerythritol diglycidyl ether p-oxy Benzoic acid glycidyl ether number ester cidyl ester (CH2), -cooed2-CH-CH2H, 1 (CH2)5 CH3 Dimer acid diglycidyl ester 22-11zya glycidyl aniline tetraglycidyl amino diphenyl methane triglycidyl isocyanurate epoxy In the above formula, R1, R2, R3 and R4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. Representation,
A, m, and n each independently represent an integer of 0 to 20.
本発明の被覆用組成物に配合される有機ケイ素化合物で
表面を処理された微粉状の無機充填剤（成分（Ｂ））と
は、微粉状のシリカやアルミナ等の表面をいわゆるシラ
ンカップリング剤で処理したものである。微粉状の無機
充填剤としては、シリカやアルミナが代表的なものとし
て挙げられるが、その他クレー、タルク、マイカ、アス
ベスト、ケイ酸カルシウム、ガラス粉末、チタニャ、マ
グネシャ等も使用できる。これら無機充填剤としてはで
きるだけ粒径の小さいものが好ましく。The finely powdered inorganic filler (component (B)) whose surface has been treated with an organosilicon compound that is blended into the coating composition of the present invention is a so-called silane coupling agent that binds the surface of finely powdered silica, alumina, etc. It was processed with. Typical fine powder inorganic fillers include silica and alumina, but clay, talc, mica, asbestos, calcium silicate, glass powder, titania, magnesia, and the like can also be used. These inorganic fillers preferably have as small a particle size as possible.
粒径が０．００１−〜１μｓ、より好ましくはＯ，ＯＯ
？ｇａ〜０．０２０ｇのものが好適に用いられる。具体
的には、シリカとしてはＡＥＲＯ９ＩＬ−３８０，−３
００，−２００゜−１３０，−Ｒ９７２（Ｄｅｇｕｓｓ
ａ社製、ドイツ）、や旧−５ＩＬ−２３３、−２１５（
ＰＰＧ社製、アメリカ）が挙げられ、アルミナとしては
ＡＬＯＮ （Ａｌｃａｎ社、カナダ）を挙げることがで
きる。Particle size is 0.001-1μs, more preferably O,OO
? ga to 0.020 g is preferably used. Specifically, the silica is AERO9IL-380,-3
00, -200° -130, -R972 (Deguss
Made by company a, Germany), and old -5IL-233, -215 (
Examples of alumina include ALON (Alcan, Canada).
また、加水分解して無機充填剤の表面を処理するために
用いる式（ＲＯ）３−ｎＳｉＲ１Ｒ２１で表わされる有
機ケイ素化合物は Ｒ１の中にエポキシ基を含むもので
ある。Further, the organosilicon compound represented by the formula (RO)3-nSiR1R21 used for hydrolyzing and treating the surface of an inorganic filler contains an epoxy group in R1.
Ｒ１としては、例えば、
ＣＨ２−ＣＨ２−０−（ＣＨ２）３ （グリシドキシ
プロピル基）等が挙げられる Ｒ２としてはエポキシ基
を含んでいても含んでいなくてもよく広い範囲から選ば
れ例えば、アルキル、シクロアルキル、アミノアルキル
、アルキルアミン、アルコキシ、アルコキシアルキル、
エポキシアルキル、エポキシシクロアルキル、アルケニ
ル、グシドキシ、メタクリロキシアルキルおよびγ−メ
ルカプトプロピルの各基から選ばれる。またＲは、メチ
ル、エチル、プロピル基のような低級アルキル基から選
ばれる。Examples of R1 include CH2-CH2-0-(CH2)3 (glycidoxypropyl group).R2 may or may not contain an epoxy group and is selected from a wide range, such as , alkyl, cycloalkyl, aminoalkyl, alkylamine, alkoxy, alkoxyalkyl,
selected from epoxyalkyl, epoxycycloalkyl, alkenyl, glucidoxy, methacryloxyalkyl and γ-mercaptopropyl groups. Further, R is selected from lower alkyl groups such as methyl, ethyl, and propyl groups.
表面処理の方法としては表面処理に用いる有機シリカ化
合物［Ｉ］を水中に分散させてアルコキシを加水分解さ
せて−ＯＲ基を−ＯＨとする。すなわち、［Ｉ］は下式
のように加水分解される。As a method for surface treatment, the organic silica compound [I] used for surface treatment is dispersed in water, and alkoxy is hydrolyzed to convert the -OR group to -OH. That is, [I] is hydrolyzed as shown in the following formula.
（ＲＯ）３−１３ｉＲ’Ｒ２１−一→（ＨＯ）３−１９
ｉＲ’Ｒ２１［Ｉ ］ ［Ｉ’］次
いでこの水溶液中に微粉状無機充填剤を分散させ檄しく
撹拌して１５分〜２時間保つと無機充填剤の表面への［
工′］の反応は完了する０次いで水を蒸発除去すること
により１表面処理された無機充填剤（成分（Ｂ））が得
られる。表面処理させる量は、無機充填剤１００重量部
に対し、有機シリカ化合物［工］ ５〜５０重量部であ
ることが好ましい、５重量部より少ない場合には処理効
果が十分でなく、５０重量部より多い場合には表面処理
化合物が未反応のまま残存して組成物の耐摩耗性を低下
させることにつながやすく好ましくない。(RO)3-13iR'R21-1 → (HO)3-19
iR'R21 [I] [I'] Next, finely powdered inorganic filler is dispersed in this aqueous solution, stirred gently and kept for 15 minutes to 2 hours, causing [I'] to the surface of the inorganic filler.
The reaction of step '] is completed. Then, water is removed by evaporation to obtain a surface-treated inorganic filler (component (B)). The amount of surface treatment is preferably 5 to 50 parts by weight of the organic silica compound per 100 parts by weight of the inorganic filler. If it is less than 5 parts by weight, the treatment effect will not be sufficient, and 50 parts by weight If the amount is more, the surface treatment compound remains unreacted, which tends to lead to a decrease in the wear resistance of the composition, which is not preferable.
成分（Ｃ）として用いられるエポキシ基を反応させ得る
ような光開始剤とは、紫外線の照射により分解または反
応しである種の酸を生成し、その酸の反応によってエポ
キシ環を開環反応せ得るような化合物であり、具体的に
はオニウムカチオンの、塩類が挙げられ、代表的には下
式に示すようなジアリルジアゾニウム［Ａ］、シアリル
ヨードニウム［Ｂ］、）リアリルスルホニウム［Ｃ］、
ジアルキルアリルスルホニウム［Ｄ］等が挙げられる。A photoinitiator used as component (C) that can react with an epoxy group is a photoinitiator that decomposes or reacts when irradiated with ultraviolet rays to produce a certain type of acid, and the reaction of the acid causes a ring-opening reaction of the epoxy ring. Specific examples include salts of onium cations, typically diallydiazonium [A], sialyliodonium [B],) realylsulfonium [C], as shown in the following formulas.
Examples include dialkylarylsulfonium [D].
［Ａ］ ［Ｂ コ ［Ｃ］
［Ｄ］ＡｒＮ２”Ｘ−Ａｒ２１ Ｘ−Ａｒ５ＳＸ
−ＡｒＳ Ｒ，ＸＸ−；ＢＦ、、−１Ｐ Ｆ６−１ Ａ
ｓＦ６−１５ｂＦ６− 、また下式に示されるようなチ
オピリリウム塩もＲ２Ｒ２
２，４，８−トリアリルチオ ２−メチル−４，６−ジ
フエニピリリウム塩 ルチオピリリウム塩Ｒ１
−Ｈ，ＣＨ３０，Ｎｏ２． ＣＩ Ｒ２＝Ｈ，ＯＨ
３，ＣＨ３０Ｘ＝ＢＦ４． ＰＦ６
特に下式に示されるオニウム塩が多用され得る。[A] [B Ko [C]
[D] ArN2”X-Ar21 X-Ar5SX
-ArS R, XX-; BF,, -1P F6-1 A
sF6-15bF6-, and thiopyrylium salts as shown in the following formula are also R2R2 2,4,8-trialylthio 2-methyl-4,6-diphenypyrylium salt Ruthiopyrylium salt R1
-H, CH30, No2. CI R2=H,OH
3, CH30X=BF4. PF6 In particular, onium salts represented by the following formula may be frequently used.
Ｒ；炭素数１〜４のアルキル基
本発明の被覆組成物は、上述した三つの成分（Ａ）、（
Ｂ）および（Ｃ）を混合分散（或いは溶解）させて得ら
れる。その混合割合は、エポキシオリゴマー（成分（Ａ
）） １００重量部に対し、処理された微粉状の無機充
填剤（成分（Ｂ））は５〜１００重量部の範囲で添加さ
れる。５重量部より少ない場合には、充填剤を添加した
効果が十分発揮できず、１００重量部より多い場合には
組成物の透明性が損なわれると同時に組成物の粘度が高
くなるため好ましくない。光開始剤（成分（Ｃ））の混
合割合は。R: Alkyl having 1 to 4 carbon atoms The coating composition of the invention contains the above-mentioned three components (A), (
It is obtained by mixing and dispersing (or dissolving) B) and (C). The mixing ratio is epoxy oligomer (component (A)
)) The treated fine powder inorganic filler (component (B)) is added in an amount of 5 to 100 parts by weight per 100 parts by weight. If it is less than 5 parts by weight, the effect of adding the filler cannot be sufficiently exhibited, and if it is more than 100 parts by weight, the transparency of the composition will be impaired and the viscosity of the composition will increase, which is not preferable. What is the mixing ratio of the photoinitiator (component (C))?
成分（Ａ） １００重量部対し０．１〜１０重量部の範
囲で添加されるが、１．０〜５．０重量部であることが
より好ましい。０．１重量部より少い場合には反応が遅
くなり、１０重量部より多い場合には開始剤成分が塗膜
物性を低下させるため好ましくない。It is added in an amount of 0.1 to 10 parts by weight, more preferably 1.0 to 5.0 parts by weight, per 100 parts by weight of component (A). If it is less than 0.1 part by weight, the reaction will be slow, and if it is more than 10 parts by weight, the initiator component will deteriorate the physical properties of the coating film, which is not preferable.
本発明の組成物は、被塗物に塗布し紫外線を照射して硬
化させて被覆膜とされるが、被塗物への塗布を容易にす
るために、従来よりエポキシ樹脂用の稀釈剤として知ら
れている各種の稀釈剤を添力臣して組成物の粘度を低下
させて使用することもできる。稀釈剤としてエポキシ基
を有するモノマー（例えばシクロヘキセンオキシドやフ
テンオキシドなど）を用いる場合には光反応により硬化
塗膜中に組み込まれるが、非反応性の通常の溶剤（例え
ばトルエン、メチルエチルケトン、酢酸エチルなど）を
用いる場合には、光硬化の前段階で加熱あるいは室温に
おいて蒸発除去する必要がある。The composition of the present invention is applied to an object to be coated and cured by irradiation with ultraviolet rays to form a coating film.In order to facilitate application to the object, conventional diluents for epoxy resins have been used. It is also possible to use various diluents known as additives to lower the viscosity of the composition. When using monomers with epoxy groups (e.g. cyclohexene oxide, phthene oxide, etc.) as diluents, they are incorporated into the cured coating film by photoreaction, but non-reactive ordinary solvents (e.g. toluene, methyl ethyl ketone, ethyl acetate, etc.) When using a compound, it is necessary to remove it by heating or evaporating at room temperature before photocuring.
本発明の被覆用組成物は、基本的には成分（Ａ）。The coating composition of the present invention basically consists of component (A).
（Ｂ）および（Ｃ）より構成されるが、塗膜表面の平滑
性を改良するためのレベリング材や各種の安定剤等を配
合することができる。Although it is composed of (B) and (C), leveling agents and various stabilizers can be added to improve the smoothness of the coating film surface.
本発明によれば、紫外線照射によって硬化し、体積収縮
率が小さく、強固で優れた耐摩耗性を有し、かつ被塗物
への密着性が改良された被覆組成物が提供される。According to the present invention, there is provided a coating composition that is cured by ultraviolet irradiation, has a small volumetric shrinkage rate, is strong and has excellent abrasion resistance, and has improved adhesion to a coated object.
以下、実施例に基すき本発明をより具体的に説明する。 Hereinafter, the present invention will be explained in more detail based on Examples.
合成例
２００ｇのβ−グリシドキシプロピル−トリメトキシシ
ランをＰＨ４，０に調整した水４０００ｇ中に撹拌して
分散させ１時間保つと透明になった。これに８００ｇの
微粉状シリカ、−ＡＥＲＯＳＩＬ−３８０を高速撹拌機
つきのホモジナイザー（ＮＩＲＯＡＴＯＫＩＺＥＲ社製
、デンマーク）で２０分撹拌して分散液を調製した。Synthesis Example 200 g of β-glycidoxypropyl-trimethoxysilane was stirred and dispersed in 4000 g of water adjusted to pH 4.0, and the mixture became transparent after being kept for 1 hour. A dispersion liquid was prepared by stirring 800 g of finely powdered silica, -AEROSIL-380, for 20 minutes using a homogenizer equipped with a high-speed stirrer (manufactured by NIROATOKIZER, Denmark).
これをスプレードライヤー（特殊機化工業社製）で脱水
乾燥させて白色の処理シリカ（以下、Ｂ−１と略記）を
得た。This was dehydrated and dried using a spray dryer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain white treated silica (hereinafter abbreviated as B-1).
実施例１
液状のビスフェノールＡ型エポキシ樹脂、エピコート
８２８（成分（Ａ）、シェル社製） １００ｇと合成
例で調製した処理シリカ日−１（成分（Ｂ） ） ２５
ｇを混合し、ボールミル中で２０時間処理して分散液を
調製した。これに光開始剤として４弗化ホウ素ジフエニ
ルジアゾニウム塩（成分（Ｃ）） ２ ｇを溶解させ被
覆組成物（組成物１）を得た。Example 1 Liquid bisphenol A epoxy resin, Epicote
828 (component (A), manufactured by Shell) 100g and treated silica prepared in the synthesis example -1 (component (B)) 25
g were mixed and treated in a ball mill for 20 hours to prepare a dispersion. 2 g of boron tetrafluoride diphenyldiazonium salt (component (C)) as a photoinitiator was dissolved in this to obtain a coating composition (composition 1).
この組成物をＰＭＭＡ樹脂板（協和ガス化学製）上にス
ピンナー（４０００ｒｐｍ ）で１２４に塗布し、１８
Ｗ／ｃ＋ｓの高圧水銀ランプ（ウシオ電機製）を１５ｃ
ｍの距離で１０秒照射して硬化させた。樹脂板上に形成
された塗膜は透明（Ｈａｚｅ Ｍｅｔｅｒによる曇り度
０．１％）で、密着性はテープテストにより評価したと
ころ１００／ ｔｏｏで良好であった。This composition was applied onto a PMMA resin plate (manufactured by Kyowa Gas Chemical Co., Ltd.) using a spinner (4000 rpm) at 124.
W/c+s high pressure mercury lamp (manufactured by Ushio Inc.) 15c
It was cured by irradiation for 10 seconds at a distance of m. The coating film formed on the resin plate was transparent (haze level determined by Haze Meter: 0.1%), and its adhesion was evaluated by a tape test and was found to be good at 100/too.
ざらにテーパ一式摩耗試験を行なった。（条件：ＡＳＴ
Ｍ Ｄ−１０４４に基づき、Ｃ３Ｉ０．５００ｇＸ２
、１００ｒｐＩＩ）試験後Ｈａｚｅ Ｍｅｔｅｒ（スガ
試験機社製）で曇り度を測定したところ０．８％でほと
んど透明性は低下せず、耐摩耗性は良好であった。A rough taper set wear test was conducted. (Condition: AST
Based on MD-1044, C3I0.500gX2
, 100rpII) After the test, the degree of haze was measured using a Haze Meter (manufactured by Suga Test Instruments Co., Ltd.), and it was found to be 0.8%, with almost no decrease in transparency and good abrasion resistance.
実施例２〜４および比較例１
成分（Ａ）、（Ｂ、）および（Ｃ）を表１に示したよう
に変更したことを除いては実施例１と同様にして被覆用
組成物を調製した。これら組成物を実施例１と全く同様
にして塗布、硬化させて塗膜を形成し、これら被膜につ
いての密着性試験およびテーパー摩耗試験を行なった。Examples 2 to 4 and Comparative Example 1 A coating composition was prepared in the same manner as in Example 1, except that components (A), (B, ), and (C) were changed as shown in Table 1. did. These compositions were applied and cured to form coating films in exactly the same manner as in Example 1, and these coatings were subjected to adhesion tests and taper abrasion tests.
結果を表２に示した。The results are shown in Table 2.
表−１
表２ 塗膜の評価
本発明の実施例２〜４においては耐摩耗性は優れている
が、成分（２）が配合されていない比較例１においては
＃摩耗性が十分でなかった。Table 1 Table 2 Evaluation of coating film Examples 2 to 4 of the present invention had excellent abrasion resistance, but Comparative Example 1, which did not contain component (2), had insufficient #abrasion resistance. .
比較例２
光反応性のアクリロイル基を有するトリメチロールプロ
パントリアクリレート５０ｇおよびペンタエリスリトー
ルアクリレート５０ｇにラジカル開始型光開始剤ベンゾ
インメチルエーテル３ｇを溶解させた。この組成物をス
ピンナーでＰＭＭＡ樹脂板 に１５１Ｌ１１の厚みに塗
布し、実施例１の同様の条件で紫外線を照射して硬化塗
膜を形成させた。Comparative Example 2 3 g of radical-initiated photoinitiator benzoin methyl ether was dissolved in 50 g of trimethylolpropane triacrylate and 50 g of pentaerythritol acrylate having a photoreactive acryloyl group. This composition was applied to a PMMA resin plate to a thickness of 151L11 using a spinner, and irradiated with ultraviolet rays under the same conditions as in Example 1 to form a cured coating film.
この塗膜は透明（曇り度二０．１％）であった、実施例
１と同様の条件でテーパー摩耗試験を行なったところ曇
り度１７％で十分ではなかった。アクリロイル基の重合
反応により硬化させる従来のタイプの充硬化組成物は、
反応による体積収縮が大きいため、硬化塗膜に否を生じ
るために密着性が劣るものと考えられる。This coating film was transparent (haze level: 20.1%). When a taper abrasion test was conducted under the same conditions as in Example 1, the haze level was 17%, which was not sufficient. Conventional charged and cured compositions that are cured by the polymerization reaction of acryloyl groups are
It is thought that the large volumetric shrinkage caused by the reaction causes defects in the cured coating film, resulting in poor adhesion.
比較例３
実施例１において、成分（Ｂ）処理シリカの代わりに未
処理のシリカ、ＡＥＲＯＳＩＬ ８１１１Ｇを用いた他
は全く同じ配合で組成物１′を調製した６組成物１′は
全く不透明となり、かつその製造中に増粘しチキントロ
ピックとなり全く流動性を示さず塗布剤としては使用し
得なかった。すなわち未処理のシリカを均一に分散させ
て流動性の良い組成物を得ることは困難であった。Comparative Example 3 Composition 1' was prepared using exactly the same formulation as in Example 1 except that untreated silica, AEROSIL 8111G, was used instead of component (B) treated silica.6 Composition 1' became completely opaque, During its production, it thickened and became chicken-tropic, showing no fluidity and could not be used as a coating agent. That is, it has been difficult to obtain a composition with good fluidity by uniformly dispersing untreated silica.
Claims (1)
能エポキシオリゴマー１００重量部、（Ｂ）一般式（Ｒ
Ｏ）＿３＿−＿ｎＳｉＲ＾１Ｒ＾２＿ｎ・・・［ I ］
［Ｉ式中、ｎは０または１、Ｒはメチル、エチルまたは
プロピル基、Ｒ＾１はエポキシアルキル、エポキシシク
ロアルキルおよび、グリシドキシ基より選ばれる炭素数
１〜２０のエポキシ基含有有機残基、Ｒ＾２はアルキル
シクロアルキル、アミノアルキル、アルキルアミン、ア
ルコキシ、アルコキシアルキル、エポキシアルキル、エ
ポキシシクロアルキル、アルケニル、クリシドキ、メタ
クリロキシアルキルおよびγ−メルカプトプロピル基か
らなる群より選ばれた炭素数１〜２０の有機残基］で表
わされる化合物を加水分解したものでその表面を処理さ
れた微粉状の無機充填剤５〜１００重量部、 （Ｃ）紫外線の照射によりエポキシ基を反応させ得る光
開始剤０．１〜１０重量部、 を必須成分として含有する紫外線硬化性被覆用組成物。[Scope of Claims] 1) The following components (A), (B) and (C), (A) 100 parts by weight of polyfunctional epoxy oligomer, (B) general formula (R
O)_3_-_nSiR^1R^2_n...[I]
[In formula I, n is 0 or 1, R is a methyl, ethyl or propyl group, R^1 is an epoxy group-containing organic residue having 1 to 20 carbon atoms selected from epoxyalkyl, epoxycycloalkyl and glycidoxy group, R^2 is a carbon number of 1 to 1 selected from the group consisting of alkylcycloalkyl, aminoalkyl, alkylamine, alkoxy, alkoxyalkyl, epoxyalkyl, epoxycycloalkyl, alkenyl, cycloalkyl, methacryloxyalkyl, and γ-mercaptopropyl group 5 to 100 parts by weight of a finely powdered inorganic filler whose surface has been treated with a hydrolyzed compound represented by [20 organic residues]; (C) a photoinitiator capable of reacting epoxy groups by irradiation with ultraviolet rays; An ultraviolet curable coating composition containing 0.1 to 10 parts by weight of the following as essential components.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10176585A JPS61261365A (en) | 1985-05-14 | 1985-05-14 | Photo-curable coating composition |
| GB08611144A GB2177093B (en) | 1985-05-14 | 1986-05-07 | Photo-curable coating composition |
| DE19863615790 DE3615790A1 (en) | 1985-05-14 | 1986-05-10 | THROUGH LIGHT-CURABLE COATING COMPOSITION |
| FR8606937A FR2582005A1 (en) | 1985-05-14 | 1986-05-14 | PHOTO-CURABLE COATING COMPOSITION COMPRISING A MULTIFUNCTIONAL EPOXY OLIGOMER, A SURFACE-TREATED NON-ORGANIC LOAD AND A PHOTO-INITIATOR, IN PARTICULAR FOR THE PROTECTION OF PLASTIC ARTICLES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10176585A JPS61261365A (en) | 1985-05-14 | 1985-05-14 | Photo-curable coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61261365A true JPS61261365A (en) | 1986-11-19 |
Family
ID=14309319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10176585A Pending JPS61261365A (en) | 1985-05-14 | 1985-05-14 | Photo-curable coating composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS61261365A (en) |
| DE (1) | DE3615790A1 (en) |
| FR (1) | FR2582005A1 (en) |
| GB (1) | GB2177093B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245062A (en) * | 1988-03-25 | 1989-09-29 | Asahi Glass Co Ltd | Coating composition and plastic molded article with film therefrom |
| JP2002129066A (en) * | 2000-10-21 | 2002-05-09 | Degussa Ag | Radiation-curable coating system |
| JP2008518067A (en) * | 2004-10-25 | 2008-05-29 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Functional nanoparticles |
| JP2009543920A (en) * | 2006-07-18 | 2009-12-10 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Composite compositions for micropatterned layers |
| JP2012509212A (en) * | 2008-11-19 | 2012-04-19 | エルジー・ケム・リミテッド | Multilayer film and method for producing the same |
| US8535796B2 (en) | 2005-01-21 | 2013-09-17 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetzige Gmbh | Composite composition for micropatterned layers having high relaxation ability, high chemical resistance and mechanical stability |
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|---|---|---|---|---|
| US4997717A (en) * | 1987-03-27 | 1991-03-05 | Ciba-Geigy Corporation | Photocurable abrasives |
| DE3852661D1 (en) * | 1987-03-27 | 1995-02-16 | Ciba Geigy Ag | Photo-curable abrasives. |
| US4828583A (en) * | 1987-04-02 | 1989-05-09 | Minnesota Mining And Manufacturing Company | Coated abrasive binder containing ternary photoinitiator system |
| US5023140A (en) * | 1988-06-20 | 1991-06-11 | Armstrong World Industries, Inc. | Floor covering having a modified glass wear layer |
| JPH0368478A (en) * | 1989-08-07 | 1991-03-25 | Kansai Paint Co Ltd | Formation of coating film |
| US5064719A (en) * | 1989-09-26 | 1991-11-12 | E. I. Du Pont De Nemours And Company | Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane |
| US4988759A (en) * | 1989-09-26 | 1991-01-29 | E. I. Du Pont De Nemours And Company | Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane |
| JPH03160071A (en) * | 1989-11-18 | 1991-07-10 | Somar Corp | Photo-setting electroless plating resist ink composition |
| JP2697937B2 (en) * | 1989-12-15 | 1998-01-19 | キヤノン株式会社 | Active energy ray-curable resin composition |
| JP3097867B2 (en) * | 1990-03-07 | 2000-10-10 | ダウ・コ−ニング・コ−ポレ−ション | Radiation curable protective coating composition containing epoxide and colloidal silica |
| DE4133290A1 (en) * | 1991-10-08 | 1993-04-15 | Herberts Gmbh | METHOD FOR PRODUCING MULTILAYER LACQUERING USING RADICALLY AND / OR CATIONICALLY POLYMERIZABLE CLEAR VARNISHES |
| DE4141245A1 (en) * | 1991-12-14 | 1993-06-17 | Abb Patent Gmbh | CONTROL ELEMENTS OF INSTALLATION DEVICES |
| DE4142735A1 (en) * | 1991-12-21 | 1993-06-24 | Hoechst Ag | POLYMERIZABLE MIXTURE BY RADIATION AND METHOD FOR PRODUCING A SOLDER STOP MASK |
| DE19635447C1 (en) * | 1996-08-31 | 1997-11-20 | Herberts Gmbh | Multilayer repair painting process, especially for car repairs |
| JP4050370B2 (en) * | 1998-01-07 | 2008-02-20 | 株式会社Ｋｒｉ | Inorganic-containing photosensitive resin composition and inorganic pattern forming method |
| JP4389315B2 (en) * | 1999-12-28 | 2009-12-24 | Ｊｓｒ株式会社 | Reactive particles, curable composition containing the same, and cured product |
| US6358354B1 (en) | 2000-07-05 | 2002-03-19 | Lexmark International, Inc. | UV and thermally curable adhesive formulation |
| US6596837B2 (en) | 2001-03-27 | 2003-07-22 | Acushnet Company | Abrasion resistant coated golf equipment |
| US6425655B1 (en) | 2001-06-05 | 2002-07-30 | Lexmark International, Inc. | Dual curable encapsulating material |
| US20050008865A1 (en) * | 2003-07-07 | 2005-01-13 | General Electric Company | Curable epoxy compositions and articles made therefrom |
| US7622514B2 (en) | 2005-05-09 | 2009-11-24 | Sabic Innovative Plastics Ip B.V. | Curable composition and article possessing protective layer obtained therefrom |
| US7571979B2 (en) | 2005-09-30 | 2009-08-11 | Lexmark International, Inc. | Thick film layers and methods relating thereto |
| EP2475718A1 (en) | 2009-09-09 | 2012-07-18 | Felix Winkelmann | Polymer materials comprising coupled components |
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| DE3265242D1 (en) * | 1981-09-17 | 1985-09-12 | Ciba Geigy Ag | Light-sensitive coating agent and its use in protection purposes |
| US4482656A (en) * | 1983-09-29 | 1984-11-13 | Battelle Development Corporation | Method for manufacturing a composition for coating substrates with an abrasion-resistant transparent and translucent film |
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-
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- 1986-05-07 GB GB08611144A patent/GB2177093B/en not_active Expired
- 1986-05-10 DE DE19863615790 patent/DE3615790A1/en not_active Withdrawn
- 1986-05-14 FR FR8606937A patent/FR2582005A1/en active Pending
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245062A (en) * | 1988-03-25 | 1989-09-29 | Asahi Glass Co Ltd | Coating composition and plastic molded article with film therefrom |
| JP2002129066A (en) * | 2000-10-21 | 2002-05-09 | Degussa Ag | Radiation-curable coating system |
| JP2008518067A (en) * | 2004-10-25 | 2008-05-29 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Functional nanoparticles |
| US8877954B2 (en) | 2004-10-25 | 2014-11-04 | Basf Se | Functionalized nanoparticles |
| US8535796B2 (en) | 2005-01-21 | 2013-09-17 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetzige Gmbh | Composite composition for micropatterned layers having high relaxation ability, high chemical resistance and mechanical stability |
| JP2009543920A (en) * | 2006-07-18 | 2009-12-10 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Composite compositions for micropatterned layers |
| US8680179B2 (en) | 2006-07-18 | 2014-03-25 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetzige Gmbh | Composite composition for micropatterned layers |
| JP2012509212A (en) * | 2008-11-19 | 2012-04-19 | エルジー・ケム・リミテッド | Multilayer film and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2177093B (en) | 1988-08-24 |
| GB2177093A (en) | 1987-01-14 |
| DE3615790A1 (en) | 1986-11-20 |
| GB8611144D0 (en) | 1986-06-11 |
| FR2582005A1 (en) | 1986-11-21 |
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