JP2007277332A - UV-curable coating composition and resin-coated article formed by coating the composition - Google Patents
UV-curable coating composition and resin-coated article formed by coating the composition Download PDFInfo
- Publication number
- JP2007277332A JP2007277332A JP2006103005A JP2006103005A JP2007277332A JP 2007277332 A JP2007277332 A JP 2007277332A JP 2006103005 A JP2006103005 A JP 2006103005A JP 2006103005 A JP2006103005 A JP 2006103005A JP 2007277332 A JP2007277332 A JP 2007277332A
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- Prior art keywords
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- composition
- meth
- acrylate
- coating
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 29
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 229910020175 SiOH Inorganic materials 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 66
- 239000000126 substance Substances 0.000 claims description 33
- 229920000620 organic polymer Polymers 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000012663 cationic photopolymerization Methods 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000005504 styryl group Chemical group 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
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- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 230000021615 conjugation Effects 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
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- 238000001723 curing Methods 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 4
- 238000003847 radiation curing Methods 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 10
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
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- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
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- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
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- 239000003822 epoxy resin Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
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- 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
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Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
【課題】シロキサン結合を有する無機系硬化性組成物の特長を損なうことなく、この種の無機系硬化性組成物において解決困難な問題とされていた硬化後のクラック発生の問題がなく、従来にない高いレベルの耐擦傷性を付与することができ、その上保存性にも優れたラジエーション硬化型のコーティング用組成物およびその樹脂被覆品を提供すること。
【解決手段】（Ａ）金属酸化物コロイドゾル、（Ｂ）アルコキシシラン加水分解縮合物、（Ｃ）光重合開始剤を必須成分とし、かつ、（Ｂ）アルコキシシラン加水分解縮合物の少なくとも一部が特定の有機官能基を含み、分子量分布が制御されてなることを特徴とする実質的に末端がＳｉＯＨ型である紫外線硬化型コーティング用組成物、およびこれを被覆してなる樹脂被覆品である。
【選択図】なしThe present invention eliminates the problem of crack generation after curing, which has been considered difficult to solve in this type of inorganic curable composition without impairing the characteristics of the inorganic curable composition having a siloxane bond. The present invention provides a radiation-curing coating composition and a resin-coated article thereof that can impart a high level of scratch resistance and excellent storage stability.
(A) a metal oxide colloidal sol, (B) an alkoxysilane hydrolysis condensate, (C) a photopolymerization initiator as an essential component, and (B) at least a part of the alkoxysilane hydrolysis condensate. A UV-curable coating composition having a specific organic functional group and having a molecular weight distribution controlled and having a terminal end of SiOH type, and a resin-coated article formed by coating the composition.
[Selection figure] None
Description
本発明は紫外線（ＵＶ）硬化型のコーティング用として好適なコーティング用樹脂組成物に関し、さらに詳しくは金属酸化物コロイドゾルを利用した、プラスチック、フィルム、軽金属など表面が軟質な基材に優れた耐擦傷性の保護被膜を形成するＵＶ硬化型のコーティング剤として有用なコーティング用組成物およびこれを被覆してなる樹脂被覆品に関する。 The present invention relates to a coating resin composition suitable for an ultraviolet (UV) curable coating, and more particularly, an excellent scratch resistance to a substrate having a soft surface such as plastic, film and light metal using a metal oxide colloidal sol. The present invention relates to a coating composition useful as a UV-curable coating agent for forming a protective protective film and a resin-coated article formed by coating the same.
従来、基材の表面保護には現在までに種々のものが使用されている。プラスチック材料は軽量性、加工性などの特徴をいかして多くの用途で用いられているが表面の耐擦傷性に劣る欠点がある。
表面が軟質であるプラスチック、軽金属など特に高いレベルの耐擦傷性を要求される用途ではシロキサン系の熱硬化型ハードコート剤が使用されている。このシロキサン系ハードコート剤については数多くの技術提案がなされてきた。例えば特許文献１には、トリヒドロキシシラン部分縮合物とコロイダルシリカからなるコーティング用組成物が開示されている。しかし、加熱硬化型ハードコーティング剤は、その硬化に関して多大な熱エネルギーを要することから経済的でなく、基材によっては加えられる熱により変形してしまうなどの問題点がある。
Conventionally, various materials have been used for protecting the surface of a substrate. Plastic materials are used in many applications by taking advantage of their characteristics such as light weight and workability, but have a drawback of being inferior in surface scratch resistance.
Siloxane-based thermosetting hard coating agents are used in applications that require a particularly high level of scratch resistance, such as soft plastic surfaces and light metals. Many technical proposals have been made on this siloxane-based hard coat agent. For example, Patent Document 1 discloses a coating composition comprising a trihydroxysilane partial condensate and colloidal silica. However, the heat-curable hard coating agent is not economical because it requires a large amount of heat energy for its curing, and there is a problem that it is deformed by heat applied depending on the substrate.
これらの問題点を解消するためにラジエーション硬化させるタイプのコーティング剤が提案されている。ここで、ラジエーションとは電子線、紫外線などの電離放射線のエネルギーによって硬化することを意味する。なお、本明細書並びに本発明において「紫外線（ＵＶ）硬化型」と称する場合には、紫外線（ＵＶ）のみならず、電子線を含む広く電離放射線のエネルギーによって硬化し得る性質を意味するものとし、実質的に「ラジエーション硬化型」と同義とする。 In order to solve these problems, a radiation curing type coating agent has been proposed. Here, the radiation means curing by the energy of ionizing radiation such as an electron beam and ultraviolet rays. In the present specification and the present invention, the term “ultraviolet (UV) curable” refers to a property that can be cured by the energy of not only ultraviolet (UV) but also ionizing radiation including electron beams. Substantially synonymous with “radiation curable type”.
このようなラジエーション硬化型コーティグ剤としては、シリカ粒子、アクリロキシ官能基シランもしくはその加水分解物、およびアクリレート化合物よりなる組成物として特許文献２が開示されている。しかし、この場合アクリレート化合物は光開始剤により硬化するが、シリカ粒子、シラン部位の光硬化に関しては考慮されておらず、硬度が十分に発現するとは言いがたい。 As such a radiation curable coating agent, Patent Document 2 is disclosed as a composition comprising silica particles, acryloxy functional group silane or a hydrolyzate thereof, and an acrylate compound. However, in this case, the acrylate compound is cured by the photoinitiator, but the photocuring of the silica particles and the silane site is not considered, and it cannot be said that the hardness is sufficiently developed.
近年、特許文献３に、シリカなどの粒子表面に重合性官能基を導入する試みが開示されているが、このような変性シリカ粒子を作成する場合使用する不飽和二重結合を有する物質中に水酸基などの官能基が必要であり設計の自由度が少なくなるという欠点がある。上述したすべての系にいえることは、硬度、耐擦傷性のみ追い続けるあまり、硬く、脆いものとなってしまい、それ以外の例えば耐クラック性、可撓性、難燃性などの諸特性を付与するゆとりはない。 In recent years, Patent Document 3 discloses an attempt to introduce a polymerizable functional group on the surface of a particle such as silica, but the substance having an unsaturated double bond to be used when producing such a modified silica particle is used. There is a drawback that a functional group such as a hydroxyl group is required and design freedom is reduced. What can be said for all the systems mentioned above is that it is hard and brittle because it keeps chasing only hardness and scratch resistance, and other properties such as crack resistance, flexibility and flame retardancy are given. There is no room to do.
すなわち、これまでに提案されているラジエーション硬化型無機骨格硬化性樹脂組成物においては、硬化性に問題がなく、造膜性や耐衝撃性、種々の外部刺激に対するクラック発生の問題がなく、しかも、経時安定性、耐擦傷性に優れ、かつ有機ポリマーの諸物性をも併有するラジエーション硬化型ハードコーティング剤組成物は、未だに実用化されていない。 In other words, the radiation curable inorganic skeleton curable resin composition proposed so far has no problem in curability, no film forming property, impact resistance, and no problem of crack generation due to various external stimuli. Further, a radiation curable hard coating agent composition having excellent stability over time and scratch resistance and having various physical properties of an organic polymer has not been put into practical use yet.
本発明は、シロキサン結合を有する無機系硬化性組成物の特長を損なうことなく、この種の無機系硬化性組成物において解決困難な問題とされていた硬化後のクラック発生の問題がなく、従来にない高いレベルの耐擦傷性を付与することができ、その上保存性にも優れたラジエーション硬化型のコーティング用組成物および樹脂被覆品を提供することを目的とする。 The present invention has no problem of crack generation after curing, which has been regarded as a difficult problem to be solved in this type of inorganic curable composition, without impairing the characteristics of the inorganic curable composition having a siloxane bond. An object of the present invention is to provide a radiation-curable coating composition and a resin-coated article that can impart a high level of scratch resistance, and that is excellent in storage stability.
さらに本発明は、硬化性を阻害することなく、ラジエーションにより瞬時に硬質皮膜を形成せしめ、かつ、無機オルガノシロキサン化合物の硬質物性、含有する無機金属酸化物による導電性、光触媒活性、屈折率制御と有機ポリマーの造膜性、耐クラック性、可撓性、セルフヒーリング性、耐溶剤性、耐アルカリ性、耐炎性などの諸特性を併有する複合皮膜を形成し得るコーティング用組成物およびその樹脂被覆品を提供することを目的とする。 Furthermore, the present invention allows a hard film to be instantaneously formed by radiation without inhibiting the curability, and the hard physical properties of the inorganic organosiloxane compound, the conductivity by the contained inorganic metal oxide, the photocatalytic activity, the refractive index control and Coating composition capable of forming a composite film having various properties such as organic polymer film-forming property, crack resistance, flexibility, self-healing property, solvent resistance, alkali resistance, flame resistance and the like, and resin-coated article thereof The purpose is to provide.
本発明者らは上記課題を解決すべく鋭意検討した結果、
（Ａ）金属酸化物コロイドゾル、（Ｂ）アルコキシシラン加水分解縮合物、（Ｃ）光重合開始剤を必須成分とし、かつ、（Ｂ）アルコキシシラン加水分解縮合物の少なくとも一部が特定の有機官能基を含み、分子量分布が制御されてなることを特徴とする実質的に末端がＳｉＯＨ型である紫外線硬化型コーティング用組成物が上述問題点を解決するのに有効であることを見出した。
As a result of intensive studies to solve the above problems, the present inventors,
(A) metal oxide colloidal sol, (B) alkoxysilane hydrolysis condensate, (C) a photopolymerization initiator as an essential component, and (B) at least part of the alkoxysilane hydrolysis condensate is a specific organic function The present inventors have found that a UV-curable coating composition having a terminal and having a SiOH type substantially containing a group and having a controlled molecular weight distribution is effective in solving the above-mentioned problems.
本発明における組成について述べる。
（Ａ）のソリッド分は（Ａ）のソリッド分および（Ｂ）のソリッド分の合計量に対して５〜８０質量％、好ましくは１０〜６０質量％、最も好ましくは２０〜４０％であり、同様に、（Ｂ）のソリッド分は（Ａ）のソリッド分および（Ｂ）のソリッド分の合計量に対して２０〜９５質量％、好ましくは４０〜９０質量％、もっとも好ましくは６０〜８０質量％であるオルガノシロキサン樹脂組成物である。
The composition in the present invention will be described.
The solid content of (A) is 5 to 80% by mass, preferably 10 to 60% by mass, most preferably 20 to 40% with respect to the total amount of the solid content of (A) and the solid content of (B). Similarly, the solid content of (B) is 20 to 95 mass%, preferably 40 to 90 mass%, most preferably 60 to 80 mass%, based on the total amount of the solid content of (A) and the solid content of (B). % Organosiloxane resin composition.
（Ｃ）光重合開始剤としては、ラジカル系光重合開始剤およびカチオン系光重合開始剤が挙げられ、これら双方を含むことが好ましく、ラジカル系光重合開始剤０．００５〜１０質量％およびカチオン系光重合開始剤０．００５〜１０質量％を含むことがより好ましい。
上述した各成分の添加量、存在量がこれより少な過ぎる場合、目的とする効果を期待することが困難な場合があり、多過ぎる場合は安定性、透明性、耐クラック性など溶液特性、皮膜特性上不利となる懸念がある。
(C) As a photoinitiator, a radical photoinitiator and a cationic photoinitiator are mentioned, It is preferable that both are included, Radical photoinitiator 0.005-10 mass% and a cation More preferably, it contains 0.005 to 10% by mass of a photopolymerization initiator.
If the amount of each component mentioned above is too small, the target effect may be difficult to expect. If it is too much, solution properties such as stability, transparency, crack resistance, and coating There is a concern that it is disadvantageous in characteristics.
また、当該コーティング用組成物の合成条件としては、（Ｂ）アルコキシシラン加水分解縮合物のピーク分子量がポリスチレン換算で１０００以下となるように分子量が制御された合成条件で合成されたものが好ましい。当該分子量が大き過ぎると、硬度の発現、特に耐擦傷性が不十分となる懸念がある。 Moreover, as a synthetic | combination condition of the said composition for coating, what was synthesize | combined on the synthetic | combination conditions by which molecular weight was controlled so that the peak molecular weight of (B) alkoxysilane hydrolysis-condensation product may be 1000 or less in polystyrene conversion is preferable. If the molecular weight is too large, there is a concern that the expression of hardness, particularly the scratch resistance, may be insufficient.
また、上記ＳｉＯＨ型オルガノシロキサン樹脂組成物の−ＳｉＯＨ基、もしくは含有する他の官能基と反応する、もしくは水素結合、および／または、π−π共役、配位結合などの化学的相互作用により安定化する官能基、部分を有する有機重合体を当該オルガノシロキサン樹脂組成物反応系に存在させることにより、容易に無機−有機ハイブリッド体を形成することが可能となる。そして、そのようにして得られた硬化皮膜は均質で、実質的に無色透明で、無機シロキサン樹脂組成物の硬度、耐擦傷性、耐熱性、耐候性、耐熱性、耐酸性など諸特性とハイブリッド化して導入される有機成分の諸特性を併有させることが可能となることを見出した。 In addition, it reacts with the -SiOH group of the above-mentioned SiOH type organosiloxane resin composition or other functional groups contained therein, or is stable due to chemical interaction such as hydrogen bonding and / or π-π conjugation or coordination bonding. It is possible to easily form an inorganic-organic hybrid by allowing an organic polymer having functional groups and moieties to be present to exist in the organosiloxane resin composition reaction system. The cured film thus obtained is homogeneous, substantially colorless and transparent, and hybrids with various properties such as hardness, scratch resistance, heat resistance, weather resistance, heat resistance and acid resistance of the inorganic siloxane resin composition. It has been found that it is possible to combine the various characteristics of the organic components introduced after the formation.
本発明の紫外線硬化型コーティング用組成物（以下、単に「本発明のコーティング用組成物」という場合がある。）における（Ａ）金属酸化物コロイドゾルとしては、コロイダルシリカが代表的なものとして例示される。これは、直径５〜２００ｎｍ、好ましくは５〜４０ｎｍのシリカ微粒子が水または有機溶媒中にコロイド状に分散されたものである。なかでも酸性水溶液分散型コロイダルシリカが、（Ｂ）アルコキシシラン加水分解縮合物との反応を考慮した場合、容易に化合出来るＳｉＯＨ表面状態を有しているため最も適している。 Colloidal silica is typically exemplified as the metal oxide colloidal sol (A) in the ultraviolet curable coating composition of the present invention (hereinafter sometimes simply referred to as “the coating composition of the present invention”). The In this, silica fine particles having a diameter of 5 to 200 nm, preferably 5 to 40 nm, are colloidally dispersed in water or an organic solvent. Among them, acidic aqueous dispersion type colloidal silica is most suitable because it has a SiOH surface state that can be easily combined when considering the reaction with (B) alkoxysilane hydrolysis condensate.
かかるコロイダルシリカの具体例として、日産化学工業（株）製のスノーテックスＯ、触媒化成工業（株）製のカタロイドＳＮ、日本化学工業（株）製のシリカドール３０Ａなどが挙げられる。また、アルカリ性コロイダルシリカに種々の有機酸、無機酸を添加することにより、ｐＨを３〜５のコロイダルシリカ酸性準安定域に安定化させ、その表面をＳｉＯＨ型としたものも同様に使用できる。 Specific examples of such colloidal silica include Snowtex O manufactured by Nissan Chemical Industries, Ltd., Cataloid SN manufactured by Catalytic Chemical Industry Co., Ltd., Silica Doll 30A manufactured by Nippon Chemical Industry Co., Ltd., and the like. Further, by adding various organic acids and inorganic acids to alkaline colloidal silica, the pH is stabilized in the colloidal silica acidic metastable region of 3 to 5, and the surface of which is made SiOH type can be used as well.
有機溶媒分散型としては、具体的に日産化学工業（株）製のＭＡ−ＳＴ、ＩＰＡ−ＳＴ、ＮＢＡ−ＳＴ、ＩＢＡ−ＳＴ、ＥＧ−ＳＴ、ＸＢＡ−ＳＴ、ＮＰＣ−ＳＴ、ＤＭＡＣ−ＳＴ、触媒化成工業（株）製のＯＳＣＡＬ１１３２、ＯＳＣＡＬ１２３２、ＯＳＣＡＬ１３３２、ＯＳＣＡＬ１４３２、ＯＳＣＡＬ１５３２、ＯＳＣＡＬ１６３２、ＯＳＣＡＬ１７３２などが挙げられる。 Specific examples of the organic solvent dispersion type include MA-ST, IPA-ST, NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST, manufactured by Nissan Chemical Industries, Ltd. Examples include OSCAL1132, OSCAL1232, OSCAL1332, OSCAL1432, OSCAL1532, OSCAL1632, and OSCAL1732, manufactured by Catalytic Chemical Industry Co., Ltd.
その他の金属酸化物コロイドゾルは、種々の機能性付与、例えば、導電性、光触媒活性、屈折率制御の目的で添加される。具体的には、マグネシウム酸化物、珪素酸化物とマグネシウム酸化物との共酸化物、カルシウム酸化物、バリウム酸化物、ホウ素酸化物、アルミニウム酸化物、インジウム酸化物、ゲルマニウム酸化物、錫酸化物、亜鉛酸化物、チタン酸化物、ジルコニウム酸化物、セシウム酸化物、インジウム錫酸化物、および錫アンチモン酸化物のコロイドゾルが単独であるいは混合物として用いることができる。 Other metal oxide colloidal sols are added for the purpose of imparting various functions, for example, conductivity, photocatalytic activity, and refractive index control. Specifically, magnesium oxide, co-oxide of silicon oxide and magnesium oxide, calcium oxide, barium oxide, boron oxide, aluminum oxide, indium oxide, germanium oxide, tin oxide, Colloidal sols of zinc oxide, titanium oxide, zirconium oxide, cesium oxide, indium tin oxide, and tin antimony oxide can be used alone or as a mixture.
これら金属酸化物コロイドゾルは、金属原子−酸素原子の繰り返しで構成されるが、末端部位においては金属原子と結合しない酸素原子の結合手（例えば、ヒドロキシ基、カルボキシル基のような形態）が存在し、オルガノシロキサンのＳｉＯＨと反応し得る。また、これらの金属コロイドゾルの粒子径は、０．００５μｍ〜１μｍであることが好ましい。 These metal oxide colloidal sols are composed of repeating metal atoms-oxygen atoms, but there are oxygen oxygen bonds (for example, forms such as hydroxy groups and carboxyl groups) that do not bond to metal atoms at the terminal sites. It can react with SiOH of organosiloxane. Moreover, it is preferable that the particle diameter of these metal colloid sols is 0.005 micrometer-1 micrometer.
本発明のコーティング用組成物において、（Ｂ）として用いるアルコキシシラン加水分解縮合物は、下記式（１）のアルコキシシランを加水分解縮合反応させたものであることが好ましい。
Ｒ1 aＲ2 bＳｉ（Ｒ3）4-a-b ・・・ （１）
（式中、Ｒ1は炭素数１〜１０のアルキル基を表し、Ｒ2はアリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルケニル基、エポキシ基、（メタ）アクリロイル基、ビニル基、スチリル基、メルカプト基、アミノ基、ウレイド基およびシアノ基からなる群より選ばれる１以上の基を含む有機官能基を表し、Ｒ3は炭素数１〜１０のアルコキシ基、アルケニロキシ基、アシロキシ基またはアルコキシアルコキシ基を表し、ａ，ｂはおのおの０，１，２のいずれかの整数であり、ａ＋ｂは０，１，２のいずれかの整数である。）
In the coating composition of the present invention, the alkoxysilane hydrolysis condensate used as (B) is preferably a product obtained by subjecting an alkoxysilane of the following formula (1) to a hydrolysis condensation reaction.
R 1 a R 2 b Si (R 3 ) 4-ab (1)
(In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, and R 2 represents an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, a (meth) acryloyl group, a vinyl group, and styryl. Represents an organic functional group containing one or more groups selected from the group consisting of a group, a mercapto group, an amino group, a ureido group and a cyano group, and R 3 represents an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group, an acyloxy group or an alkoxy group Represents an alkoxy group, a and b are each an integer of 0, 1 or 2; a + b is an integer of 0, 1 or 2)
当該アルコキシシランとしては、例えばテトラメトキシシラン、テトラエトキシシラン、テトラｎ−プロポキシシラン、テトライソプロポキシシラン、テトラｎ−ブトキシシラン、テトライソブトキシシラン、メチルトリメトキシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、ジメチルジメトキシシラン、ビニルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−ウレイドプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、γ−イソシアナトプロピルトリメトキシシラン、γ−イソシアナトプロピルトリエトキシシラン、フェニルトリエトキシシラン、フェニルトリメトキシシラン等が挙げられる。これらは単独でも、混合して使用してもよく、あらかじめ部分的に加水分解を施しておいたものを使用してもかまわない。 Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxy. Silane, isobutyltrimethoxysilane, vinyltrimethoxycin, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, Nylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane and the like. These may be used alone or in combination, and may be used after partial hydrolysis.
また、後述する種々の有機ポリマーとのハイブリッド化を促進する目的で、目的とする有機ポリマーとの相溶性、反応性、種々の化学的インタラクションを形成する有機化合物を予め反応せしめたものを使用することも可能である。 In addition, for the purpose of promoting hybridization with various organic polymers described later, a compound obtained by reacting an organic compound that forms compatibility with the target organic polymer, reactivity, and various chemical interactions in advance is used. It is also possible.
本発明のコーティング用組成物において、上述した（Ｂ）アルコキシシラン加水分解縮合物のうちの少なくとも一部が、前記式（１）中のｂが１または２であり、かつ、Ｒ2が、（メタ）アクリロイル基、ビニル基、スチリル基、エポキシ基およびメルカプト基からなる群より選ばれるいずれかの基を含む特定の有機官能基であることが好ましい。これら官能基は、本発明に必須の「特定の有機官能基」に相当するものであり、（Ｂ）アルコキシシラン加水分解縮合物中のうちの少なくとも一部について、いずれかの箇所に導入されていることが必須であり、上記のようにＲ2の基として含まれることが好ましい。 In the coating composition of the present invention, at least a part of the above-mentioned (B) alkoxysilane hydrolysis condensate is such that b in the formula (1) is 1 or 2, and R 2 is ( A specific organic functional group including any group selected from the group consisting of a (meth) acryloyl group, a vinyl group, a styryl group, an epoxy group, and a mercapto group is preferable. These functional groups correspond to “specific organic functional groups” essential for the present invention, and (B) at least a part of the alkoxysilane hydrolyzed condensate is introduced at any position. It is essential that it is contained as a group of R 2 as described above.
これらラジカル反応性基（アクリロイル基、ビニル基、スチリル基等）、カチオン反応性基（エポキシ基等）を含むアルコキシシラン加水分解縮合物は、金属酸化物−オルガノシロキサン硬化成分とＵＶラジカルおよびＵＶカチオン硬化成分とを共重合せしめる反応性無機−有機架橋剤として作用する。当該特定の有機官能基を含むアルコキシシラン加水分解縮合物成分の存在量としては、全アルコキシシラン加水分解縮合物中、２０〜８０モル％が好ましく、４０〜６０モル％がより好ましい。 Alkoxysilane hydrolysis condensates containing these radical reactive groups (acryloyl group, vinyl group, styryl group, etc.) and cation reactive groups (epoxy group, etc.) are metal oxide-organosiloxane curing components, UV radicals and UV cations. It acts as a reactive inorganic-organic crosslinking agent that is copolymerized with the curing component. The abundance of the alkoxysilane hydrolysis condensate component containing the specific organic functional group is preferably 20 to 80 mol% and more preferably 40 to 60 mol% in the total alkoxysilane hydrolysis condensate.
本発明によれば、シロキサン結合を有する無機系硬化性組成物の特長を損なうことなく、この種の無機系硬化性組成物において解決困難な問題とされていた硬化後のクラック発生の問題がなく、従来にない高いレベルの耐擦傷性を付与することができ、その上保存性にも優れたラジエーション硬化型（詳しくは、紫外線硬化型）のコーティング用組成物および樹脂被覆品を提供することができる。 According to the present invention, there is no problem of generation of cracks after curing, which has been regarded as a difficult problem to be solved in this type of inorganic curable composition without impairing the characteristics of the inorganic curable composition having a siloxane bond. It is possible to provide a radiation-curable coating composition (specifically, an ultraviolet-curable coating composition) and a resin-coated article that can impart an unprecedented high level of scratch resistance and also have excellent storage stability. it can.
また、本発明によれば、硬化性を阻害することなく、紫外線により瞬時に硬質皮膜を形成せしめ、かつ、無機オルガノシロキサン化合物の硬質物性と有機ポリマーの造膜性、耐クラック性、可撓性、セルフヒーリング性、耐溶剤性、耐アルカリ性、耐炎性などの諸特性を併有する複合皮膜を形成し得るコーティング用組成物およびその樹脂被覆品を提供することができる。 In addition, according to the present invention, a hard film is instantaneously formed by ultraviolet rays without inhibiting the curability, and the hard physical properties of the inorganic organosiloxane compound and the film forming property of the organic polymer, crack resistance, flexibility Further, it is possible to provide a coating composition capable of forming a composite film having various properties such as self-healing property, solvent resistance, alkali resistance and flame resistance, and a resin-coated article thereof.
以下、本発明のコーティング用組成物について詳細に説明する。
本発明のコーティング用組成物は、（Ａ）金属酸化物コロイドゾル、（Ｂ）アルコキシシラン加水分解縮合物、（Ｃ）光重合開始剤を必須成分とし、かつ、（Ｂ）アルコキシシラン加水分解縮合物の少なくとも一部が特定の有機官能基を含み、分子量分布が制御されてなることを特徴とするものである。
Hereinafter, the coating composition of the present invention will be described in detail.
The coating composition of the present invention comprises (A) a metal oxide colloidal sol, (B) an alkoxysilane hydrolysis condensate, (C) a photopolymerization initiator as an essential component, and (B) an alkoxysilane hydrolysis condensate. At least a part of which contains a specific organic functional group, and the molecular weight distribution is controlled.
本発明のコーティング用組成物における（Ａ）金属酸化物コロイドゾルと（Ｂ）アルコキシシラン加水分解縮合物との使用割合は、組成物の安定性、得られる硬化膜の透明性、耐摩耗性、耐擦傷性、密着性および耐クラック性の点から設計される。（Ａ）および（Ｂ）のソリッド合計量に対して（Ａ）ソリッド分が５〜８０質量％、好ましくは１０〜６０質量％、もっとも好ましくは２０〜４０％、（Ｂ）ソリッド分が２０〜９５質量％、好ましくは４０〜９０質量％、もっとも好ましくは６０〜８０質量％である、実質的に末端がＳｉＯＨ型オルガノシロキサンの樹脂組成物が適している。 The ratio of (A) metal oxide colloidal sol and (B) alkoxysilane hydrolysis condensate used in the coating composition of the present invention depends on the stability of the composition, the transparency of the resulting cured film, the wear resistance, Designed from the viewpoint of scratch resistance, adhesion and crack resistance. (A) The solid content is 5 to 80% by mass, preferably 10 to 60% by mass, most preferably 20 to 40%, and (B) the solid content is 20 to 20% with respect to the total solid amount of (B). A resin composition having a terminal SiOH type organosiloxane of 95% by mass, preferably 40 to 90% by mass, and most preferably 60 to 80% by mass is suitable.
末端をＳｉＯＨ型とすることにより、当該オルガノシロキサン樹脂組成物は被塗物表面に塗布され、カチオン系光重合開始剤により発生する酸により脱水縮合し、シロキサン結合を形成することができる。この時、末端がＳｉＯＲで残っている場合は、塗布後、この加水分解が律速段階となり、生成するアルコールがラジカル、カチオン光開始剤に影響を与えるため好ましくなく、最悪の場合、硬化不良を引き起こすため適当ではない。 By setting the terminal to the SiOH type, the organosiloxane resin composition can be applied to the surface of an object to be coated and dehydrated and condensed with an acid generated by a cationic photopolymerization initiator to form a siloxane bond. At this time, if the terminal remains in SiOR, the hydrolysis becomes a rate-determining step after coating, and the generated alcohol is not preferable because it affects radicals and cationic photoinitiators. In the worst case, it causes poor curing. Therefore, it is not appropriate.
また、これまでの研究から、本発明のコーティング用組成物において（Ｂ）として用いられるアルコキシシランの加水分解縮合物は前記式（１）に示されるアルコキシシランの加水分解直後の発生期のＳｉＯＨが最も活性が高く、硬度、擦傷性が出やすいことが解っている。即ち、（Ｂ）成分のアルコキシシラン加水分解縮合物のピーク分子量がポリスチレン換算で１０００以下となるように分子量分布が制御された合成条件にて製造されることが、本発明のコーティング用組成物の最も重要な目的となる高硬度、高耐擦傷性、高耐摩耗性の発現につながることを意味する。 Further, from the studies so far, the hydrolysis condensate of alkoxysilane used as (B) in the coating composition of the present invention has a SiOH in the nascent stage immediately after hydrolysis of alkoxysilane represented by the formula (1). It has been found that it has the highest activity and is likely to have hardness and scratch resistance. That is, the coating composition of the present invention is manufactured under the synthesis conditions in which the molecular weight distribution is controlled so that the peak molecular weight of the alkoxysilane hydrolysis condensate of component (B) is 1000 or less in terms of polystyrene. This means that the most important purpose is high hardness, high scratch resistance, and high wear resistance.
上述したように、末端がＳｉＯＨでそのピーク分子量がポリスチレン換算で１０００以下となるように分子量を制御するためには、前記式（１）に示されるアルコキシシランの加水分解条件が重要となる。
即ち、下記式（１）
Ｒ1 aＲ2 bＳｉ（Ｒ3）4-a-b ・・・ （１）
（式中、Ｒ1は炭素数１〜１０のアルキル基を表し、Ｒ2はアリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルケニル基、エポキシ基、（メタ）アクリロイル基、ビニル基、スチリル基、メルカプト基、アミノ基、ウレイド基およびシアノ基からなる群より選ばれる１以上の基を含む有機官能基を表し、Ｒ3は炭素数１〜１０のアルコキシ基、アルケニロキシ基、アシロキシ基またはアルコキシアルコキシ基を表し、ａ，ｂはおのおの０，１，２のいずれかの整数であり、ａ＋ｂは０，１，２のいずれかの整数である。）
のアルコキシシランモノマー１モルに対して水の添加量を（（４−ａ−ｂ）＋０．２）／２モル〜２０モル、好ましくは３モル〜１０モル、最も好ましくは３．１モル〜６モルとすることにより達成される。
As described above, in order to control the molecular weight so that the terminal is SiOH and the peak molecular weight is 1000 or less in terms of polystyrene, the hydrolysis condition of the alkoxysilane represented by the formula (1) is important.
That is, the following formula (1)
R 1 a R 2 b Si (R 3 ) 4-ab (1)
(In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, and R 2 represents an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, a (meth) acryloyl group, a vinyl group, and styryl. Represents an organic functional group containing one or more groups selected from the group consisting of a group, a mercapto group, an amino group, a ureido group and a cyano group, and R 3 represents an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group, an acyloxy group or an alkoxy group Represents an alkoxy group, a and b are each an integer of 0, 1 or 2; a + b is an integer of 0, 1 or 2)
The amount of water added per mole of alkoxysilane monomer is ((4-ab) +0.2) / 2 to 20 moles, preferably 3 to 10 moles, most preferably 3.1 to 6 moles. This is achieved by making a mole.
水の添加量が不足する場合、末端がＳｉＯＨとなり得ず、アルコキシシリル基が残存してしまい、硬度の面で目的を十分に達成することができない可能性がある。一方、水の添加量が多過ぎる場合、得られた系が不安定化してしまう問題や、塗膜形成時の各種問題（白化、泡、不均質など）が生ずる懸念があるため好ましくない。
上述した水とは、系に添加されるすべての水分に言及される。即ち、添加される水分散金属酸化物コロイドゾル、加水分解触媒、有機ポリマーなどに含まれる水分を含めた総和である。
If the amount of water added is insufficient, the terminal cannot be SiOH, and alkoxysilyl groups remain, and the object may not be sufficiently achieved in terms of hardness. On the other hand, when the amount of water added is too large, there is a concern that the obtained system may become unstable and various problems (whitening, bubbles, heterogeneity, etc.) may occur during film formation, which is not preferable.
The water mentioned above refers to all moisture added to the system. That is, it is the sum including water contained in the added water-dispersed metal oxide colloidal sol, hydrolysis catalyst, organic polymer and the like.
本発明の紫外線硬化型コーティング用組成物として、上記（Ａ）金属酸化物コロイドゾル、（Ｂ）（特定の有機官能基を含む）アルコキシシラン加水分解縮合物および（Ｃ）光重合開始剤だけで使用することもできるが、さらに不飽和二重結合を１個以上有する化合物を配合して使用することができる。 As the ultraviolet curable coating composition of the present invention, only (A) metal oxide colloidal sol, (B) alkoxysilane hydrolyzed condensate (containing a specific organic functional group) and (C) photopolymerization initiator are used. It is also possible to use a compound having one or more unsaturated double bonds.
不飽和二重結合を１個以上有する化合物として具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシエチレングリコール（メタ）アクリレート等、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート等のアルコキシポリアルキレングリコール（メタ）アクリレート類、 Specific examples of compounds having one or more unsaturated double bonds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy Alkoxy polyalkylene glycol (meth) acrylates such as triethylene glycol (meth) acrylate,
２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート等の水酸基含有（メタ）アクリレート類、（メタ）アクリルアミド、及びＮ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、アクリロイルモルホリン等のＮ置換型（メタ）アクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリレート類、（メタ）アクリロニトリルなどのニトリル類、スチレン、α−メチルスチレン等のスチレン類、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテルなどのビニルエーテル類、酢酸ビニル、プロピオン酸ビニルなどの脂肪酸ビニル類、 Hydroxyl content such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. (Meth) acrylates, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. N-substituted (meth) acrylamides, amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate , Nitriles such as (meth) acrylonitrile, styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, vinyl acetate, vinyl propionate Fatty acid vinyls such as
また、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート等のアルキレングリコールジ（メタ）アクリレート、グリセリンプロピレンオキサイド変性トリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド変性トリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイド変性トリ（メタ）アクリレート、イソシアール酸エチレンオキサイド変性トリ（メタ）アクリレート、イソシアール酸エチレンオキサイド変性ε−カプロラクトン変性トリ（メタ）アクリレート、１，３，５−トリアクリロイルヘキサヒドロ−Ｓ−トリアジン、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレートトリプロピオネートなどの３官能（メタ）アクリレート類；また、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートモノプロピオネート、ジペンタエリスリトールヘキサ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、オリゴエステルテトラ（メタ）アクリレート、トリス（（メタ）アクリロイルオキシ）ホスフェ−ト、ＰＰＺなどの多官能（メタ）アクリレートが挙げられる。 Further, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanic acid ethylene oxide modified tri (meth) acrylate, isocyanic acid ethylene oxide modified ε -Caprolactone-modified tri (meth) acrylate, 1,3,5-triacryloylhexahydro-S-triazine, pentaerythritol Trifunctional (meth) acrylates such as li (meth) acrylate and dipentaerythritol tri (meth) acrylate tripropionate; pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, Examples include polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, oligoester tetra (meth) acrylate, tris ((meth) acryloyloxy) phosphate, and PPZ. .
さらに上記したような化合物の他にポリエステル（メタ）アクリレート、ポリウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、（メタ）アクリル化マレイン酸変性ポリブタジエン等を挙げることができる。
これらアクリレートの添加量としては（Ａ）金属酸化物コロイドゾルのソリッド分に（Ｂ）アルコキシシラン加水分解縮合物のソリッド分を加えた無機成分に対して、上記有機成分のソリッド比を無機／有機としたとき、９５／５質量比〜５／９５質量比、好ましくは７０／３０質量比〜３０／７０質量比が好ましい。
In addition to the above-described compounds, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, (meth) acrylated maleic acid-modified polybutadiene and the like can be exemplified.
The amount of these acrylates added is (A) the solid content of the metal oxide colloidal sol and (B) the solid content of the alkoxysilane hydrolysis condensate is added to the inorganic component, and the solid ratio of the organic component is inorganic / organic. 95/5 mass ratio to 5/95 mass ratio, preferably 70/30 mass ratio to 30/70 mass ratio.
また、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートなどアルコール含有多官能アクリレートをγ−イソシアナトプロピルトリメトキシシランなどでシリル化し、本発明における（Ｂ）成分として用いることは、前述反応性無機−有機架橋剤として働くためこれも有用である。 In addition, silylation of alcohol-containing polyfunctional acrylates such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate with γ-isocyanatopropyltrimethoxysilane and the like, and use as the component (B) in the present invention, This is also useful because it acts as a reactive inorganic-organic crosslinking agent as described above.
本発明においては、上記ＳｉＯＨ型オルガノシロキサン樹脂組成物の−ＳｉＯＨ基、もしくは含有する他の官能基と反応する、もしくは水素結合、π−π共役、配位結合などの化学的相互作用により安定化する官能基、部分を有する有機重合体を、反応系中に存在させることができる。 In the present invention, it reacts with -SiOH group of the above-mentioned SiOH type organosiloxane resin composition or other functional groups contained, or is stabilized by chemical interaction such as hydrogen bond, π-π conjugation, coordination bond, etc. An organic polymer having a functional group and a moiety can be present in the reaction system.
上記ＳｉＯＨ型オルガノシロキサン樹脂組成物の−ＳｉＯＨ基と反応する、もしくは水素結合により安定化する官能基、部分を有する有機重合体としては、アクリルシリコーン、アルコキシシリル基変性エポキシ樹脂、アルコキシシリル基変性ウレタン樹脂、アルコキシシリル基変性ポリエステル、アルコキシシリル基変性ポリブタジエン、アルコキシシリル基変性フッ素樹脂など各種シリル化ポリマー、エポキシ樹脂、各種グリシジルエーテル、アクリルポリオール、エポキシポリオールなどポリオール類、ポリウレタン樹脂、ポリアミド（ナイロン）樹脂、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリオキサゾリン樹脂、ポリチオール樹脂、フェノール樹脂、メラミン樹脂などが例示される。 Examples of the organic polymer having a functional group or moiety that reacts with -SiOH group of the SiOH type organosiloxane resin composition or is stabilized by hydrogen bond include acrylic silicone, alkoxysilyl group-modified epoxy resin, and alkoxysilyl group-modified urethane. Various silylated polymers such as resins, alkoxysilyl group-modified polyesters, alkoxysilyl group-modified polybutadienes, alkoxysilyl group-modified fluororesins, epoxy resins, various glycidyl ethers, acrylic polyols, epoxy polyols such as epoxy polyols, polyurethane resins, polyamide (nylon) resins , Polyvinyl alcohol resin, polyvinyl butyral resin, polyoxazoline resin, polythiol resin, phenol resin, melamine resin and the like.
また、π−π共役や配位結合などの化学的相互作用により安定化する官能基、部分を有する有機重合体としては、ポリスチレン、ビスフェノール型エポキシ樹脂、スチレン−マレイン酸共重合樹脂、各種アイオノマー樹脂、有機金属含有ポリマーなどが例示される。これら有機重合体はオルガノシロキサン部位と安定化、一体化して樹脂の骨格に取り込まれ、オルガノシロキサンの無機特性に対して有機特性を付与する特性上、合成のはじめの段階で仕込まれるべきである。いわゆる、オルガノシロキサン加水分解重縮合の系中に添加されるｉｎ ｓｉｔｕゾルゲル法が適用される。これら有機重合体の配合量としては（Ａ） 金属酸化物コロイドゾルのソリッド分に（Ｂ）アルコキシシラン加水分解縮合物のソリッド分を加えた無機成分に対して、上記有機成分のソリッド比を無機／有機としたとき、９５／５質量比〜５０／５０質量比が好ましい。この範囲を超えて有機重合体配合量が減ると、その添加効果が出にくくなり、また、多くなりすぎると、無機特性、特に耐擦傷性が低下するため好ましくない。 In addition, as an organic polymer having functional groups and moieties that are stabilized by chemical interaction such as π-π conjugation or coordination bond, polystyrene, bisphenol type epoxy resin, styrene-maleic acid copolymer resin, various ionomer resins And organic metal-containing polymers. These organic polymers should be charged at the beginning of the synthesis because they are stabilized and integrated with the organosiloxane moiety and incorporated into the resin skeleton to impart organic properties to the inorganic properties of the organosiloxane. The so-called in situ sol-gel method added to the so-called organosiloxane hydrolysis polycondensation system is applied. The blending amount of these organic polymers is (A) the solid content of the metal oxide colloidal sol and the inorganic component obtained by adding the solid content of (B) alkoxysilane hydrolysis condensate to the solid content ratio of the above organic component. When organic, 95/5 mass ratio to 50/50 mass ratio is preferable. If the amount of the organic polymer blended is less than this range, the effect of addition becomes difficult to occur, and if it is too large, the inorganic properties, particularly the scratch resistance, is undesirably lowered.
本発明のコーティング用組成物には、さらに（Ｃ）光重合開始剤が使用される。本発明における（Ｃ）光重合開始剤には、ラジカル系光重合開始剤およびカチオン系光重合開始剤が挙げられ、これら双方が併用されることが好ましい。ラジカル系光重合開始剤は、本発明のコーティング用組成物におけるアクリレート部位の硬化に利用され、カチオン系光重合開始剤は末端ＳｉＯＨの脱水縮合反応を促進させ、かつ、エポキシ部のカチオン重合にも利用される。即ち、本発明においては、無機成分と有機成分が光で開始される２つの別種の反応により一体化して硬化する反応機構によって進行するため、無機の特性と有機の特性を併有する硬化体が得られるのである。 In the coating composition of the present invention, (C) a photopolymerization initiator is further used. Examples of the photopolymerization initiator (C) in the present invention include radical photopolymerization initiators and cationic photopolymerization initiators, and it is preferable that both of them are used in combination. The radical photopolymerization initiator is used for curing the acrylate moiety in the coating composition of the present invention, and the cationic photopolymerization initiator promotes the dehydration condensation reaction of the terminal SiOH and is also used for cationic polymerization of the epoxy part. Used. In other words, in the present invention, the inorganic component and the organic component proceed by a reaction mechanism in which they are integrated and cured by two different reactions initiated by light, so that a cured product having both inorganic and organic properties is obtained. It is done.
使用されるラジカル系光重合開始剤としては、光励起によってラジカル重合を開始できる機能を有するものであれば特に限定はなく、例えばモノカルボニル化合物、ジカルボニル化合物、アセトフェノン化合物、ベンゾインエーテル化合物、アシルフォスフィンオキシド化合物、アミノカルボニル化合物などが使用できる。 The radical photopolymerization initiator used is not particularly limited as long as it has a function capable of initiating radical polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine. An oxide compound, an aminocarbonyl compound, etc. can be used.
同様に、使用されるカチオン系光重合開始剤としては、下記式２で表される、いわゆるラジエーション感受性芳香族オニウム塩であれば、特に限定されない。
（Ｒ3−Ｃ6Ｈ4）nＸ+ＭＱh - ・・・ （２）
（式中、ＸはＩ，ＰおよびＳからなる群より選択されるいずれかの基であり、Ｍは金属または半金属であり、ＱはＣｌ、Ｆ、ＢｒおよびＩからなる群より選択されるいずれかのハロゲンであり、Ｒ3は水素または炭素数１〜１２の一価炭化水素基であり、ｈは４〜６の整数であり、ｎは２または３の整数である。）
上記式中のＭＱh -が、ＳｂＦ6 -、ＡｓＦ6 -、ＢＦ4 -あるいはＰＦ6 -である化合物が、一般には使用される。
Similarly, the cationic photopolymerization initiator used is not particularly limited as long as it is a so-called radiation-sensitive aromatic onium salt represented by the following formula 2.
(R 3 -C 6 H 4) n X + MQ h - ··· (2)
Wherein X is any group selected from the group consisting of I, P and S, M is a metal or metalloid, and Q is selected from the group consisting of Cl, F, Br and I Any halogen, R 3 is hydrogen or a monovalent hydrocarbon group having 1 to 12 carbon atoms, h is an integer of 4 to 6, and n is an integer of 2 or 3.)
A compound in which MQ h − in the above formula is SbF 6 − , AsF 6 − , BF 4 − or PF 6 − is generally used.
本発明のコーティング用組成物に使用されるラジカル系光重合開始剤およびカチオン系光重合開始剤の添加量としては、それぞれ０．００５〜１０質量％の範囲が好ましい。この範囲を超えて少ない場合は、硬化不良、硬度の不足などの問題が生じる懸念があり、多い場合は、着色の問題が発生する懸念があるため、それぞれ好ましくない。 The addition amount of the radical photopolymerization initiator and the cationic photopolymerization initiator used in the coating composition of the present invention is preferably in the range of 0.005 to 10% by mass. If the amount is more than this range, there is a concern that problems such as poor curing and insufficient hardness may occur, and if the amount is large, there is a concern that a coloring problem may occur.
本発明の紫外線硬化型コーティング用組成物には、目的を損なわない範囲で溶媒が使用されうる。この溶媒としては前記オルガノシロキサン樹脂固形分が安定に溶解することが必要である。そのためには、使用される溶媒はアルコールを含むものであることが望ましい。かかるアルコールとしては例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチル−１プロパノール、２−エトキシエタノール、２−ブトキシエタノールなどが挙げられ、炭素数１〜４の低沸点アルコールが好ましく、溶解性、安定性、及び塗工性の点で２−プロパノールが特に好ましい。 A solvent can be used in the ultraviolet curable coating composition of the present invention as long as the purpose is not impaired. As this solvent, it is necessary that the organosiloxane resin solid content is stably dissolved. For that purpose, it is desirable that the solvent used contains an alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1propanol, 2-ethoxyethanol, 2-butoxyethanol, and the like. A low-boiling alcohol of ˜4 is preferred, and 2-propanol is particularly preferred from the viewpoint of solubility, stability, and coatability.
これに、アクリレート成分の良溶媒であるメチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）などのケトン類；酢酸エチル、酢酸ブチルなどのエステル類；グリコールエーテル類；グリコールエーテルエステル類；芳香族炭化水素類；が推奨される。ただし、溶剤には各種法規制があるためそれを考慮すべきである。 In addition, ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), which are good solvents for the acrylate component; esters such as ethyl acetate and butyl acetate; glycol ethers; glycol ether esters; aromatic hydrocarbons Is recommended. However, there are various laws and regulations for solvents, which should be considered.
かかる溶媒中には水分散型コロイダルシリカ中の水で加水分解反応に関与しない水分、アルコキシシランの加水分解に伴って発生する低級アルコール、有機溶媒分散型のコロイダルシリカを使用した場合にはその分散媒の有機溶媒、有機重合体が配合されれば、それに含まれる溶媒、コーティング用組成物のｐＨ調整のために添加される酸も含まれる。ｐＨ調整のために使用される酸としては塩酸、硫酸、燐酸、亜硝酸、硝酸。過塩素酸、スルファミン酸などの無機酸、蟻酸、酢酸、プロピオン酸、酪酸、シュウ酸、コハク酸、マレイン酸、乳酸、パラトルエンスルホン酸などの有機酸が挙げられ、ｐＨ調整の容易さの観点から、蟻酸、酢酸、プロピオン酸、酪酸、シュウ酸、コハク酸、マレイン酸などの有機カルボン酸が好ましい。 In such a solvent, when water in water-dispersed colloidal silica is used, water that does not participate in the hydrolysis reaction, lower alcohol generated by hydrolysis of alkoxysilane, and organic solvent-dispersed colloidal silica are dispersed. If an organic solvent or an organic polymer as a medium is blended, the solvent contained therein and an acid added for adjusting the pH of the coating composition are also included. Acids used for pH adjustment include hydrochloric acid, sulfuric acid, phosphoric acid, nitrous acid, and nitric acid. Examples include inorganic acids such as perchloric acid and sulfamic acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, and paratoluenesulfonic acid. Therefore, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid and maleic acid are preferred.
本発明のコーティング用組成物は、酸、溶剤の含有量を調整することによりｐＨを３．０〜６．０に調整することが好ましく、４．０〜５．５に調整することがより好ましい。これにより、常温でのコーティング用組成物のゲル化を防止し、保存安定性を増すことができる。 In the coating composition of the present invention, the pH is preferably adjusted to 3.0 to 6.0 by adjusting the contents of the acid and solvent, and more preferably adjusted to 4.0 to 5.5. . Thereby, the gelatinization of the coating composition at room temperature can be prevented, and the storage stability can be increased.
なお、本発明のコーティング用組成物には、塗工性および得られる塗膜の平滑性、外観を向上させる目的で公知のレベリング剤、消泡剤などの添加剤を配合することができる。かかる添加剤の配合量としては、既述の（Ａ）〜（Ｃ）および溶媒の全成分１００質量部に対して０．００１〜２質量部の範囲が好ましい。また、本発明の目的を損なわない範囲で紫外線吸収剤、光安定剤、染料、顔料、フィラーなどを配合してもかまわない。 In the coating composition of the present invention, additives such as known leveling agents and antifoaming agents can be blended for the purpose of improving the coatability and smoothness and appearance of the resulting coating film. As a compounding quantity of this additive, the range of 0.001-2 mass parts is preferable with respect to 100 mass parts of all the components of the above-mentioned (A)-(C) and a solvent. Moreover, you may mix | blend a ultraviolet absorber, a light stabilizer, dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.
本発明のコーティング用組成物の基材（被塗物）への塗布は、バーコート法、ディップコート法、フローコート法、スプレーコート法、スピンコート法、ローラーコート法、リバースコートあるいはグラビア印刷、フレキソ印刷、スクリーン印刷、インクジェット印刷などといったあらゆる塗装、印刷が可能であり、塗装される基材の形状に応じて適宜選択することができる。 Application of the coating composition of the present invention to a substrate (object) includes bar coating, dip coating, flow coating, spray coating, spin coating, roller coating, reverse coating or gravure printing, All kinds of coating and printing such as flexographic printing, screen printing, and inkjet printing are possible, and can be appropriately selected according to the shape of the base material to be coated.
また、本発明の紫外線硬化型コーティング用組成物は、塗料、グラビア印刷インキ、フレキソ印刷インキ、インクジェット印刷インキなどのインキバインダー、およびラミネーション接着剤を含む各種接着剤として使用することができる。本発明の紫外線硬化型コーティング用組成物は、公知の紫外線硬化方法により硬化させることができ、特に紫外線もしくは電子線を用いることが好ましい。 Further, the ultraviolet curable coating composition of the present invention can be used as various adhesives including ink binders such as paints, gravure printing inks, flexographic printing inks and inkjet printing inks, and lamination adhesives. The ultraviolet curable coating composition of the present invention can be cured by a known ultraviolet curing method, and it is particularly preferable to use ultraviolet rays or electron beams.
紫外線照射装置としては光源として、通常２００〜５００ｎｍの範囲の光を含む光源、例えば高圧水銀灯、超高圧水銀灯、メタルハライド灯、ガリウム灯、キセノン灯、カーボンアーク灯等を有するものが使用できる。紫外線の積算光量は、用途、膜厚、着色剤の有無、光重合開始剤の種類と量により必要最低積算光量が左右されるため制限はない。
これら紫外線、電子線と赤外線、遠赤外線、熱風、高周波加熱等による熱の併用は効果的である。
As the ultraviolet irradiation device, a light source usually containing light in the range of 200 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like can be used. The accumulated amount of ultraviolet light is not limited because the required minimum accumulated amount of light depends on the application, film thickness, presence / absence of a colorant, and the type and amount of the photopolymerization initiator.
The combined use of heat by ultraviolet rays, electron beams and infrared rays, far infrared rays, hot air, high-frequency heating or the like is effective.
また、本発明の紫外線硬化型コーティング用組成物は、フリーラジカルによるアクリレート成分とカチオンによるシロキサンおよびエポキシ成分の複合架橋により硬化していく。反応速度としては「ラジカル反応＞カチオン反応」であり、無機／有機配合量、有機成分、無機成分の選択により硬化性、柔軟性を制御したり、ＵＶ照射後に後加工することも可能となる。 Further, the ultraviolet curable coating composition of the present invention is cured by complex crosslinking of an acrylate component by free radicals and a siloxane and epoxy component by cations. The reaction rate is “radical reaction> cation reaction”, and it is possible to control the curability and flexibility by selecting the inorganic / organic blending amount, the organic component, and the inorganic component, or to perform post-processing after UV irradiation.
本発明の紫外線硬化型コーティング用組成物の厚みは、通常０．１〜２０μｍ、好ましくは２〜１０μｍ、最も好ましくは３〜８μｍである。コート層の厚みがかかる範囲内で塗布された場合には、硬化時に発生する応力の為にコート層と基材との密着性が低下したりすることなく、本発明の目的とする十分な硬度、耐擦傷性、耐摩耗性を有するコート層が得られることとなる。 The thickness of the ultraviolet curable coating composition of the present invention is usually 0.1 to 20 μm, preferably 2 to 10 μm, and most preferably 3 to 8 μm. When applied within a range where the thickness of the coat layer is applied, sufficient hardness as an object of the present invention can be obtained without reducing the adhesion between the coat layer and the substrate due to stress generated during curing. Thus, a coating layer having scratch resistance and abrasion resistance can be obtained.
次に、実施例および比較例を挙げて本発明をより具体的に説明するが、これにより本発明が限定されるものでないことは言うまでもない。
以下に実施例を挙げて説明する。
Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, it cannot be overemphasized that this invention is not limited by this.
Hereinafter, an example will be described.
＜合成例１：シリル化多官能アクリレートの合成＞
窒素導入管および温度計を取り付けた３００ｍｌの４口フラスコに、ペンタエリスリトールトリアクリレート（共栄社化学社製、商品名ライトアクリレートＰＥ−３Ａ）１４９ｇを秤量して仕込み、１０２．５ｇのγ−イソシアナトプロピルトリメトキシシラン（日本ユニカー社製、商品名Ｙ−５１８７）を室温で１ｈかけて滴下した。これを６０℃に昇温し３ｈ反応させた。
ＦＴ−ＩＲにより、２２００ｃｍ-1のイソシアネートの吸収が消え、３３００ｃｍ-1に−ＮＨの吸収が現れ、１７００ｃｍ-1以下にウレタンの吸収が出現したことから、ペンタエリスリトールトリアクリレートがシリル化されたことを確認した。
<Synthesis Example 1: Synthesis of silylated polyfunctional acrylate>
A 300 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer was weighed with 149 g of pentaerythritol triacrylate (trade name: Light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) and charged with 102.5 g of γ-isocyanatopropyl. Trimethoxysilane (Nihon Unicar Co., Ltd., trade name Y-5187) was added dropwise at room temperature over 1 h. This was heated to 60 ° C. and reacted for 3 hours.
The FT-IR, disappears absorption of isocyanate 2200 cm -1, absorption of -NH appeared in 3300 cm -1, since the absorption of the urethane appeared to 1700 cm -1 or less, the pentaerythritol triacrylate is silylated It was confirmed.
［実施例１］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、３５．７ｇのメチルトリメトキシシラン、２０．７ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、１５ｇのγ−グリシドキシプロピルトリメトキシシラン（チッソ社製サイラエースＳ５１０）、１９．２ｇの合成例１のシリル化多官能アクリレート、１１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、１１３．８ｇのイソプロピルアルコール（ＩＰＡ）を仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 1]
In a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 35.7 g of methyltrimethoxysilane, 20.7 g of γ-acryloxypropyltrimethoxysilane (trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 15 g of γ-glycidoxypropyltrimethoxysilane (Silas Ace S510 manufactured by Chisso Corporation), 19.2 g of silylated polyfunctional acrylate of Synthesis Example 1, 115 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), 113.8 g Of isopropyl alcohol (IPA) was added and stirred uniformly while bubbling nitrogen.
別に、スノーテックスＯ４０｛日産化学工業社製シリカゾル、ＮＶ（固形分濃度）４０％｝３７．５ｇ、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液４．５ｇ、蒸留水２２．５ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, Snowtex O40 {Silica sol manufactured by Nissan Chemical Industries, NV (solid content concentration) 40%} 37.5 g, 1 mol / l (1N) acetic acid aqueous solution 4.5 g, and distilled water 22.5 g were weighed to be uniform. Until mixed. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、３時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を７．７ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）７．７ｇ、ＭＥＫを３８．５ｇ添加してコーティング液を得た。
After completion of the dropwise addition, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 3 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Next, the synthesized product was transferred to a brown bottle, and 7.7 g of Irgacure 184 (Ciba Specialty Chemicals), 7.7 g of Sun-Aid SI100L (Sanshin Chemical Co., Ltd.), and 38.5 g of MEK were added to the coating solution. Got.
［実施例２］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、２５ｇのセルナックスＣＸ−Ｚ６１０Ｍ−Ｆ２（日産化学工業社製導電性複酸化物ゾル）、３５．７ｇのメチルトリメトキシシラン、３５．７ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、１９．２ｇの合成例１のシリル化多官能アクリレート、１１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、１０３．８ｇのＩＰＡを仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 2]
Into a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 25 g of Celnax CX-Z610M-F2 (Nissan Chemical Industries conductive double oxide sol), 35.7 g of methyltrimethoxysilane, 35. 7 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103), 19.2 g of silylated polyfunctional acrylate of Synthesis Example 1, 115 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) , 103.8 g of IPA was charged and stirred uniformly while bubbling nitrogen.
別に、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液４．５ｇ、蒸留水４５．０ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, 4.5 g of 1 mol / l (1N) acetic acid aqueous solution and 45.0 g of distilled water were weighed and mixed until uniform. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、２時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を７．７ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）７．７ｇ、ＭＥＫを３８．５ｇ添加してコーティング液を得た。
After completion of the dropping, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 2 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Next, the synthesized product was transferred to a brown bottle, and 7.7 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 7.7 g of Sun-Aid SI100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and 38.5 g of MEK were added to the coating solution. Got.
［実施例３］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、３５．７ｇのメチルトリメトキシシラン、３５．７ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、１９．２ｇの合成例１のシリル化多官能アクリレート、１１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、６７．３ｇのライトアクリレートＢＰ−４ＥＡ（共栄社化学社製）、１１３．８ｇのＩＰＡを仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 3]
To a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 35.7 g of methyltrimethoxysilane, 35.7 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103), 19.2 g of the silylated polyfunctional acrylate of Synthesis Example 1, 115 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), 67.3 g of light acrylate BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.), 113.8 g of IPA The mixture was stirred and stirred uniformly while bubbling nitrogen.
別に、スノーテックスＯ４０（日産化学工業社製シリカゾル、ＮＶ４０％）１８．８ｇ、アルミナゾル５２０（日産化学工業社製アルミナゾル、ＮＶ２０％）３７．５ｇ、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液４．５ｇ、蒸留水３．７ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, Snowtex O40 (silica sol manufactured by Nissan Chemical Industries, NV 40%) 18.8 g, alumina sol 520 (alumina sol manufactured by Nissan Chemical Industries, NV 20%) 37.5 g, 4.5 g of 1 mol / l (1N) acetic acid aqueous solution, distilled 3.7 g of water was weighed and mixed until uniform. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、３時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を７．７ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）７．７ｇ、ＭＥＫを３８．５ｇ添加してコーティング液を得た。
After completion of the dropwise addition, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 3 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Next, the synthesized product was transferred to a brown bottle, and 7.7 g of Irgacure 184 (Ciba Specialty Chemicals), 7.7 g of Sun-Aid SI100L (Sanshin Chemical Co., Ltd.), and 38.5 g of MEK were added to the coating solution. Got.
［実施例４］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、３４．３ｇのメチルトリメトキシシラン、３４．３ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、２．０ｇの合成例１のシリル化多官能アクリレート、１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、２２０．５ｇのＩＰＡを仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 4]
In a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 34.3 g of methyltrimethoxysilane, 34.3 g of γ-acryloxypropyltrimethoxysilane (trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 2.0 g of the silylated polyfunctional acrylate of Synthesis Example 1, 15 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 220.5 g of IPA were charged and stirred uniformly while bubbling nitrogen.
別に、シリカドール３３Ａ（日本化学工業社製シリカゾル、ＮＶ３３％）１５３ｇ、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液４．３ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, 153 g of silica doll 33A (Nippon Chemical Industry Co., Ltd. silica sol, NV33%), 4.3 g of 1 mol / l (1N) acetic acid aqueous solution, was weighed and mixed until uniform. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、３時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を４．２ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）４．２ｇを添加してコーティング液を得た。
After completion of the dropwise addition, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 3 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Subsequently, the synthesized product was transferred to a brown bottle, and 4.2 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 4.2 g of Sun Aid SI100L (manufactured by Sanshin Chemical Industry) were added to obtain a coating solution.
［実施例５］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、２７．５のメチルトリメトキシシラン、２７．５ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、２．０ｇの合成例１のシリル化多官能アクリレート、１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、３０．５ｇのコンポブリッドＡＢ３０７３（アトミクス社製アクリルシリコーン樹脂、ＮＶ５５％、メタノール溶液）、２３０ｇのＩＰＡを仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 5]
To a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 27.5 methyltrimethoxysilane, 27.5 g γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103), 2.0 g of silylated polyfunctional acrylate of Synthesis Example 1, 15 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), 30.5 g of compound AB3073 (acrylic silicone resin manufactured by Atomics Co., Ltd., NV55%, methanol solution), 230 g of IPA was charged and stirred uniformly while bubbling nitrogen.
別に、シリカドール３３Ａ（日本化学工業社製シリカゾル、ＮＶ３３％）１２２ｇ、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液３．４ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, 122 g of silica doll 33A (Nippon Chemical Industry Co., Ltd. silica sol, NV 33%), 3.4 g of 1 mol / l (1N) acetic acid aqueous solution, was weighed and mixed until uniform. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、３時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を４．２ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）４．２ｇを添加してコーティング液を得た。
After completion of the dropwise addition, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 3 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Subsequently, the synthesized product was transferred to a brown bottle, and 4.2 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 4.2 g of Sun Aid SI100L (manufactured by Sanshin Chemical Industry) were added to obtain a coating solution.
［実施例６］
窒素導入管および温度計を取り付けた５００ｍｌの４口フラスコに、２７．５のメチルトリメトキシシラン、２７．５ｇのγ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、２．０ｇの合成例１のシリル化多官能アクリレート、１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）、５６．０ｇのバーノック１８−４７２（大日本インキ化学工業社製ウレタン樹脂、ＮＶ＝３０％）、２０４．３ｇのＩＰＡを仕込み、窒素をバブリングしながら均一に攪拌した。
[Example 6]
To a 500 ml four-necked flask equipped with a nitrogen inlet tube and a thermometer, 27.5 methyltrimethoxysilane, 27.5 g γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103), 2.0 g of the silylated polyfunctional acrylate of Synthesis Example 1, 15 g of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), 56.0 g of Barnock 18-472 (Dainippon Ink Chemical Industries, Ltd. urethane resin, NV = 30) %), 204.3 g of IPA was charged and stirred uniformly while bubbling nitrogen.
別にシリカドール３３Ａ（日本化学工業社製シリカゾル、ＮＶ３３％）１２２ｇ、１ｍｏｌ／ｌ（１Ｎ）酢酸水溶液３．４ｇを秤量し、均一になるまで混合した。これを上記４口フラスコに１時間かけて滴下ロートにて滴下した。この時、フラスコ内の温度は３５℃に保った。 Separately, 122 g of silica doll 33A (Nippon Chemical Industry Co., Ltd. silica sol, NV 33%), 3.4 g of 1 mol / l (1N) acetic acid aqueous solution, was weighed and mixed until uniform. This was dripped at the said 4-neck flask with the dropping funnel over 1 hour. At this time, the temperature in the flask was kept at 35 ° C.
滴下終了後３５℃に３０分間保ち、その後３０分かけて６０℃に昇温し、３時間反応させ目的物を得た。得られた溶液は乳白色透明低粘性液体であった。
次いで、合成物を褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を４．２ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）４．２ｇを添加してコーティング液を得た。
After completion of the dropwise addition, the temperature was maintained at 35 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. over 30 minutes and reacted for 3 hours to obtain the desired product. The resulting solution was a milky white transparent low viscosity liquid.
Subsequently, the synthesized product was transferred to a brown bottle, and 4.2 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 4.2 g of Sun Aid SI100L (manufactured by Sanshin Chemical Industry) were added to obtain a coating solution.
［比較例１］
実施例１において、スノーテックスＯ４０（日産化学工業社製シリカゾル、ＮＶ４０％）を加えなかったこと以外は実施例１と同様にして合成したものを比較例１とした。
[Comparative Example 1]
Comparative Example 1 was synthesized in the same manner as in Example 1 except that Snowtex O40 (Nissan Chemical Industries silica sol, NV 40%) was not added.
［比較例２］
実施例１において、γ−アクリロキシプロピルトリメトキシシラン（信越化学社製、商品名ＫＢＭ−５１０３）、γ−グリシドキシプロピルトリメトキシシラン（チッソ社製サイラエースＳ５１０）および合成例１のシリル化多官能アクリレートを加えなかったこと以外は実施例１と同様にして合成したものを比較例２とした。
[Comparative Example 2]
In Example 1, γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103), γ-glycidoxypropyltrimethoxysilane (Syraace S510, manufactured by Chisso Corp.) Comparative Example 2 was synthesized in the same manner as Example 1 except that no functional acrylate was added.
［比較例３］
実施例４において、サンエイドＳＩ１００Ｌ（三新化学工業社製）４．２ｇを加えなかったこと以外は実施例１と同様にして合成したものを比較例３とした。
[Comparative Example 3]
Comparative Example 3 was synthesized in the same manner as in Example 1 except that 4.2 g of Sun Aid SI100L (manufactured by Sanshin Chemical Industry Co., Ltd.) was not added.
［比較例４］
アトムコンポブリットＸＳＧ（アトミクス社製液状無溶剤型シリコーン樹脂、末端ＳｉＯＲタイプ）５０ｇを２００ｇのＩＰＡに溶解し、１９．２ｇの合成例１のシリル化多官能アクリレート、１１５ｇのライトアクリレートＤＰＥ−６Ａ（共栄社化学社製）を添加して均一に混合した。
次いで、これを褐色瓶に移し、イルガキュアー１８４（チバスペシャルティーケミカルズ社製）を７．７ｇ、サンエイドＳＩ１００Ｌ（三新化学工業社製）７．７ｇ、ＭＥＫを３８．５ｇ添加してコーティング液を得た。
[Comparative Example 4]
Atom Compobritt XSG (Atomics Co., liquid solvent-free silicone resin, terminal SiOR type) 50 g was dissolved in 200 g of IPA, and 19.2 g of the silylated polyfunctional acrylate of Synthesis Example 1 and 115 g of light acrylate DPE-6A ( Kyoeisha Chemical Co., Ltd.) was added and mixed uniformly.
Next, this was transferred to a brown bottle, 7.7 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 7.7 g of Sun Aid SI100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and 38.5 g of MEK were added, and the coating solution was added. Obtained.
［評価塗膜作製方法］
各種塗膜評価用として、ポリカーボネート樹脂板の表面をイソブタノールで脱脂処理し、＃２０バーコーダーにて均一に塗布し、１０分間セッティングの後下記条件でＵＶ硬化させた。
[Evaluation Coating Method]
For evaluation of various coating films, the surface of the polycarbonate resin plate was degreased with isobutanol, applied uniformly with a # 20 bar coder, set for 10 minutes, and then UV cured under the following conditions.
（ＵＶ硬化条件）
ウシオ電機社製ＵＶ照射装置「ＵＶＣ−５０３４」、メタルハライドランプ４９０ｎｍ×６３０ｍｍ、８０Ｗ／ｃｍ、高さ１２０ｍｍ、コンベヤー速度４ｍ／分、２８０ｍＪ／ｃｍ2
また、鉛筆硬度の評価用として、基材をボンデライト鋼板にして、上記と同様に塗膜形成したものを作製した。
(UV curing conditions)
Ushio's UV irradiation device “UVC-5034”, metal halide lamp 490 nm × 630 mm, 80 W / cm, height 120 mm, conveyor speed 4 m / min, 280 mJ / cm 2
Further, for evaluation of pencil hardness, a substrate was formed into a bonderite steel plate and a coating film was formed in the same manner as described above.
［評価方法］
（１）溶液外観：
得られた実施例１〜６および比較例１〜４のコーティング用組成物の溶液を試験管に満たし目視にて判定した。
[Evaluation methods]
(1) Solution appearance:
The obtained solutions of the coating compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were filled in test tubes and judged visually.
（２）塗膜外観：
評価用塗膜を目視にて濁り、艶びけ、ブツ、クラックなどの有無を確認した。
(2) Appearance of coating film:
The coating film for evaluation was visually checked for the presence or absence of turbidity, glazing, bumps and cracks.
（３）鉛筆硬度：
ＪＩＳに従って実施した。当該評価のみ、基材がボンデライト鋼板のものを用いた。
(3) Pencil hardness:
It was carried out according to JIS. Only the said evaluation used the base material of the bonderite steel plate.
（４）耐擦傷性：
＃００００スチールウールを用い、５００ｇの荷重で２０回擦った後の表面の傷つき状態を観察し、以下の評価基準で評価した。
○・・・全くキズがつかない
△・・・わずかにキズがつく
×・・・はっきりとキズがつく
(4) Scratch resistance:
Using # 0000 steel wool, the surface was scratched after being rubbed 20 times with a load of 500 g, and evaluated according to the following evaluation criteria.
○ ・ ・ ・ No scratches △ ・ ・ ・ Slightly scratches × ・ ・ ・ Scratches clearly
（５）安定性：
密閉容器に封入して、恒温室に３カ月間放置した後の状態を観察し、以下の評価基準で評価した
○・・・全く変化なし
×・・・顕著な増粘〜ゲル化
(5) Stability:
It was sealed in a sealed container and observed for 3 months after standing in a temperature-controlled room, and evaluated according to the following evaluation criteria: ○ ・ ・ ・ No change × ・ ・ ・ Significant thickening to gelation
（６）耐クラック性：
ポリカーボネート樹脂板の表面をイソブタノールで脱脂処理し、乾燥膜厚が２０μｍになるように調整して皮膜を形成させた時の塗膜外観を観察し、以下の評価基準で評価した。
○・・・クラック、割れ、はがれなどなし
×・・・クラック、割れ、はがれ発生
(6) Crack resistance:
The surface of the polycarbonate resin plate was degreased with isobutanol, and the appearance of the coating film was observed when the film was formed by adjusting the dry film thickness to 20 μm, and evaluated according to the following evaluation criteria.
○ ・ ・ ・ No cracks, cracks, peeling, etc.
（７）可撓性：
（６）の評価試験で得られた塗膜をポリカーボネート基材ごと１０回たわませた後の塗膜外観を観察し、以下の評価基準で評価した。
○・・・クラック、割れ、はがれなどなし
×・・・クラック、割れ、はがれ発生
(7) Flexibility:
The coating film appearance after the coating film obtained in the evaluation test of (6) was bent 10 times together with the polycarbonate substrate was observed and evaluated according to the following evaluation criteria.
○ ・ ・ ・ No cracks, cracks, peeling, etc.
［結果］
実施例および比較例のコーティング用組成物のスペック、および上記評価試験の結果を下記表１および表２にまとめる。
[result]
Tables 1 and 2 below summarize the specifications of the coating compositions of Examples and Comparative Examples, and the results of the above evaluation tests.
［結果の考察］
以上の結果より、本発明のコーティング用組成物によるコーティング膜が、硬質で耐擦傷性に優れたものであることがわかる。
[Consideration of results]
From the above results, it can be seen that the coating film made of the coating composition of the present invention is hard and excellent in scratch resistance.
Claims (9)
Ｒ1 aＲ2 bＳｉ（Ｒ3）4-a-b ・・・ （１）
（式中、Ｒ1は炭素数１〜１０のアルキル基を表し、Ｒ2はアリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルケニル基、エポキシ基、（メタ）アクリロイル基、ビニル基、スチリル基、メルカプト基、アミノ基、ウレイド基およびシアノ基からなる群より選ばれる１以上の基を含む有機官能基を表し、Ｒ3は炭素数１〜１０のアルコキシ基、アルケニロキシ基、アシロキシ基またはアルコキシアルコキシ基を表し、ａ，ｂはおのおの０，１，２のいずれかの整数であり、ａ＋ｂは０，１，２のいずれかの整数である。）
そのうちの少なくとも一部が、式（１）中のｂが１または２であり、かつ、Ｒ2が、（メタ）アクリロイル基、ビニル基、スチリル基、エポキシ基およびメルカプト基からなる群より選ばれるいずれかの基を含む特定の有機官能基である請求項１または２に記載の紫外線硬化型コーティング用組成物。 (B) The alkoxysilane hydrolysis condensate is an alkoxysilane hydrolysis condensate represented by the following formula (1):
R 1 a R 2 b Si (R 3 ) 4-ab (1)
(In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, and R 2 represents an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, a (meth) acryloyl group, a vinyl group, and styryl. Represents an organic functional group containing one or more groups selected from the group consisting of a group, a mercapto group, an amino group, a ureido group and a cyano group, and R 3 represents an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group, an acyloxy group or an alkoxy group Represents an alkoxy group, a and b are each an integer of 0, 1 or 2; a + b is an integer of 0, 1 or 2)
At least a part of them is selected from the group consisting of b in formula (1) being 1 or 2 and R 2 being a (meth) acryloyl group, a vinyl group, a styryl group, an epoxy group and a mercapto group. The ultraviolet curable coating composition according to claim 1, which is a specific organic functional group containing any group.
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Cited By (8)
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| WO2008126902A1 (en) * | 2007-04-11 | 2008-10-23 | Mitsubishi Rayon Co., Ltd. | Composition, method for forming protective coating film, laminate and method for producing the same |
| JP2009102628A (en) * | 2007-10-01 | 2009-05-14 | Atomix Co Ltd | UV-curable coating composition, method for producing the same, and resin-coated article coated therewith |
| WO2010061744A1 (en) | 2008-11-27 | 2010-06-03 | 東レ株式会社 | Siloxane resin composition and protective film for touch panel using same |
| WO2013031985A1 (en) | 2011-08-31 | 2013-03-07 | 旭化成イーマテリアルズ株式会社 | Photosensitive alkali-soluble silicone resin composition |
| JP2015078340A (en) * | 2013-09-10 | 2015-04-23 | 昭和電工株式会社 | Organic-inorganic composite production method, curable composition, curable composition cured product, hard coat material, hard coat film, and silane coupling agent |
| EP3135739A1 (en) * | 2015-08-31 | 2017-03-01 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
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| US10522771B2 (en) | 2014-12-01 | 2019-12-31 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
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| JP2000109694A (en) * | 1998-08-04 | 2000-04-18 | Jsr Corp | Photocurable resin composition and cured film |
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| JPH0593170A (en) * | 1991-10-02 | 1993-04-16 | Mitsubishi Rayon Co Ltd | Coating composition and surface modification of synthetic resin molding |
| JPH07304954A (en) * | 1994-03-16 | 1995-11-21 | Asahi Chem Ind Co Ltd | Water-base cross-linkable resin composition |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008126902A1 (en) * | 2007-04-11 | 2008-10-23 | Mitsubishi Rayon Co., Ltd. | Composition, method for forming protective coating film, laminate and method for producing the same |
| JP2009102628A (en) * | 2007-10-01 | 2009-05-14 | Atomix Co Ltd | UV-curable coating composition, method for producing the same, and resin-coated article coated therewith |
| WO2010061744A1 (en) | 2008-11-27 | 2010-06-03 | 東レ株式会社 | Siloxane resin composition and protective film for touch panel using same |
| US8492450B2 (en) | 2008-11-27 | 2013-07-23 | Toray Industries, Inc. | Siloxane resin composition and protective film for touch panel using the same |
| WO2013031985A1 (en) | 2011-08-31 | 2013-03-07 | 旭化成イーマテリアルズ株式会社 | Photosensitive alkali-soluble silicone resin composition |
| EP2805999A1 (en) | 2011-08-31 | 2014-11-26 | Asahi Kasei E-materials Corporation | Photosensitive Alkali-Soluble Silicone Resin Composition |
| JP2015078340A (en) * | 2013-09-10 | 2015-04-23 | 昭和電工株式会社 | Organic-inorganic composite production method, curable composition, curable composition cured product, hard coat material, hard coat film, and silane coupling agent |
| US10522771B2 (en) | 2014-12-01 | 2019-12-31 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
| US10879475B2 (en) | 2014-12-01 | 2020-12-29 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
| US10358578B2 (en) | 2015-05-29 | 2019-07-23 | Samsung Electronics Co., Ltd. | Insulating ink and insulator and thin film transistor and electronic device |
| EP3135739A1 (en) * | 2015-08-31 | 2017-03-01 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
| US9988472B2 (en) | 2015-08-31 | 2018-06-05 | Samsung Electronics Co., Ltd. | Composition, electronic device, and thin film transistor |
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