JP6179150B2 - Active energy ray-curable composition and cured product - Google Patents
Active energy ray-curable composition and cured product Download PDFInfo
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- JP6179150B2 JP6179150B2 JP2013058134A JP2013058134A JP6179150B2 JP 6179150 B2 JP6179150 B2 JP 6179150B2 JP 2013058134 A JP2013058134 A JP 2013058134A JP 2013058134 A JP2013058134 A JP 2013058134A JP 6179150 B2 JP6179150 B2 JP 6179150B2
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- Prior art keywords
- meth
- acrylate
- active energy
- energy ray
- polyfunctional
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 104
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 62
- 125000004185 ester group Chemical group 0.000 claims description 31
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 12
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 33
- -1 thioxanthone compound Chemical class 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000654 additive Substances 0.000 description 10
- 239000000976 ink Substances 0.000 description 10
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- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 8
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
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- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
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- 239000004925 Acrylic resin Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
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- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Ink Jet (AREA)
Description
本発明は、アクリル基材に対し接着可能な活性エネルギー線硬化性組成物、及び該組成物の硬化物に関する。 The present invention relates to an active energy ray-curable composition that can be adhered to an acrylic substrate, and a cured product of the composition.
従来、重合性化合物を活性エネルギー線で硬化させる活性エネルギー線硬化性樹脂組成物は、無溶剤で塗装や印刷が可能であることから、様々な分野で広く使用されている。例えば塗装分野においては、木工塗料、各種建材、高光沢印刷物、光沢紙、印画紙、ベースコート剤、プラスチック基材用ハードコート剤、光ファイバー用コーティング剤等、印刷分野においては、各種プラスチック製品、紙幣等の平版インキ、グラビアインキ、フレキソインキ、スクリーンインキ、インクジェットインキ、接着用途としては、各種ラミネート、接着フィルム、光学記録ディスク等に用いられている。
また電子工学分野においては、プリント基板、磁気テープ、磁気ディスク、半導体封止材、液晶セル用接着剤等、光成型としては立体模型の成型等に用いられている。
2. Description of the Related Art Conventionally, an active energy ray-curable resin composition that cures a polymerizable compound with an active energy ray is widely used in various fields because it can be applied and printed without a solvent. For example, in the painting field, woodwork paints, various building materials, high-gloss printed matter, glossy paper, photographic paper, base coating agents, hard coating agents for plastic substrates, optical fiber coating agents, etc. In the printing field, various plastic products, banknotes, etc. As lithographic inks, gravure inks, flexographic inks, screen inks, inkjet inks, and adhesive applications, they are used in various laminates, adhesive films, optical recording disks and the like.
Further, in the field of electronics, it is used for molding a three-dimensional model, etc. as optical molding, such as a printed circuit board, a magnetic tape, a magnetic disk, a semiconductor sealing material, an adhesive for liquid crystal cells.
この中で、プラスチック基材用ハードコート剤やプラスチック基材への塗装や印刷は、例えば水性インキや水性塗料では、必要とされる溶媒の基材への染み込みや加熱乾燥が不可能あるいは限界があることから、活性エネルギー線硬化性樹脂組成物の適用が進んでいる。 Among these, coating and printing on hard coating agents for plastic substrates and plastic substrates, for example, with water-based inks and water-based paints, impregnation of the required solvent into the substrate and heat drying are impossible or limited. Therefore, application of an active energy ray-curable resin composition is progressing.
プラスチック基材の中でも、アクリル樹脂を主成分とするアクリル基材は、軽量で且つ耐衝撃性に優れ、さらに透明度も良好であることから、以前よりガラスの代用品として広く使用されている。アクリル基材は特に傷つきやすいため、耐擦傷性を付与する目的でハードコート層を設けたり、ハードコート層を設けたフィルムを貼合したりして用いている。しかしながらアクリル基材は、(メタ)アクリレート等の汎用の材料を主成分とする活性エネルギー線硬化型樹脂組成物が、密着しない場合があった。 Among plastic substrates, acrylic substrates mainly composed of acrylic resins are widely used as glass substitutes because they are lightweight, have excellent impact resistance, and have good transparency. Since the acrylic base material is particularly easily damaged, a hard coat layer is provided for the purpose of imparting scratch resistance, or a film provided with a hard coat layer is bonded. However, the active energy ray-curable resin composition mainly composed of a general-purpose material such as (meth) acrylate may not adhere to the acrylic base material.
プラスチック基材への密着性を改良する手段として、特許文献1では、使用する重合性化合物として300以下のアクリル当量を有し、且つ一分子中にエチレン性二重結合を1個有する単官能モノマーと、150以下のアクリル当量を有し、且つ一分子中にエチレン性二重結合を2個以上有する多官能モノマーとのみからなり、光重合開始剤は、α−アミノアルキルフェノン系化合物及びチオキサントン系化合物を含有するインク組成物が開示されている。
しかしながら該インク組成物は、ポリ塩化ビニルやポリエチレンテレフタレート(PET)を主成分とする基材に対する密着性は評価されているものの、アクリル基材に対しての密着性については、なんら述べられていない。
As a means for improving adhesion to a plastic substrate, Patent Document 1 discloses that a monofunctional monomer having an acrylic equivalent of 300 or less as a polymerizable compound and one ethylenic double bond in one molecule. And a polyfunctional monomer having an acrylic equivalent of 150 or less and having two or more ethylenic double bonds in one molecule, the photopolymerization initiator is an α-aminoalkylphenone compound and a thioxanthone compound. Ink compositions containing the compounds are disclosed.
However, although the ink composition has been evaluated for adhesion to a substrate mainly composed of polyvinyl chloride or polyethylene terephthalate (PET), there is no mention of adhesion to an acrylic substrate. .
本発明の課題は、アクリル基材に対し良好に接着可能な活性エネルギー線硬化性組成物を提供することにある。 The subject of this invention is providing the active energy ray-curable composition which can adhere | attach favorably with respect to an acrylic base material.
本発明者らは、アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを全活性エネルギー線重合性化合物に対し85mol%以上含有し、且つ、該組成物全量に対するエステル基濃度が少なくとも7.4 mmol/gである活性エネルギー線硬化性組成物を使用することで、上記課題を解決した。 The inventors include a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145 in an amount of 85 mol% or more based on the total active energy ray polymerizable compound, and based on the total amount of the composition. The said subject was solved by using the active energy ray-curable composition whose ester group density | concentration is at least 7.4 mmol / g.
即ち本発明は、活性エネルギー線重合性化合物及び光重合開始剤を含有し、前記活性エネルギー線重合性化合物として、アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを全活性エネルギー線重合性化合物に対し85mol%以上含有し、且つ、前記活性エネルギー線重合性化合物全量に対するエステル基濃度が少なくとも7.4mmol/gである活性エネルギー線硬化性組成物を提供する。 That is, the present invention contains an active energy ray polymerizable compound and a photopolymerization initiator, and the polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145 as the active energy ray polymerizable compound. Is provided at 85 mol% or more based on the total active energy ray polymerizable compound, and the active energy ray curable composition has an ester group concentration of at least 7.4 mmol / g with respect to the total amount of the active energy ray polymerizable compound.
本発明により、アクリル基材に対し良好に接着可能な活性エネルギー線硬化性組成物を提供することができる。 ADVANTAGE OF THE INVENTION By this invention, the active energy ray curable composition which can adhere | attach favorably with respect to an acrylic base material can be provided.
(活性エネルギー線重合性化合物)
本発明で使用する活性エネルギー線硬化性化合物は、アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを必須とする。
本発明において、アクリル当量は、以下の式で求められる。
(Active energy ray polymerizable compound)
The active energy ray-curable compound used in the present invention essentially includes a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145.
In the present invention, the acrylic equivalent is determined by the following formula.
すなわち、アクリル当量の低い多官能(メタ)アクリレートは、分子内に占める二重結合の割合が大きい。多官能(メタ)アクリレートは二重結合にエステル基を具えているため、アクリル当量の低い多官能(メタ)アクリレートは、分子内におけるエステル基の割合が高い。 That is, the polyfunctional (meth) acrylate having a low acrylic equivalent has a large proportion of double bonds in the molecule. Since the polyfunctional (meth) acrylate has an ester group in the double bond, the polyfunctional (meth) acrylate having a low acrylic equivalent has a high ratio of the ester group in the molecule.
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとは、具体的には、エチレングリコールジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,5−ペンタンジオールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、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、トリエチレングリコールジ(メタ)アクリレート、シクロヘキサンジメタノールジ(メタ)アクリレート、ジプロピレングリコールジ(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、ペンタエリスリトールトリ(メタ)アクリレート、エチレンオキサイド付加トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、エチレンオキサイド付加ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、1,10−デカンジオールジアクリレート、1,8−オクタンジオールジ(メタ)アクリレート、1,9−ノナンジオールジアクリレート、3−メチル−1,5−ペンタンジオールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリス(2−ヒドロキシエチル)イソシアヌレートトリアクリレート、プロピレンオキサイド付加グリセリルトリアクリレート等が挙げられる。 Specific examples of the polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145 include ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tylene oxide-added trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 1,10-decanediol diacrylate, 1 , 8-octanediol di (meth) acrylate, 1,9-nonanediol diacrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) ) Acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, propylene oxide-added glyceryl triacrylate, etc. That.
本発明において、前記アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートは、全活性エネルギー線重合性化合物に対し85mol%以上含有する。mol%とは、具体的には、(アクリレートモノマーのモル数/全活性エネルギー線重合性化合物の総モル数)×100の計算方法で示される。また、モル数とは、(アクリレートモノマーの配合量[g]/アクリレートモノマーの分子量[g/mol])の計算方法で示される。
本発明においては、なかでも90mol%以上が好ましい。
In this invention, the polyfunctional (meth) acrylate which has the (meth) acryloyl group whose said acrylic equivalent is 78-145 contains 85 mol% or more with respect to all the active energy ray polymeric compounds. Specifically, the mol% is represented by a calculation method of (number of moles of acrylate monomer / total number of moles of all active energy ray polymerizable compounds) × 100. The number of moles is indicated by a calculation method of (blending amount of acrylate monomer [g] / molecular weight of acrylate monomer [g / mol]).
In the present invention, 90 mol% or more is particularly preferable.
前記アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレート以外の、活性エネルギー線硬化性化合物は、特に限定はなく公知のものを使用することができる。
例えば、単官能(メタ)アクリレートとしては、メチル、エチル、プロピル、ブチル、アミル、2−エチルヘキシル、オクチル、ノニル、デシル、ラウリル、ヘキサデシル、ステアリル、シクロヘキシル、ベンジル、メトキシエチル、ブトキシエチル、フェノキシエチル、ノニルフェノキシエチル、グリシジル、ジメチルアミノエチル、ジエチルアミノエチル、イソボルニル、ジシクロペンタニル、ジシクロペンテニル、ジシクロペンテニロキシエチル、テトラヒドロフルフリル、エトキシル化テロラヒドロフランなどの置換基を有する(メタ)アクリレート類が挙げられる。多官能(メタ)アクリレートとしては、トリシクロデカンジメタノール、ポリエチレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のジ(メタ)アクリレート、ネオペンチルグリコール1モルに4モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ(メタ)アクリレート、ビスフェノールA1モルに2モルのエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ(メタ)アクリレート、トリメチロールプロパン1モルに3モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジまたはトリ(メタ)アクリレート、ビスフェノールA1モルに4モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ(メタ)アクリレート、ジペンタエリスリトールのポリ(メタ)アクリレート、エチレンオキサイド変性リン酸(メタ)アクリレート、エチレンオキサイド変性アルキルリン酸(メタ)アクリレート等が挙げられる。
また、例えば、ビニルエーテル化合物としては、アクリル酸2−(2−ビニロキシエトキシ)エチル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物の、ビニルエーテル基を有する重合性化合物等が挙げられる。
The active energy ray-curable compound other than the polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145 is not particularly limited, and known compounds can be used.
For example, monofunctional (meth) acrylates include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, decyl, lauryl, hexadecyl, stearyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, (Meth) acrylates having substituents such as nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl, tetrahydrofurfuryl, ethoxylated terahydrofuran Kind. As the polyfunctional (meth) acrylate, di (meth) acrylate such as tricyclodecane dimethanol, polyethylene glycol, tripropylene glycol and polypropylene glycol, and 4 mol or more of ethylene oxide or propylene oxide are added to 1 mol of neopentyl glycol. Di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, 3 mol or more of ethylene oxide in 1 mol of trimethylolpropane or Diol or tri (meth) acrylate of triol obtained by adding propylene oxide, 4 mol or more of ethylene oxide or propylene oxide is added to 1 mol of bisphenol A Which was obtained diol di (meth) acrylate, dipentaerythritol poly (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkyl phosphoric acid (meth) acrylate.
Examples of vinyl ether compounds include 2- (2-vinyloxyethoxy) ethyl acrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and butanediol. Examples thereof include polymerizable compounds having a vinyl ether group of di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, and trimethylolpropane trivinyl ether.
また、(メタ)アクリレートオリゴマー等の重合性オリゴマーを使用することもできる。重合性オリゴマーとしては、ポリウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリアクリル(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリアルキレングリコールポリ(メタ)アクリレート、ポリエーテル(メタ)アクリレート等が挙げられ、2種類以上併用して用いることができる。 Moreover, polymerizable oligomers, such as a (meth) acrylate oligomer, can also be used. Examples of the polymerizable oligomer include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether (meth) acrylate. Two or more types can be used in combination.
また、本発明においては、該組成物全量に対するエステル基濃度が7.4mmol/g以上であることが特徴である。エステル基濃度[mmol/g]は下記の式で表される。 Moreover, in this invention, it is the characteristics that the ester group density | concentration with respect to this composition whole quantity is 7.4 mmol / g or more. The ester group concentration [mmol / g] is represented by the following formula.
ここでエステル基は、前記(メタ)アクリレート由来のエステル基の他、(メタ)アクリレート由来ではない分子内のエステル基も含まれる。
また、分子内エステル基当量とは、下記の式で表される。
Here, the ester group includes, in addition to the ester group derived from the (meth) acrylate, an intramolecular ester group not derived from (meth) acrylate.
The intramolecular ester group equivalent is represented by the following formula.
活性エネルギー線重合性化合物がアクリレート由来のエステル基以外を持たない場合、前記エステル基濃度は、 When the active energy ray-polymerizable compound has no ester group derived from acrylate, the ester group concentration is
と書き換えることができる。
本発明におけるエステル基濃度は、なかでも8.0mmol/g以上11mmol/g以下が好ましく、9.0mmol/g以上10.0mmol/g以下がなお好ましい。
Can be rewritten.
The ester group concentration in the present invention is preferably 8.0 mmol / g or more and 11 mmol / g or less, and more preferably 9.0 mmol / g or more and 10.0 mmol / g or less.
このように、本発明においては、アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを、全活性エネルギー線重合性化合物に対し85mol%以上含有する。このようなエステル基の濃度が大きいアクリレートモノマーを用いることで、硬化後の塗膜中にはエステル基が多く存在することになる。
本発明の課題はアクリル基材に対し接着可能な、活性エネルギー線硬化性組成物を提供することにある。アクリル基材として汎用されるポリメチルメタクリレート(通常PMMAと称される)の主原料はメチルメタクリレートであるが、メチルメタクリレートアクリル当量は100、エステル基濃度は10mmol/gと高い。従って、エステル基濃度をアクリル基材のエステル基濃度に近い7.4mmol/g以上とした本発明の活性エネルギー線硬化性組成物は、アクリル基材と、エステル基の分子間相互作用によって密着性が向上し、良好な密着性を示すものと考えられる。
Thus, in this invention, the polyfunctional (meth) acrylate which has a (meth) acryloyl group whose acrylic equivalent is 78-145 is contained 85 mol% or more with respect to all the active energy ray polymeric compounds. By using such an acrylate monomer having a high concentration of ester groups, many ester groups exist in the cured coating film.
The subject of this invention is providing the active energy ray-curable composition which can be adhere | attached with respect to an acrylic base material. The main raw material of polymethyl methacrylate (usually referred to as PMMA) widely used as an acrylic substrate is methyl methacrylate, but the methyl methacrylate acrylic equivalent is 100 and the ester group concentration is as high as 10 mmol / g. Therefore, the active energy ray-curable composition of the present invention in which the ester group concentration is 7.4 mmol / g or more, which is close to the ester group concentration of the acrylic substrate, has an adhesive property due to the intermolecular interaction between the acrylic substrate and the ester group. Is considered to improve and show good adhesion.
更に本発明においては、アクリル当量が低い多官能(メタ)アクリレートを使用しているため、架橋密度が高くなり、塗膜の硬度や耐溶剤性を発現させることができる。 Furthermore, in this invention, since the polyfunctional (meth) acrylate with a low acrylic equivalent is used, a crosslinking density becomes high and the hardness of a coating film and solvent resistance can be expressed.
一方、その他の活性エネルギー線重合性化合物としてアクリル当量の低い単官能アクリレートモノマーを使用した場合、7.4mmol/g以上のエステル基濃度となるが、得られた塗膜の密着性は低下する。これは、架橋密度が下がり、架橋部分のエステル基密集による分子間相互作用の力が弱まるためと推定される。 On the other hand, when a monofunctional acrylate monomer having a low acrylic equivalent is used as the other active energy ray polymerizable compound, the concentration of the ester group is 7.4 mmol / g or more, but the adhesion of the obtained coating film is lowered. This is presumed to be because the cross-linking density decreases and the force of intermolecular interaction due to the ester group crowding in the cross-linked portion weakens.
(光重合開始剤)
本発明においては、前記特定の活性エネルギー線重合性化合物を使用する以外は特に限定なく公知の材料を使用することができる。例えば光重合開始剤は、公知のラジカル性光重合開始剤を使用することができる。具体的には、ベンゾフェノン、3,3′−ジメチル−4−メトキシベンゾフェノン、4,4′−ビスジメチルアミノベンゾフェノン、4,4′−ビスジエチルアミノベンゾフェノン、4,4′−ジクロロベンゾフェノン、ミヒラーズケトン、3,3′,4,4′-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノンなどのベンゾフェノン;キサントン、チオキサントン、2−メチルチオキサントン、2−クロロチオキサントン、2,4−ジエチルチオキサントンなどのキサントン、チオキサントン;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのアシロインエーテル;ベンジル、ジアセチルなどのα-ジケトン;テトラメチルチウラムジスルフィド、p−トリルジスルフィドなどのスルフィド;4−ジメチルアミノ安息香酸、4−ジメチルアミノ安息香酸エチルなどの安息香酸;3,3′-カルボニル-ビス(7-ジエチルアミノ)クマリン、1−ヒドロキシシクロへキシルフェニルケトン、2,2′−ジメトキシ−1,2−ジフェニルエタン−1−オン、2−メチル−1−〔4−(メチルチオ)フェニル〕−2−モルフオリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタン−1−オン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキシド、ビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキシド、1−〔4−(2−ヒドロキシエトキシ)フェニル〕−2−ヒドロキシ−2−メチル−1−プロパン−1−オン、1−(4−イソプロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、1−(4−ドデシルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、4−ベンゾイル−4′−メチルジメチルスルフィド、2,2′−ジエトキシアセトフェノン、ベンジルジメチルケタ−ル、ベンジル−β−メトキシエチルアセタール、o−ベンゾイル安息香酸メチル、ビス(4−ジメチルアミノフェニル)ケトン、p−ジメチルアミノアセトフェノン、α,α−ジクロロ−4−フェノキシアセトフェノン、ペンチル−4−ジメチルアミノベンゾエート、2−(o−クロロフェニル)−4,5−ジフェニルイミダゾリルニ量体、2,4−ビス−トリクロロメチル−6−[ジ−(エトキシカルボニルメチル)アミノ]フェニル−S−トリアジン、2,4−ビス−トリクロロメチル−6−(4−エトキシ)フェニル−S−トリアジン、2,4−ビス−トリクロロメチル−6−(3−ブロモ−4−エトキシ)フェニル−S−トリアジンアントラキノン、2−t−ブチルアントラキノン、2−アミルアントラキノン、β−クロルアントラキノン等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。
(Photopolymerization initiator)
In the present invention, known materials can be used without particular limitation, except that the specific active energy ray polymerizable compound is used. For example, a known radical photopolymerization initiator can be used as the photopolymerization initiator. Specifically, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, Michler's ketone, 3, Benzophenone such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; xanthone such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, thioxanthone; benzoin, Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; α-diketones such as benzyl and diacetyl; tetramethylthiuram disulfide, p-tolyl disulfi Sulfides such as; 4-benzoic acid such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate; 3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2 '-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4 , 6-Trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydride Roxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolylni 2,4-bis-trichloromethyl-6- [di- (ethoxycal Nylmethyl) amino] phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- Ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone and the like. These may be used alone or in combination of two or more.
また上記光重合開始剤に対し、増感剤として例えば、トリメチルアミン、メチルジメタノールアミン、トリエタノールアミン、p−ジエチルアミノアセトフェノン、p−ジメチルアミノ安息香酸エチル、p−ジメチルアミノ安息香酸イソアミル、N,N−ジメチルベンジルアミンおよび4,4’−ビス(ジエチルアミノ)ベンゾフェノン等の、前述重合性成分と付加反応を起こさないアミン類を併用することもできる。 For the above photopolymerization initiator, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N An amine that does not cause an addition reaction with the polymerizable component, such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone, can also be used in combination.
前記光重合開始剤と増感剤は、前記活性エネルギー線硬化性組成物に対し、通常使用する範囲、例えば0.1〜20質量%の範囲で添加して使用することができる。 The photopolymerization initiator and the sensitizer can be used by adding to the active energy ray-curable composition in a range usually used, for example, in a range of 0.1 to 20% by mass.
(その他の成分)
本発明においては、本発明の効果を損なわない範囲において、その他目的に応じて適宜、添加剤を加えてもよい。例えば本発明の活性エネルギー線硬化性組成物をコーティング剤として使用する場合は、紫外線吸収剤、酸化防止剤、シリコン系添加剤、フッ素系添加剤、帯電防止剤等の添加剤を添加することができる。
(Other ingredients)
In the present invention, additives may be appropriately added according to other purposes within a range not impairing the effects of the present invention. For example, when the active energy ray-curable composition of the present invention is used as a coating agent, additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, and an antistatic agent may be added. it can.
前記紫外線吸収剤は、例えば、2−[4−{(2−ヒドロキシ−3−ドデシルオキシプロピル)オキシ}−2−ヒドロキシフェニル]−4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン、2−[4−{(2−ヒドロキシ−3−トリデシルオキシプロピル)オキシ}−2−ヒドロキシフェニル]−4,6−ビス(2,4−ジメチルフェニル)−1,3,5−トリアジン等のトリアジン誘導体、2−(2′−キサンテンカルボキシ−5′−メチルフェニル)ベンゾトリアゾール、2−(2′−o−ニトロベンジロキシ−5′−メチルフェニル)ベンゾトリアゾール、2−キサンテンカルボキシ−4−ドデシロキシベンゾフェノン、2−o−ニトロベンジロキシ−4−ドデシロキシベンゾフェノン等が挙げられる。 Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 2,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.
前記酸化防止剤は、例えば、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、有機硫黄系酸化防止剤、リン酸エステル系酸化防止剤等が挙げられる。
前記シリコン系添加剤は、例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、環状ジメチルポリシロキサン、メチルハイドロゲンポリシロキサン、ポリエーテル変性ジメチルポリシロキサン共重合体、ポリエステル変性ジメチルポリシロキサン共重合体、フッ素変性ジメチルポリシロキサン共重合体、アミノ変性ジメチルポリシロキサン共重合体など如きアルキル基やフェニル基を有するポリオルガノシロキサン類が挙げられる。
Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.
Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples thereof include polyorganosiloxanes having an alkyl group and a phenyl group, such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.
前記フッ素系添加剤は、例えば、DIC株式会社製「メガファック」シリーズ等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the fluorine-based additive include “Megafac” series manufactured by DIC Corporation. These may be used alone or in combination of two or more.
前記帯電防止剤は、例えば、ビス(トリフルオロメタンスルホニル)イミド又はビス(フルオロスルホニル)イミドのピリジニウム、イミダゾリウム、ホスホニウム、アンモニウム又はリチウム塩等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the antistatic agent include bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide pyridinium, imidazolium, phosphonium, ammonium, or lithium salt. These may be used alone or in combination of two or more.
前記種々の添加剤は、その効果を十分発揮し、また紫外線硬化を阻害しない範囲で用いることが好ましく、具体的には、本発明の活性エネルギー線硬化型樹脂組成物100質量部中、0.01〜10質量部の範囲で用いることが好ましい。 The various additives are preferably used within the range where the effects are sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in 100 parts by mass of the active energy ray-curable resin composition of the present invention, 0. It is preferable to use in the range of 01-10 mass parts.
また、活性エネルギー線硬化性組成物をインクジェット記録用クリアインクとして使用する場合は、重合禁止剤等の添加剤を添加することができる。
前記重合禁止剤としては、例えば、ハイドロキノン、メトキノン、ジ−t−ブチルハイドロキノン、P−メトキシフェノール、ブチルヒドロキシトルエン、ニトロソアミン塩等が挙げられる。
Moreover, when using an active energy ray curable composition as a clear ink for inkjet recording, additives, such as a polymerization inhibitor, can be added.
Examples of the polymerization inhibitor include hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salts and the like.
(その他の添加剤)
その他、本発明の効果を損なわない範囲で、汎用の有機溶剤、界面活性剤、レベリング添加剤、マット剤、皮膜形成性樹脂としてポリエステル系樹脂、ポリウレタン系樹脂、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類を添加することが出来る。
(Other additives)
In addition, as long as the effects of the present invention are not impaired, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber as general-purpose organic solvents, surfactants, leveling additives, matting agents, and film-forming resins Series resins and waxes can be added.
(硬化方法)
本発明の活性エネルギー線硬化性組成物は、活性エネルギー線、好ましくは紫外線等の光照射をすることにより硬化反応を行う。紫外線等の光源としては、例えばメタルハライドランプ、キセノンランプ、カーボンアーク灯、ケミカルランプ、低圧水銀ランプ、高圧水銀ランプ等であれば問題なく硬化させることができる。例えばFusion System社製のHランプ、Dランプ、Vランプ等の市販されているものを用いて行うことができる。
(Curing method)
The active energy ray-curable composition of the present invention undergoes a curing reaction by irradiation with active energy rays, preferably light such as ultraviolet rays. For example, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low-pressure mercury lamp, or a high-pressure mercury lamp can be cured without any problem as a light source such as ultraviolet rays. For example, a commercially available product such as an H lamp, D lamp, or V lamp manufactured by Fusion System can be used.
(基材)
本発明の活性エネルギー線硬化性組成物は、特にアクリル基材に対し密着性に優れる。アクリル基材の主成分であるアクリル樹脂は、アクリル系、メタアクリル系のモノマーに代表されるような、炭素−炭素二重結合を持つ重合性モノマーからなる重合体である。これらは、単独重合体あるいは共重合体いずれでも差し支えない。また、それら重合体と他のポリマー(例えばポリエステル、ポリウレタン等)との共重合体であってもよい。
(Base material)
The active energy ray-curable composition of the present invention is particularly excellent in adhesion to an acrylic substrate. The acrylic resin that is the main component of the acrylic substrate is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) may be sufficient.
上記炭素−炭素二重結合を持つ重合性モノマーとしては、特に限定はしないが、特に代表的な化合物としては、例えば、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、フマル酸、マレイン酸、シトラコン酸のような各種カルボキシル基含有モノマー類、およびそれらの塩;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、4−ヒドロキシブチル(メタ)アクリレート、モノブチルヒドロキルフマレート、モノブチルヒドロキシイタコネートのような各種の水酸基含有モノマー類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ラウリル(メタ)アクリレートのような各種の(メタ)アクリル酸エステル類;(メタ)アクリルアミド、ジアセトンアクリルアミド、N−メチロールアクリルアミドまたは(メタ)アクリロニトリル等のような種々の窒素含有化合物;スチレン、α−メチルスチレン、ジビニルベンゼン、ビニルトルエンのような各種スチレン誘導体、プロピオン酸ビニルのような各種のビニルエステル類;γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン等のような種々の珪素含有重合性モノマー類;燐含有ビニル系モノマー類;塩化ビニル、塩化ビリデンのような各種のハロゲン化ビニル類;ブタジエンのような各種共役ジエン類が挙げられる。
これらの樹脂からなるアクリル基材は、製法により押出し板とキャスト板とがあるが、本発明においては、インクによる溶解性の高い押出し板がより好ましい。
The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citracone. Various carboxyl group-containing monomers such as acids, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, Various hydroxyl group-containing monomers such as monobutylhydroxy itaconate; various monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) acrylic acid esters; Various nitrogen-containing compounds such as meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate Various vinyl esters such as: Various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; Phosphorus-containing vinyl monomers; Various such as vinyl chloride and biridene chloride And various conjugated dienes such as butadiene.
The acrylic base material made of these resins includes an extruded plate and a cast plate depending on the production method. In the present invention, an extruded plate having high solubility by ink is more preferable.
以下、実施例により、本発明をさらに詳しく説明するが、本発明は下記実施例に何ら制限されるものではない。なお、以下実施例中にある部、%は質量換算である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to the following Example at all. In the following examples, “part” and “%” are based on mass.
(実施例1)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして、「TMPTA(トリメチロールプロパントリアクリレート)」を83.3部、その他のアクリレートモノマーとして「THFA(テトラヒドロフルフリルアクリレート)」を9.3部、光重合開始剤として「D1173(2-ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン)」を4.6部、「ルシリンTPO(ジフェニル−2,4,6−トリメチルベンゾイルフォスフィンオキサイド)」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させて、活性エネルギー線硬化性組成物(1)を得た。
Example 1
As a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 83.3 parts of “TMPTA (trimethylolpropane triacrylate)” and “THFA (tetrahydrofurfuryl) as another acrylate monomer are used. Acrylate) ”, 9.3 parts“ D1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) ”as a photopolymerization initiator, and“ lucillin TPO (diphenyl-2,4) , 6-trimethylbenzoylphosphine oxide) ”is mixed with 2.8 parts and stirred for 30 minutes or more while heating to 60 ° C. to completely dissolve the photopolymerization initiator, and the active energy ray-curable composition ( 1) was obtained.
(実施例2)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPGDA(ジプロピレングリコールジアクリレート)」を75.0部、その他のアクリレートモノマーとして「PO2NPGDA(プロピレンオキサイド2mol変性ネオペンチルグリコールジアクリレート)」を17.6部、光重合開始剤として「D1173」を4.6部、「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させて、活性エネルギー線硬化性組成物(2)を得た。
(Example 2)
75.0 parts of “DPGDA (dipropylene glycol diacrylate)” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, and “PO2NPGDA (propylene oxide 2 mol modified) as another acrylate monomer 17.6 parts of “Neopentyl glycol diacrylate”, 4.6 parts of “D1173” as a photopolymerization initiator, and 2.8 parts of “Lucirin TPO” are mixed and stirred for 30 minutes or more while heating to 60 ° C. Then, the photopolymerization initiator was completely dissolved to obtain an active energy ray-curable composition (2).
(実施例3)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPGDA」83.3部、その他のアクリレートモノマーとして「PO2NPGDA」を9.3部、光重合開始剤として「D1173」4.6部、「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させて、活性エネルギー線硬化性組成物(3)を得た。
(Example 3)
83.3 parts of “DPGDA” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 9.3 parts of “PO2NPGDA” as the other acrylate monomer, and “ 4.6 parts of D1173 "and 2.8 parts of" Lucirin TPO "are mixed and stirred for 30 minutes or more while heating to 60 ° C to completely dissolve the photopolymerization initiator. (3) was obtained.
(実施例4)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「TMPTA」46.3部、「DPGDA」37.0部、その他のアクリレートモノマーとして「THFA」:4.6部、「PEA(フェノキシエチルアクリレート)」4.6部、光重合開始剤として「D1173」4.6部と「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(4)を得た。
Example 4
46.3 parts of “TMPTA”, 37.0 parts of “DPGDA” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, “THFA” as another acrylate monomer: 4.6 , 4.6 parts of “PEA (phenoxyethyl acrylate)”, 4.6 parts of “D1173” as photopolymerization initiator and 2.8 parts of “Lucirin TPO” are mixed and heated to 60 ° C. for 30 minutes or more. The mixture was stirred to completely dissolve the photopolymerization initiator to obtain an active energy ray-curable composition (4).
(比較例1)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPGDA」59.3部、その他のアクリレートモノマーとして「EO10BP−DA(エチレンオキサイド10mol変性ビスフェノールAジアクリレート)」33.3部、光重合開始剤として「D1173」4.6部と「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(H1)を得た。
(Comparative Example 1)
59.3 parts of “DPGDA” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, and “EO10BP-DA (ethylene oxide 10 mol modified bisphenol A diacrylate)” as the other acrylate monomer 33.3 parts, 4.6 parts of “D1173” as a photopolymerization initiator and 2.8 parts of “Lucirin TPO” are mixed and stirred for 30 minutes or more while heating to 60 ° C. to completely remove the photopolymerization initiator. The active energy ray-curable composition (H1) was obtained by dissolution.
(比較例2)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「TMPTA」56.5部、「HDDA(ヘキサンジオールジアクリレート)」を22.2部、その他のアクリレートモノマーとして「IOA(イソオクチルアクリレート)」13.9部、「光重合開始剤」として「Irg.907(2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン)」4.6部、「CHEMCURE JETX(ジエチルチオキサントン)」2.8部を混合し、これらを60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(H2)を得た。
(Comparative Example 2)
As a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 56.5 parts of “TMPTA”, 22.2 parts of “HDDA (hexanediol diacrylate)”, and other acrylate monomers 13.9 parts of “IOA (isooctyl acrylate)”, “Irg.907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) as“ photopolymerization initiator ” "4.6 parts" and "CHEMCURE JETX (diethylthioxanthone)" 2.8 parts are mixed and stirred for 30 minutes or more while heating to 60 ° C to completely dissolve the photopolymerization initiator, and active energy rays A curable composition (H2) was obtained.
(比較例3)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPHA(ジペンタエリスリトールヘキサアクリレート)」63.0部、その他のアクリレートモノマーとして「PO2NPGDA」29.6部、光重合開始剤として「D1173」2.1部、「ルシリンTPO」1.3部、「Irg.907」2.5部、「CHEMCURE JETX」1.5部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(H3)を得た。
(Comparative Example 3)
63.0 parts of “DPHA (dipentaerythritol hexaacrylate)” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 29.6 parts of “PO2NPGDA” as another acrylate monomer, As a photopolymerization initiator, 2.1 parts of “D1173”, 1.3 parts of “Lucirin TPO”, 2.5 parts of “Irg.907” and 1.5 parts of “CHEMCURE JETX” were mixed and heated to 60 ° C. While stirring for 30 minutes or longer, the photopolymerization initiator was completely dissolved to obtain an active energy ray-curable composition (H3).
(比較例4)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを含まず、その他のアクリレートモノマーとして「PO2NPGDA」83.8部、「PEA」8.8部、光重合開始剤として「D1173」4.6部、「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成(H4)を得た。
(Comparative Example 4)
It does not contain a polyfunctional (meth) acrylate having a (meth) acryloyl group with an acrylic equivalent of 78 to 145, and as other acrylate monomers, “PO2NPGDA” 83.8 parts, “PEA” 8.8 parts, photopolymerization initiator As a mixture, 4.6 parts of “D1173” and 2.8 parts of “Lucirin TPO” were stirred for 30 minutes or more while heating to 60 ° C. to completely dissolve the photopolymerization initiator, and the active energy ray-curable composition (H4) was obtained.
(比較例5)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPGDA」64.8部、その他のアクリレートモノマーとして「PEA」27.8部、光重合開始剤として「D1173」4.6部、「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(H5)を得た。
(Comparative Example 5)
64.8 parts of “DPGDA” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 27.8 parts of “PEA” as another acrylate monomer, and “D1173 as a photopolymerization initiator” "4.6 parts" and "2.8 parts of" Lucirin TPO "are mixed and stirred for 30 minutes or longer while heating to 60 ° C to completely dissolve the photopolymerization initiator, and the active energy ray-curable composition (H5 )
(比較例6)
アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートとして「DPGDA」37.0部、その他のアクリレートモノマーとして「PEA」55.6部、光重合開始剤として「D1173」4.6部、「ルシリンTPO」2.8部を混合し、60℃に加温しながら30分以上攪拌し、光重合開始剤を完全に溶解させ、活性エネルギー線硬化性組成物(H6)を得た。
(Comparative Example 6)
37.0 parts of “DPGDA” as a polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145, 55.6 parts of “PEA” as another acrylate monomer, and “D1173 as a photopolymerization initiator” "4.6 parts" and "2.8 parts of" Lucirin TPO "are mixed and stirred for 30 minutes or more while heating to 60 ° C to completely dissolve the photopolymerization initiator, and the active energy ray-curable composition (H6 )
以上、実施例及び比較例における組成を表1及び表2に示す。 The compositions in Examples and Comparative Examples are shown in Tables 1 and 2 above.
表1,2中、空欄は「ゼロ」を表す。また記号は以下の通りである。
TMPTA:トリメチロールプロパントリアクリレート
DPGDA:ジプロピレングリコールジアクリレート
HDDA:ヘキサンジオールジアクリレート
DPHA:ジペンタエリスリトールヘキサアクリレート
PO2NPGDA:プロピレンオキサイド2mol変性ネオペンチルグリコールジアクリレート
EO10BP−DA:エチレンオキサイド10mol変性ビスフェノールAジアクリレート
PEA:フェノキシエチルアクリレート
THFA:テトラヒドロフルフリルアクリレート
IOA:イソオクチルアクリレート
D1173:2-ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン
ルシリンTPO:ジフェニル−2,4,6−トリメチルベンゾイルフォスフィンオキサイド
Irg.907:2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン
CHEMCURE JETX:ジエチルチオキサントン
In Tables 1 and 2, a blank represents “zero”. The symbols are as follows.
TMPTA: Trimethylolpropane triacrylate DPGDA: Dipropylene glycol diacrylate HDDA: Hexanediol diacrylate DPHA: Dipentaerythritol hexaacrylate PO2NPGDA: Propylene oxide 2 mol modified neopentyl glycol diacrylate EO10BP-DA: Ethylene oxide 10 mol modified bisphenol A diacrylate PEA: Phenoxyethyl acrylate THFA: Tetrahydrofurfuryl acrylate IOA: Isooctyl acrylate D1173: 2-hydroxy-2-methyl-1-phenylpropane-1-one lucillin TPO: Diphenyl-2,4,6-trimethylbenzoylphosphine oxide Irg . 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one CHEMCURE JETX: diethylthioxanthone
これら実施例及び比較例について、密着性、耐溶剤性、鉛筆硬度についての試験を行った。
<試験塗膜の作製>
アクリル板((株)クラレ製「コモグラスP」)にスピンコーターにて膜厚10ミクロンの膜を塗布し、メタルハライドランプを積算光量が220mJ/平方cmとなるように照射し、試験塗膜を得た。
About these Examples and comparative examples, the test about adhesiveness, solvent resistance, and pencil hardness was done.
<Preparation of test coating film>
A 10 micron film thickness was applied to an acrylic plate ("Komo Glass P" manufactured by Kuraray Co., Ltd.) with a spin coater, and a metal halide lamp was irradiated so that the integrated light intensity was 220 mJ / square cm to obtain a test coating film. It was.
<密着性>
試験塗膜に、5×5の25マス様にカッターナイフで切り込みを入れた後、ニチバン製セロハンテープを貼り付け、10回程爪で擦りつけた。次いで、剥離速度約1cm/secの速度にて勢い良くテープを剥がし、基材に塗膜の残ったマス目の数を確認した。残ったマス目の割合により、10(全て密着し残った)〜1(全て剥がれた)の10段階評価を行った。
<Adhesion>
The test coating was cut into 5 × 5 25 squares with a cutter knife, and then a Nichiban cellophane tape was applied and rubbed with nails about 10 times. Next, the tape was peeled off vigorously at a peeling speed of about 1 cm / sec, and the number of squares with the coating film remaining on the substrate was confirmed. A 10-step evaluation of 10 (all remained adhered) to 1 (all peeled) was performed according to the ratio of the remaining cells.
<耐溶剤性>
試験塗膜を、エタノール(95vol%)を含浸させた綿棒で20往復こすり、表面の状態を目視で確認した。表面の状態により、4(全く変化がない)、3(わずかに跡が確認できる)、2(跡が確認できる)、1(白く残る)の4段階評価を行った。
<Solvent resistance>
The test coating was rubbed 20 times with a cotton swab impregnated with ethanol (95 vol%), and the surface condition was visually confirmed. Depending on the state of the surface, a four-step evaluation was performed: 4 (no change at all), 3 (a trace can be confirmed), 2 (a trace can be confirmed), and 1 (remains white).
<鉛筆硬度>
JIS−K5600−5−4に従い、手かき法にて試験した。試験結果を4段階で示した。
<Pencil hardness>
According to JIS-K5600-5-4, it tested by the handwriting method. The test results are shown in four stages.
実施例及び比較例のmol濃度、エステル基濃度の計算結果と試験結果を表3に示す。 Table 3 shows calculation results and test results of mol concentration and ester group concentration in Examples and Comparative Examples.
空欄は「ゼロ」を表す。
A blank represents “zero”.
実施例1〜4により、アクリル当量が78〜145以下であるアクリレートモノマーが塗膜中に85mol%以上であり、かつ塗膜のエステル基濃度が7.4mmol/g以上となる場合、該アクリル当量が78〜145以下であるアクリレートモノマー以外のアクリレートモノマーが、単官能(実施例1)、多官能(実施例2・3)にかかわらず、あるいは複数のアクリレートモノマーの組み合わせ(実施例4)であっても、良密着性と耐溶剤性・硬度を両立した塗膜を得ることができた。 According to Examples 1 to 4, when the acrylate monomer having an acrylic equivalent of 78 to 145 or less is 85 mol% or more in the coating film and the ester group concentration of the coating film is 7.4 mmol / g or more, the acrylic equivalent An acrylate monomer other than an acrylate monomer having an A of 78 to 145 is monofunctional (Example 1), polyfunctional (Examples 2 and 3), or a combination of a plurality of acrylate monomers (Example 4). However, it was possible to obtain a coating film having both good adhesion, solvent resistance and hardness.
一方、アクリル当量が78〜145以下であるアクリレートモノマーが塗膜中に85mol%以上含まれていても、塗膜のエステル基濃度が7.4mmol/g未満である比較例1は、密着性が悪化した。またエステル基濃度が7.4mmol/g以上であってもアクリル当量が78〜145以下であるアクリレートモノマーが85mol%未満の比較例2や3も、密着性が悪化した。また、多官能であるがアクリル当量が78〜145以下のアクリレートモノマーを使用しない比較例4や、アクリル当量が78〜145以下であるアクリレートモノマーが塗膜中に85mol%未満である比較例5や6は、密着性と耐溶剤性や硬度が低下した。 On the other hand, even if an acrylate monomer having an acrylic equivalent of 78 to 145 or less is contained in the coating film in an amount of 85 mol% or more, the comparative example 1 in which the ester group concentration of the coating film is less than 7.4 mmol / g has an adhesive property. It got worse. Moreover, even if the ester group concentration was 7.4 mmol / g or more, Comparative Examples 2 and 3 in which the acrylate monomer having an acrylic equivalent of 78 to 145 or less was less than 85 mol% also deteriorated the adhesion. Further, Comparative Example 4 which is polyfunctional but does not use an acrylate monomer having an acrylic equivalent of 78 to 145 or less, or Comparative Example 5 in which an acrylate monomer having an acrylic equivalent of 78 to 145 or less is less than 85 mol% in the coating film. In No. 6, adhesion, solvent resistance and hardness decreased.
(アクリル基材に対する密着性)
特に重要な効果であるアクリル基材に対する密着性について、アクリル当量が78〜145の範囲である(メタ)アクリロイル基を有する多官能(メタ)アクリレートと、アクリル当量が78〜145の範囲外である(メタ)アクリロイル基を有する多官能(メタ)アクリレート及び単官能(メタ)アクリレートを使用し、これらから任意に2種を組み合わせて得た組成物を作製し、密着性試験を行った。
(Adhesion to acrylic substrate)
Regarding adhesion to an acrylic substrate, which is a particularly important effect, a polyfunctional (meth) acrylate having a (meth) acryloyl group with an acrylic equivalent of 78 to 145 and an acrylic equivalent outside the range of 78 to 145 A polyfunctional (meth) acrylate having a (meth) acryloyl group and a monofunctional (meth) acrylate were used, and a composition obtained by arbitrarily combining two kinds thereof was prepared, and an adhesion test was performed.
<アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレート>
TMPTA
DPGDA
HDDA
DEGDA(ジエチレングリコールジアクリレート)
<アクリル当量が78〜145の範囲外である(メタ)アクリロイル基を有する多官能(メタ)アクリレート>
PEA
THFA
IOA
IBOA(イソボルニルアクリレート)
HBA(4−ヒドロキシブチルアクリレート)
TPGDA(トリプロピレングリコールジアクリレート)
PEG−DA(ポリエチレングリコールジアクリレート)
HPA(2−ヒドロキシ−3−フェノキシプロピルアクリレート)
EO3BPA−DA(エチレンオキサイド3mol変性ビスフェノールAジアクリレート)
<光重合開始剤>
D1173:4.6部
ルシリンTPO:2.8部
<Polyfunctional (meth) acrylate having (meth) acryloyl group with acrylic equivalent of 78 to 145>
TMPTA
DPGDA
HDDA
DEGDA (diethylene glycol diacrylate)
<Polyfunctional (meth) acrylate having a (meth) acryloyl group whose acrylic equivalent is outside the range of 78 to 145>
PEA
THFA
IOA
IBOA (isobornyl acrylate)
HBA (4-hydroxybutyl acrylate)
TPGDA (Tripropylene glycol diacrylate)
PEG-DA (polyethylene glycol diacrylate)
HPA (2-hydroxy-3-phenoxypropyl acrylate)
EO3BPA-DA (ethylene oxide 3 mol modified bisphenol A diacrylate)
<Photopolymerization initiator>
D1173: 4.6 parts Lucillin TPO: 2.8 parts
結果を図1に示す。図1中、黒の四角で表されるものが、多官能(メタ)アクリレートを85mol%未満で含む組成物の、エステル基濃度と密着性との関係をプロットしたものである。また、図1中、白の四角で表されるものが、多官能(メタ)アクリレートを85mol%以上含む組成物の、エステル基濃度と密着性との関係をプロットしたものである。図1からわかるように、エステル基濃度が7.4mmol/g未満では、密着性が得られないことがわかる。一方、エステル基濃度が7.4mmol/g以上の場合、アクリル当量が78〜145である(メタ)アクリロイル基を有する多官能(メタ)アクリレートを、全活性エネルギー線重合性化合物に対し85mol%以上含有する組成物が、アクリル基材に対して良密着性を示すことがわかる。 The results are shown in FIG. In FIG. 1, what is represented by a black square is a plot of the relationship between the ester group concentration and the adhesiveness of a composition containing less than 85 mol% of polyfunctional (meth) acrylate. Moreover, what is represented by a white square in FIG. 1 is a plot of the relationship between the ester group concentration and the adhesiveness of a composition containing 85 mol% or more of polyfunctional (meth) acrylate. As can be seen from FIG. 1, when the ester group concentration is less than 7.4 mmol / g, the adhesion cannot be obtained. On the other hand, when the ester group concentration is 7.4 mmol / g or more, the polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145 is 85 mol% or more based on the total active energy ray polymerizable compound. It turns out that the composition to contain shows good adhesiveness with respect to an acrylic base material.
Claims (6)
且つ、前記活性エネルギー線重合性化合物全量に対するエステル基濃度が少なくとも7.4mmol/gであることを特徴とする活性エネルギー線硬化性組成物。 A polyfunctional (meth) acrylate having a (meth) acryloyl group containing an active energy ray polymerizable compound and a photopolymerization initiator and having an acrylic equivalent of 121 to 145 as the active energy ray polymerizable compound is a total active energy ray. Containing 85 mol% or more of the polymerizable compound and an active energy ray-curable compound other than the polyfunctional (meth) acrylate having a (meth) acryloyl group having an acrylic equivalent of 78 to 145;
The active energy ray-curable composition is characterized in that the ester group concentration relative to the total amount of the active energy ray-polymerizable compound is at least 7.4 mmol / g.
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JP5623997B2 (en) * | 2011-08-29 | 2014-11-12 | 東洋インキScホールディングス株式会社 | Active energy ray curable inkjet magenta ink |
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WO2023055587A1 (en) * | 2021-09-29 | 2023-04-06 | Illuming Power Inc. | Improved monomer compositions for temperature resistance after curing |
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