JP2022180796A - Active energy ray-curable composition, cured product and film - Google Patents
Active energy ray-curable composition, cured product and film Download PDFInfo
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- JP2022180796A JP2022180796A JP2021087491A JP2021087491A JP2022180796A JP 2022180796 A JP2022180796 A JP 2022180796A JP 2021087491 A JP2021087491 A JP 2021087491A JP 2021087491 A JP2021087491 A JP 2021087491A JP 2022180796 A JP2022180796 A JP 2022180796A
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- Prior art keywords
- meth
- acrylate
- film
- active energy
- curable composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 108
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 13
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 13
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 23
- 239000005056 polyisocyanate Substances 0.000 claims description 22
- 229920001228 polyisocyanate Polymers 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
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- 230000004913 activation Effects 0.000 claims 1
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 4
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- 238000011156 evaluation Methods 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
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- 229910052753 mercury Inorganic materials 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- 230000001678 irradiating effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229940117969 neopentyl glycol Drugs 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
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- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
Description
本発明は、活性エネルギー線硬化性組成物及びその硬化物、並びに当該組成物を用いたフィルムに関する。 TECHNICAL FIELD The present invention relates to an active energy ray-curable composition, a cured product thereof, and a film using the composition.
環状オレフィン樹脂（ＣＯＰ）フィルムは、高透明性、低複屈折、低吸湿性、低透湿性等に優れており、光学部材、医療、包装フィルム、自動車、半導体等の用途に幅広く用いられている。特に光学用途では、テレビ等のディスプレイの大面積化に伴い、従来用いられていたポリエチレンテレフタレート（ＰＥＴ）やトリアセチルセルロース（ＴＡＣ）等のプラスチックフィルムの代替としてＣＯＰフィルムを用いることが検討されている。 Cyclic olefin resin (COP) films are excellent in high transparency, low birefringence, low hygroscopicity, low moisture permeability, etc., and are widely used in applications such as optical members, medical care, packaging films, automobiles, and semiconductors. . In particular, for optical applications, the use of COP films as a substitute for conventionally used plastic films such as polyethylene terephthalate (PET) and triacetylcellulose (TAC) is being studied as displays such as televisions become larger. .
一方で、ＣＯＰフィルムは表面硬度が不十分であるため加工時や使用時に傷が付くおそれがあり、耐摩耗性及び耐擦傷性の向上を目的として、表面に活性エネルギー線硬化性組成物の硬化塗膜からなるハードコート層等の保護層を設けることがある。
しかしながら、ＣＯＰフィルムはその主構造が脂環構造であることからフィルム表面の極性が低く、表面の濡れ性が悪く、溶剤によって浸食され難いという特徴を有する。そのため、ＣＯＰフィルム上にハードコート層形成用の活性エネルギー線硬化性組成物を塗工した場合、塗材が塗れ広がりにくく、ＣＯＰ表面とハードコート層との間の密着性が低いという問題があった。
On the other hand, since COP films have insufficient surface hardness, they may be scratched during processing or use. A protective layer such as a hard coat layer made of a coating film may be provided.
However, since the main structure of the COP film is an alicyclic structure, the polarity of the film surface is low, the wettability of the surface is poor, and it is difficult to be eroded by solvents. Therefore, when an active energy ray-curable composition for forming a hard coat layer is applied to a COP film, the coating material is difficult to spread and there is a problem that the adhesion between the COP surface and the hard coat layer is low. rice field.
ＣＯＰフィルムとハードコート層との間の密着性を向上する方法として、プライマー処理やコロナ処理等の前処理をすることでＣＯＰフィルム表面を親水化する方法が提案されている（例えば、特許文献１参照。）。この方法によりＣＯＰフィルム表面とハードコート層との間の密着性を向上することはできるが、プライマー層の塗工、乾燥により工程数が増加し、歩留まり低下、コストアップ、環境負荷発生等の問題があるため、前処理無しでＣＯＰフィルムに密着する塗材が求められている。 As a method for improving the adhesion between the COP film and the hard coat layer, a method of making the surface of the COP film hydrophilic by pretreatment such as primer treatment or corona treatment has been proposed (for example, Patent Document 1 reference.). Although this method can improve the adhesion between the COP film surface and the hard coat layer, it increases the number of steps due to the coating and drying of the primer layer, resulting in problems such as a decrease in yield, an increase in cost, and the occurrence of environmental impact. Therefore, there is a demand for a coating material that adheres to the COP film without pretreatment.
上述のような課題に対し、特許文献２に記載の発明では、ハードコート層形成用の活性エネルギー線硬化性組成物として、ベンゾフェノン系開始剤及び／又はチオキサントン系開始剤と、シリカ微粒子と、特定のウレタン（メタ）アクリレートとを用いることで、前処理を施すことなく、耐擦傷性及び基材密着性に優れたハードコート層を得ることが提案されている。
しかしながら、特許文献２に記載の発明では密着性は改善されているものの、ハードコート性（硬度及び耐擦傷性）に未だ改良の余地があった。また、光開始剤として特定の化合物を用いる必要があるため、所望の特性等に応じて重合開始剤を選択することができず、組成物の選択の幅が狭まるという問題もあった。
In order to solve the above-described problems, the invention described in Patent Document 2 provides a benzophenone-based initiator and/or a thioxanthone-based initiator and silica fine particles as an active energy ray-curable composition for forming a hard coat layer. It is proposed to obtain a hard coat layer excellent in scratch resistance and substrate adhesion without pretreatment by using urethane (meth)acrylate.
However, although the invention described in Patent Document 2 improves adhesion, there is still room for improvement in hard coat properties (hardness and scratch resistance). Moreover, since it is necessary to use a specific compound as a photoinitiator, the polymerization initiator cannot be selected according to the desired properties, etc., and there is also a problem that the range of selection of the composition is narrowed.
本発明が解決しようとする課題は、ＣＯＰフィルム等の基材表面に塗工して硬化させることで、プライマー処理やコロナ処理等の前処理を必要とすることなく、基材との優れた密着性とハードコート性とを両立得る活性エネルギー線硬化性組成物、並びに、その硬化物及びそれを用いたフィルムを提供することである。 The problem to be solved by the present invention is that by coating and curing the surface of a substrate such as a COP film, excellent adhesion to the substrate can be achieved without the need for pretreatment such as primer treatment or corona treatment. An object of the present invention is to provide an active energy ray-curable composition having both good properties and hard coat properties, a cured product thereof, and a film using the same.
本発明者らは、上記課題を解決すべく鋭意研究した結果、環状又は直鎖状のヘキサメチレン骨格を有するウレタン（メタ）アクリレートと、多官能（メタ）アクリレートとを併用することにより、プライマー処理やコロナ処理等の前処理を省略し、且つ、一般的な光開始剤を用いた場合であっても、基材と硬化塗膜との密着性に優れ、優れたハードコート性を達成できることを見出し、本発明を完成させた。 As a result of intensive research to solve the above problems, the present inventors have found that by using a combination of a urethane (meth)acrylate having a cyclic or linear hexamethylene skeleton and a polyfunctional (meth)acrylate, primer treatment and corona treatment, etc., and even when a general photoinitiator is used, the adhesion between the substrate and the cured coating film is excellent, and excellent hard coat properties can be achieved. He found the headline and completed the present invention.
すなわち本発明は、以下の発明に関するものである。
（１）環状又は直鎖状のヘキサメチレン骨格を有するウレタン（メタ）アクリレート（Ａ）と、多官能（メタ）アクリレート（Ｂ）と、重合開始剤（Ｃ）と、を含有することを特徴とする活性エネルギー線硬化性組成物。
（２）前記多官能（メタ）アクリレート（Ｂ）の配合量が、前記ウレタン（メタ）アクリレート（Ａ）と前記多官能（メタ）アクリレート（Ｂ）との合計１００質量部に対して、５０～９０質量部の範囲である、前記（１）の活性エネルギー線硬化性組成物。
（３）前記ヘキサメチレン骨格を有するウレタン（メタ）アクリレート（Ａ）が、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシレンジイソアネートの水素添加物、又は、ジフェニルメタンジイソシアネートの水素添加物からなる群から選ばれる１種以上のポリイソシアネートと、水酸基を有する（メタ）アクリレートとの反応生成物である、前記（１）の活性エネルギー線硬化性組成物。
（４）前記（１）～（３）のいずれかの活性エネルギー線硬化性組成物の硬化物。
（５）環状オレフィン樹脂フィルム基材の少なくとも１面に、前記（１）～（３）のいずれかの活性エネルギー線硬化性組成物の硬化塗膜を有するフィルム。
That is, the present invention relates to the following inventions.
(1) characterized by containing a urethane (meth)acrylate (A) having a cyclic or linear hexamethylene skeleton, a polyfunctional (meth)acrylate (B), and a polymerization initiator (C); Active energy ray-curable composition.
(2) The blending amount of the polyfunctional (meth)acrylate (B) is 50 to 50 parts per 100 parts by mass in total of the urethane (meth)acrylate (A) and the polyfunctional (meth)acrylate (B). The active energy ray-curable composition of (1), which is in the range of 90 parts by mass.
(3) The urethane (meth)acrylate (A) having a hexamethylene skeleton is selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, or hydrogenated diphenylmethane diisocyanate. The active energy ray-curable composition according to (1), which is a reaction product of at least one polyisocyanate and a (meth)acrylate having a hydroxyl group.
(4) A cured product of the active energy ray-curable composition according to any one of (1) to (3).
(5) A film having, on at least one surface of a cyclic olefin resin film substrate, a cured coating film of the active energy ray-curable composition according to any one of (1) to (3).
本発明の活性エネルギー線硬化性組成物は、ＣＯＰフィルム等の基材表面に塗工した後に硬化させることで、基材のプライマー処理やコロナ処理等の前処理を必要とすることなく、基材との密着性に優れたハードコート層を形成することができるものである。
また、本発明の活性エネルギー線硬化性組成物の硬化物や硬化塗膜は、硬度が高く、耐擦傷性に優れることから、幅広い用途で使用することができる。
The active energy ray-curable composition of the present invention can be applied to the surface of a substrate such as a COP film and then cured, so that the substrate can be cured without pretreatment such as primer treatment or corona treatment. It is possible to form a hard coat layer having excellent adhesion to.
Moreover, since the cured product and cured coating film of the active energy ray-curable composition of the present invention have high hardness and excellent scratch resistance, they can be used in a wide range of applications.
本発明の活性エネルギー線硬化性組成物（以下、単に「組成物」ということがある。）は、環状又は直鎖状のヘキサメチレン骨格を有するウレタン（メタ）アクリレート（Ａ）と、多官能（メタ）アクリレート（Ｂ）と、重合開始剤（Ｃ）と、を含有するものである。なお、本発明において、「（メタ）アクリレート」とは、アクリレートとメタクリレートの一方又は両方をいい、「（メタ）アクリロイル基」とは、アクリロイル基とメタクリロイル基の一方又は両方をいう。 The active energy ray-curable composition of the present invention (hereinafter sometimes simply referred to as "composition") comprises a urethane (meth)acrylate (A) having a cyclic or linear hexamethylene skeleton and a polyfunctional ( It contains a meth)acrylate (B) and a polymerization initiator (C). In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acryloyl group" refers to one or both of acryloyl group and methacryloyl group.
［ウレタン（メタ）アクリレート（Ａ）］
ウレタン（メタ）アクリレート（Ａ）（以下「（Ａ）成分」ということがある。）は環状又は直鎖状のヘキサメチレン骨格を有するものである。
ウレタン（メタ）アクリレート（Ａ）は、ポリイソシアネート（ａ１）と水酸基を有する（メタ）アクリレート（ａ２）とを反応させて得ることができる。環状又は直鎖状のヘキサメチレン骨格は、ポリイソシアネート（ａ１）由来であってもよく、水酸基を有する（メタ）アクリレート（ａ２）由来であってもよいが、ポリイソシアネート（ａ１）が環状又は直鎖状のヘキサメチレン骨格を有することが好ましい。
[Urethane (meth)acrylate (A)]
Urethane (meth)acrylate (A) (hereinafter sometimes referred to as "component (A)") has a cyclic or linear hexamethylene skeleton.
A urethane (meth)acrylate (A) can be obtained by reacting a polyisocyanate (a1) with a (meth)acrylate (a2) having a hydroxyl group. The cyclic or linear hexamethylene skeleton may be derived from the polyisocyanate (a1) or may be derived from the (meth)acrylate (a2) having a hydroxyl group, but the polyisocyanate (a1) may be cyclic or linear. It preferably has a chain hexamethylene skeleton.
（ポリイソシアネート（ａ１））
ポリイソシアネート（ａ１）としては、脂肪族ポリイソシアネートと芳香族ポリイソシアネートとが挙げられるが、本発明で用いる活性エネルギー線硬化性組成物の硬化塗膜の着色をより低減できることから、脂肪族ポリイソシアネートが好ましい。
脂肪族ポリイソシアネートは、イソシアネート基を除く部位が脂肪族炭化水素から構成される化合物である。脂肪族ポリイソシアネートの具体例としては、ヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等の脂肪族ポリイソシアネート；ノルボルナンジイソシアネート、イソホロンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、１，３－ビス（イソシアナトメチル）シクロヘキサン、２－メチル－１，３－ジイソシアナトシクロヘキサン、２－メチル－１，５－ジイソシアナトシクロヘキサン等の脂環式ポリイソシアネート等が挙げられる。また、前記脂肪族ポリイソシアネート又は脂環式ポリイソシアネートを３量化した３量化物も前記脂肪族ポリイソシアネートとして用いることができる。これらの脂肪族ポリイソシアネートは、１種で用いることも２種以上併用することもできる。
(Polyisocyanate (a1))
Examples of the polyisocyanate (a1) include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition used in the present invention can be further reduced, aliphatic polyisocyanates is preferred.
Aliphatic polyisocyanates are compounds in which the sites other than isocyanate groups are composed of aliphatic hydrocarbons. Specific examples of aliphatic polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; ) alicyclic polyisocyanates such as cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane. A trimerized product obtained by trimerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. These aliphatic polyisocyanates can be used alone or in combination of two or more.
なかでもポリイソシアネート（ａ１）としては、直鎖状のヘキサメチレン骨格を有するヘキサメチレンジイソシアネート、又は、環状のヘキサメチレン骨格を有するイソホロンジイソシアネート、キシレンジイソアネートの水素添加物、又は、ジフェニルメタンジイソシアネートの水素添加物を用いることが好ましい。これらのポリイソシアネート（ａ１）を用いることにより、塗膜の耐擦傷性を向上するのみならず、ＣＯＰフィルム等の基材に対する密着性を向上させることができる。 Among them, the polyisocyanate (a1) includes hexamethylene diisocyanate having a linear hexamethylene skeleton, isophorone diisocyanate having a cyclic hexamethylene skeleton, a hydrogenated product of xylene diisocyanate, or hydrogen of diphenylmethane diisocyanate. Additives are preferably used. By using these polyisocyanates (a1), it is possible not only to improve the scratch resistance of the coating film, but also to improve the adhesion to a substrate such as a COP film.
（水酸基を有する（メタ）アクリレート（ａ２））
水酸基を有する（メタ）アクリレート（ａ２）（以下、単に「（メタ）アクリレート（ａ２）」ということがある。）は、水酸基と（メタ）アクリロイル基とを有する化合物である。
（メタ）アクリレート（ａ２）の具体例としては、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、４－ヒドロキシブチル（メタ）アクリレート、１，５－ペンタンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールモノ（メタ）アクリレート等の２価アルコールのモノ（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、エチレンオキサイド（ＥＯ）変性トリメチロールプロパン（メタ）アクリレート、プロピレンオキサイド（ＰＯ）変性トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ビス（２－（メタ）アクリロイルオキシエチル）ヒドロキシエチルイソシアヌレート等の３価のアルコールのモノ又はジ（メタ）アクリレート、あるいは、これらのアルコール性水酸基の一部をε－カプロラクトンで変性した水酸基を有するモノ及びジ（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、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の１官能の水酸基と３官能以上の（メタ）アクリロイル基を有する化合物、あるいは、該化合物をさらにε－カプロラクトンで変性した水酸基を有する多官能（メタ）アクリレート；ジプロピレングリコールモノ（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のオキシアルキレン鎖を有する（メタ）アクリレート；ポリエチレングリコール－ポリプロピレングリコールモノ（メタ）アクリレート、ポリオキシブチレン－ポリオキシプロピレンモノ（メタ）アクリレート等のブロック構造のオキシアルキレン鎖を有する（メタ）アクリレート；ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のランダム構造のオキシアルキレン鎖を有する（メタ）アクリレート等が挙げられる。これらの（メタ）アクリレート（ａ２）は、１種で用いることも２種以上併用することもできる。
((Meth)acrylate (a2) having a hydroxyl group)
The (meth)acrylate (a2) having a hydroxyl group (hereinafter sometimes simply referred to as "(meth)acrylate (a2)") is a compound having a hydroxyl group and a (meth)acryloyl group.
Specific examples of (meth)acrylates (a2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1 ,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, neopentylglycol hydroxypivalate mono(meth)acrylate, etc. (Meth)acrylate; trimethylolpropane di(meth)acrylate, ethylene oxide (EO)-modified trimethylolpropane (meth)acrylate, propylene oxide (PO)-modified trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, Mono- or di(meth)acrylates of trihydric alcohols such as bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone mono- and di(meth)acrylates; monofunctional hydroxyl groups such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and trifunctional or higher (meth)acryloyl groups; or a polyfunctional (meth)acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene (Meth) acrylate having an oxyalkylene chain such as glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate, etc. block structure oxyalkylene chain (meth)acrylate having random structure oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. is mentioned. These (meth)acrylates (a2) can be used alone or in combination of two or more.
ウレタン（メタ）アクリレート（Ａ）は、本発明の組成物を硬化してなる硬化物及び硬化塗膜の耐擦傷性を向上させるため、１分子中に４つ以上の（メタ）アクリロイル基を有するものが好ましい。ウレタン（メタ）アクリレート（Ａ）が１分子中に４つ以上の（メタ）アクリロイル基を有するため、水酸基を有する（メタ）アクリレート（ａ２）としては、（メタ）アクリロイル基を２つ以上有するものが好ましい。このような（メタ）アクリレート（ａ２）としては、例えば、トリメチロールプロパンジ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ビス（２－（メタ）アクリロイルオキシエチル）ヒドロキシエチルイソシアヌレート、ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。
なかでも、これらの（メタ）アクリレート（ａ２）の中でも、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）アクリレートは、耐擦傷性を向上できるため特に好ましい。
これらの（メタ）アクリレート（ａ２）は、ポリイソシアネート（ａ１）の１種に対して、１種を用いることも２種以上併用することもできる。
The urethane (meth)acrylate (A) has four or more (meth)acryloyl groups in one molecule in order to improve the scratch resistance of the cured product and the cured coating film obtained by curing the composition of the present invention. things are preferred. Since the urethane (meth)acrylate (A) has 4 or more (meth)acryloyl groups in one molecule, the (meth)acrylate (a2) having a hydroxyl group has two or more (meth)acryloyl groups. is preferred. Examples of such (meth)acrylates (a2) include trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, propylene oxide-modified trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, (Meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and the like. .
Among these (meth)acrylates (a2), pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are particularly preferable because they can improve scratch resistance.
These (meth)acrylates (a2) can be used singly or in combination of two or more for one polyisocyanate (a1).
ポリイソシアネート（ａ１）と（メタ）アクリレート（ａ２）との反応は、常法のウレタン化反応により行うことができる。また、ウレタン化反応の進行を促進するために、ウレタン化触媒の存在下でウレタン化反応を行うことが好ましい。前記ウレタン化触媒としては、例えば、ピリジン、ピロール、トリエチルアミン、ジエチルアミン、ジブチルアミン等のアミン化合物；トリフェニルホスフィン、トリエチルホスフィン等のリン化合物；ジブチル錫ジラウレート、オクチル錫トリラウレート、オクチル錫ジアセテート、ジブチル錫ジアセテート、オクチル酸錫等の有機錫化合物、オクチル酸亜鉛等の有機亜鉛化合物などが挙げられる。 The reaction between the polyisocyanate (a1) and the (meth)acrylate (a2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate the progress of the urethanization reaction, it is preferable to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, and dibutyltin. Diacetate, organic tin compounds such as tin octylate, organic zinc compounds such as zinc octylate, and the like.
（Ａ）成分は、１種で用いることも、２種以上併用することもできる。 The component (A) may be used singly or in combination of two or more.
［多官能（メタ）アクリレート（Ｂ）］
多官能（メタ）アクリレート（Ｂ）（以下「（Ｂ）成分」ということがある。）は、１分子中に２つ以上の（メタ）アクリロイル基を有する化合物のうち、前記（Ａ）成分に該当しないものである。
この多官能（メタ）アクリレート（Ｂ）としては、例えば、１，４－ブタンジオールジ（メタ）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、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、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、２－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレングリコールジ（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、トリエチレングリコールジ（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、トリプロピレングリコールジ（メタ）アクリレート等の２価アルコールのジ（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、ポリプロピレングリコールジ（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Ａの１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トリ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパントリ（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、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート、グリセリントリ（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、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トリ（メタ）アクリレート、ジ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、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、ポリペンタエリスリトールポリ（メタ）アクリレート等の多官能（メタ）アクリレート、前記（Ａ）成分に該当しないウレタン（メタ）アクリレート（例えば、ヘキサメチレン骨格を有さないノルボルナンジイソシアネート等と水酸基を有し、ヘキサメチレン骨格を有さない（メタ）アクリレートとの反応生成物）が挙げられる。
[Polyfunctional (meth)acrylate (B)]
Polyfunctional (meth)acrylate (B) (hereinafter sometimes referred to as "(B) component") is a compound having two or more (meth)acryloyl groups in one molecule, and the (A) component Not applicable.
Examples of the polyfunctional (meth)acrylate (B) include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (meth)acrylates, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate ) dihydric alcohol di(meth)acrylate such as acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, neopentyl glycol 1 di(meth)acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide per mol; ) acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra( meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, polypentaerythritol poly( Polyfunctional (meth)acrylates such as meth)acrylates G, urethane (meth)acrylates that do not correspond to the above component (A) (for example, reaction products of norbornane diisocyanate having no hexamethylene skeleton and (meth)acrylates having hydroxyl groups and no hexamethylene skeleton ).
なかでも（Ｂ）成分としては、硬化後に高い架橋度が得られ、硬化物及び硬化被膜の硬度及び耐擦傷性がより一層向上することから、４官能以上の（メタ）アクリレートが好ましく、ペンタエリスリトールトリアクリレート、又はジペンタエリスリトールヘキサアクリレートが好ましい。 Among them, as the component (B), a high degree of cross-linking is obtained after curing, and the hardness and scratch resistance of the cured product and cured film are further improved. Triacrylate or dipentaerythritol hexaacrylate are preferred.
（Ｂ）成分は、１種で用いることも、２種以上併用することもできる。
（Ｂ）成分の配合量は、（Ａ）成分と（Ｂ）成分との合計１００質量部に対して、２０～９５質量部が好ましく、４０～９０質量部がより好ましく、５０～９０質量部が特に好ましい。
The component (B) may be used singly or in combination of two or more.
The amount of component (B) is preferably 20 to 95 parts by mass, more preferably 40 to 90 parts by mass, and 50 to 90 parts by mass, based on 100 parts by mass of components (A) and (B) combined. is particularly preferred.
［重合開始剤（Ｃ））］
本発明の活性エネルギー線硬化性組成物は、基材上に塗工後、活性エネルギー線を照射することで硬化塗膜とすることができる。この活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等の電離放射線をいい、工業的には紫外線が広く用いられている。
重合開始剤（Ｃ）（以下「（Ｃ）成分」ということがある。）は、活性エネルギー線の照射に応じて（Ａ）成分及び（Ｂ）成分の重合反応を開始させるために本発明の組成物に含有されるものであって、光重合開始剤として一般的に知られている化合物を用いることができる。
[Polymerization initiator (C))]
The active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray onto a substrate and then irradiating it with an active energy ray. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays, and ultraviolet rays are widely used industrially.
The polymerization initiator (C) (hereinafter sometimes referred to as "component (C)") is used in the present invention to initiate the polymerization reaction of components (A) and (B) in response to irradiation with active energy rays. A compound generally known as a photopolymerization initiator that is contained in the composition can be used.
光重合開始剤として具体的には、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、オリゴ｛２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン｝、ベンジルジメチルケタール、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、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－２－モルホリノ（４－チオメチルフェニル）プロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン等のアセトフェノン系化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン系化合物；２，４，６－トリメチルベンゾイン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等のアシルホスフィンオキシド系化合物；ベンジル（ジベンゾイル）、メチルフェニルグリオキシエステル、オキシフェニル酢酸２－（２－ヒドロキシエトキシ）エチルエステル、オキシフェニル酢酸２－（２－オキソ－２－フェニルアセトキシエトキシ）エチルエステル等のベンジル系化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）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、２，４，６－トリメチルベンゾフェノン、４－メチルベンゾフェノン等のベンゾフェノン系化合物；２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等のチオキサントン系化合物；ミヒラ－ケトン、４，４’－ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、カンファーキノン、１－［４－（４－ベンゾイルフェニルサルファニル）フェニル］－２－メチル－２－（４－メチルフェニルサルフォニル）プロパン－１－オン等が挙げられる。 Specific photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methyl vinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2- propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone acetophenone-based compounds such as; benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin-based compounds; Acylphosphine oxide compounds; benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester, etc. Benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3' , 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, benzophenone compounds such as 4-methylbenzophenone; 2-isopropyl Thioxanthone compounds such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michra-ketone and 4,4'-diethylaminobenzophenone; 10-butyl- 2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methyl phenylsulfonyl)propane- 1-one and the like.
（Ｃ）成分としては、市販品を用いることもできる。市販品として具体的には、アルキルフェノン系化合物：Ｏｍｎｉｒａｄ １８４、Ｏｍｎｉｒａｄ １１７３、Ｏｍｎｉｒａｄ １１１６、Ｏｍｎｉｒａｄ ９０７、Ｏｍｎｉｒａｄ ６５１、Ｏｍｎｉｒａｄ ２９５９、Ｏｍｎｉｒａｄ １２７、Ｏｍｎｉｒａｄ ３６９、Ｏｍｎｉｒａｄ ３７９（以上、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）、
アシルホスフィンオキサイド系化合物：Ｏｍｎｉｒａｄ ＴＰＯ、Ｏｍｎｉｒａｄ ８１９（以上、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．株式会社製）、
オキシムエステル系化合物：イルガキュアＯＸＥ０１、イルガキュアＯＸＥ０２、イルガキュアＯＸＥ０３、イルガキュアＯＸＥ０４（以上、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製）、
水素引き抜き型化合物：ＳＢ－ＰＩ ７０１、ＳＢ－ＰＩ ７０１、ＳＢ－ＰＩ ７０７、ＳＢ－ＰＩ ７１１、ＳＢ－ＰＩ ７１２、ＳＢ－ＰＩ ７１６（以上、三陽貿易社製）、カヤキュアＤＥＴＸ－Ｓ、カヤキュアＥＰＡ（以上、日本化薬社製）、カンタキュア－ＩＴＸ（ワ－ドプレキンソップ社製）等が挙げられる。
(C) A commercial item can also be used as a component. Specific examples of commercial products include alkylphenone-based compounds: Omnirad 184, Omnirad 1173, Omnirad 1116, Omnirad 907, Omnirad 651, Omnirad 2959, Omnirad 127, Omnirad 369, Omnirad 379 (these are B. Resins manufactured by IGM V. Resins). ),
Acylphosphine oxide compounds: Omnirad TPO, Omnirad 819 (manufactured by IGM Resins B.V.),
Oxime ester compounds: Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by IGM Resins B.V.),
Hydrogen-abstraction compounds: SB-PI 701, SB-PI 701, SB-PI 707, SB-PI 711, SB-PI 712, SB-PI 716 (manufactured by Sanyo Trading Co., Ltd.), Kayacure DETX-S, Kayacure EPA (manufactured by Nippon Kayaku Co., Ltd.), Cantacure-ITX (manufactured by Ward Prekinsop) and the like.
（Ｃ）成分は、１種で用いることも、２種以上併用することもできる。
（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対し、０．０５～３０質量部が好ましく、０．５～２０質量部がより好ましく、１～１５質量部がさらに好ましく、２～１０質量部が特に好ましい。
Component (C) may be used alone or in combination of two or more.
The amount of component (C) is preferably 0.05 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 15 parts by mass, based on 100 parts by mass of component (A). ~10 parts by weight is particularly preferred.
本発明の活性エネルギー線硬化性組成物には、上記の成分（Ａ）～（Ｃ）以外のその他の成分として、用途、要求特性に応じて、有機溶剤、光増感剤、重合禁止剤、消泡剤、レベリング剤以外の表面調整剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、有機顔料、無機顔料、顔料分散剤、シリカビーズ、有機ビーズ等の添加剤；酸化ケイ素、酸化アルミニウム、酸化チタン、ジルコニア、五酸化アンチモン等の無機充填剤などを配合することができる。これらその他の配合物は、１種で用いることも２種以上併用することもできる。 The active energy ray-curable composition of the present invention may contain, as components other than the above components (A) to (C), organic solvents, photosensitizers, polymerization inhibitors, Antifoaming agents, surface modifiers other than leveling agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic Additives such as beads; Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. can be blended. These other formulations can be used alone or in combination of two or more.
なかでも有機溶媒は、本発明の組成物の溶液粘度を適宜調整する上で有用であり、特に薄膜コーティングを行うためには、膜厚を調整することが容易となる。ここで使用できる有機溶媒としては、例えば、トルエン、キシレン等の芳香族炭化水素；メタノール、エタノール、イソプロパノール、ｔ－ブタノール等のアルコール類；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、プロピレングリコールモノメチルエーテル等のグリコールエーテル類等が挙げられる。これらの溶剤は、１種で用いることも、２種以上を併用することもできる。 Among them, the organic solvent is useful for appropriately adjusting the viscosity of the solution of the composition of the present invention, and facilitates the adjustment of the film thickness particularly for thin film coating. Examples of organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and glycol ethers such as propylene glycol monomethyl ether. These solvents can be used singly or in combination of two or more.
本発明の組成物は、フィルム等の基材の少なくとも１面に塗工した後に活性エネルギー線を照射して硬化塗膜として用いてもよく、基材を用いずに活性エネルギー線を照射して硬化物としてもよい。 The composition of the present invention may be used as a cured coating film by applying an active energy ray after coating at least one surface of a substrate such as a film, or by irradiating an active energy ray without using a substrate. It may be a cured product.
硬化塗膜を得る際の基材の材質としては、透明性の高い樹脂が好ましく、例えば、環状オレフィン共重合体；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂；ポリプロピレン、ポリエチレン、ポリメチルペンテン－１等のポリオレフィン系樹脂；セルロースアセテート（ジアセチルセルロース、トリアセチルセルロース等）、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースアセテートプロピオネートブチレート、セルロースアセテートフタレート、硝酸セルロース等のセルロース系樹脂；ポリメチルメタクリレート等のアクリル系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン等の塩化ビニル系樹脂；ポリビニルアルコール；エチレン－酢酸ビニル共重合体；ポリスチレン；ポリアミド；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルエーテルケトン；ポリイミド、ポリエーテルイミド等のポリイミド系樹脂；ノルボルネン系樹脂（例えば、日本ゼオン株式会社製「ゼオノア」）、変性ノルボルネン系樹脂（例えば、ＪＳＲ株式会社製「アートン」）等が挙げられる。さらに、これらの樹脂からなる基材を２種以上貼り合わせたものを用いても構わない。 As the material of the substrate for obtaining the cured coating film, highly transparent resins are preferable, and examples thereof include cyclic olefin copolymers; Polyolefin resins such as polymethylpentene-1; cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate, etc. Cellulose resins; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; Polystyrene; polyether ether ketone; polyimide-based resins such as polyimide and polyetherimide; be done. Furthermore, two or more types of base materials made of these resins may be bonded together to be used.
本発明の活性エネルギー線硬化性組成物は、従来ハードコート層の基材密着性向上が難しいとされていた環状オレフィン樹脂（ＣＯＰ）に対して良好な密着性を有する。そのため、本発明の組成物は、ＣＯＰを基材とする硬化塗膜として好適に用いることができる。 ADVANTAGE OF THE INVENTION The active-energy-ray-curable composition of this invention has favorable adhesiveness with respect to the cyclic olefin resin (COP) which was considered difficult to improve the substrate adhesiveness of a hard-coat layer conventionally. Therefore, the composition of the present invention can be suitably used as a cured coating film using COP as a base material.
硬化塗膜を得る際の基材は、フィルム状でもシート状でもよく、その厚さは、１～５００μｍの範囲が好ましい。また、フィルム状の基材フィルムを用いる場合には、その厚さは、２０～２００μｍの範囲が好ましく、３０～１５０μｍの範囲がより好ましく、４０～１３０μｍの範囲がさらに好ましい。フィルム基材の厚さを当該範囲とすることで、フィルムの片面に、本発明の活性エネルギー線硬化性組成物によりハードコート層を設けた場合にもカールを抑制しやすくなる。 The substrate for obtaining the cured coating film may be in the form of a film or a sheet, and its thickness is preferably in the range of 1 to 500 μm. When a film-like base film is used, its thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, even more preferably in the range of 40 to 130 μm. By setting the thickness of the film substrate within this range, curling can be easily suppressed even when a hard coat layer is provided on one side of the film using the active energy ray-curable composition of the present invention.
ＣＯＰフィルム基材は、ＣＯＰをフィルム上に成形したものである。ＣＯＰの市販品としては、例えば、日本ゼオン株式会社製の「ＺＥＯＮＯＲ（登録商標）」、「ＺＥＯＮＥＸ（登録商標）」；ＪＳＲ株式会社製の「ＡＲＴＯＮ（登録商標）」；ポリプラスチックス株式会社製の「ＴＯＰＡＳ（登録商標）」；三井化学株式会社製「アペル（登録商標）」等が挙げられる。
本発明の組成物は、ＣＯＰフィルム基材に対して前処理を施さない場合にも、ＣＯＰフィルムに対して良好な密着性が得られるものである。しかしながら、さらなる密着性の向上を目的として、ＣＯＰフィルムに対して予めサンドブラスト法、溶剤処理法等による表面の凹凸化処理、電気的処理（コロナ放電処理、大気圧プラズマ処理）、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線・電子線照射処理、酸化処理等の処理をしてもよい。
A COP film substrate is obtained by forming a COP on a film. Commercially available COPs include, for example, “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)” manufactured by Zeon Corporation; “ARTON (registered trademark)” manufactured by JSR Corporation; "TOPAS (registered trademark)" manufactured by Mitsui Chemicals, Inc.; "APEL (registered trademark)" manufactured by Mitsui Chemicals, Inc.;
The composition of the present invention provides good adhesion to the COP film even when the COP film substrate is not pretreated. However, for the purpose of further improving the adhesion, the surface of the COP film is subjected to roughening treatment such as sandblasting, solvent treatment, electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, and flame treatment. treatment, hot air treatment, ozone/ultraviolet/electron beam irradiation treatment, oxidation treatment, and the like.
前記フィルム基材に本発明の活性エネルギー線硬化性組成物を塗工する方法としては、例えば、ダイコート、マイクログラビアコート、グラビアコート、ロールコート、コンマコート、エアナイフコート、キスコート、スプレーコート、ディップコート、スピンナーコート、刷毛塗り、シルクスクリーンによるベタコート、ワイヤーバーコート、フローコート等が挙げられる。 Examples of methods for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating, and the like.
本発明の活性エネルギー線硬化性組成物を硬化させる活性エネルギー線としては、上記の通り、紫外線、電子線、α線、β線、γ線等の電離放射線である。ここで、活性エネルギー線として紫外線を用いる場合、その紫外線を照射する装置としては、例えば、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、無電極ランプ（フュージョンランプ）、ケミカルランプ、ブラックライトランプ、水銀－キセノンランプ、ショートアーク灯、ヘリウム・カドミニウムレーザー、アルゴンレーザー、太陽光、ＬＥＤランプ等が挙げられる。 As described above, the active energy rays for curing the active energy ray-curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when ultraviolet rays are used as active energy rays, devices for irradiating the ultraviolet rays include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps and the like.
前記フィルム基材上に本発明の活性エネルギー線硬化性組成物の硬化塗膜を形成する際の硬化塗膜の膜厚は、硬化塗膜の硬さを充分なものとし、かつ塗膜の硬化収縮によるフィルムのカールを抑制できることから、１～３０μｍの範囲が好ましいが、２～１５μｍの範囲がより好ましく、３～１０μｍの範囲がさらに好ましい。 When forming a cured coating film of the active energy ray-curable composition of the present invention on the film substrate, the thickness of the cured coating film is such that the cured coating film has sufficient hardness and the coating film is cured. Since curling of the film due to shrinkage can be suppressed, the range is preferably 1 to 30 μm, more preferably 2 to 15 μm, and even more preferably 3 to 10 μm.
以下、実施例により本発明をより具体的に説明する。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
（実施例１）
ウレタンアクリレート（ヘキサメチレンジイソシアネート（ＨＤＩ）とジペンタエリスリトールペンタアクリレート（ＤＰＰＡ）との反応物；固形分１００質量％；以下、「ＵＡ１」と略記する。）５０質量部、ペンタエリスリトールテトラアクリレート（ＰＥＴＴＡ）５０質量部、アルキルフェノン系光重合開始剤（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製「Ｏｍｎｉｒａｄ １８４」；以下、「開始剤１」と略記する。）５質量部、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）３１５質量部を均一に混合して、活性エネルギー線硬化性組成物（１）を調製した。
(Example 1)
Urethane acrylate (reaction product of hexamethylene diisocyanate (HDI) and dipentaerythritol pentaacrylate (DPPA); solid content 100% by mass; hereinafter abbreviated as “UA1”) 50 parts by mass, pentaerythritol tetraacrylate (PETTA) 50 parts by mass, alkylphenone-based photopolymerization initiator (IGM Resins B.V. "Omnirad 184"; hereinafter abbreviated as "initiator 1".) 5 parts by mass, propylene glycol monomethyl ether (PGME) 315 mass The parts were uniformly mixed to prepare an active energy ray-curable composition (1).
（実施例２～７、比較例１～６）
表１～２に示した組成に変更した以外は実施例１と同様にして、活性エネルギー線硬化性組成物（２）～（７）、（Ｒ１）～（Ｒ６）を得た。
(Examples 2 to 7, Comparative Examples 1 to 6)
Active energy ray-curable compositions (2) to (7) and (R1) to (R6) were obtained in the same manner as in Example 1, except that the compositions were changed to those shown in Tables 1 and 2.
［評価用サンプルの作製］
各例の活性エネルギー線硬化性組成物を、厚さ１００μｍのＣＯＰフィルム（日本ゼオン株式会社製「ＺＥＯＮＯＲ（登録商標）フィルム「ＺＦ１６－１００」、）に、バーコーターで塗工し、６０℃で６０秒間間乾燥した後、窒素囲気下で紫外線照射装置（アイグラフィックス株式会社製、高圧水銀ランプ）を用いて照射光量３ｋＪ／ｍ２で照射し、膜厚４μｍの硬化塗膜を有するＣＯＰフィルムを得た。
[Preparation of sample for evaluation]
The active energy ray-curable composition of each example was applied to a 100 μm-thick COP film (“ZEONOR (registered trademark) film “ZF16-100”, manufactured by Nippon Zeon Co., Ltd.) with a bar coater, and was heated at 60°C. After drying for 60 seconds, the COP film having a cured coating film with a thickness of 4 μm was irradiated with an irradiation light amount of 3 kJ/m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in a nitrogen atmosphere. got
［密着性評価］
各例のＣＯＰフィルムの硬化塗膜表面に１ｍｍ間隔で縦、横１１本の切れ目を入れて１００個のマス目を作製した。次いで、セロハンテープ（ニチバン株式会社製「セロテープ（登録商標） ＣＴ－１８」）をその表面に密着させた後、一気に剥がす操作を２回繰り返した。剥離せずに残った残面積比率から、下記の基準により初期密着性を評価した。Ａ評価以上を合格と判定した。
Ａ：残面積比率が１００％である。
Ｂ：残面積比率が９５％以上１００％未満である。
Ｃ：残面積比率が１０％以上９５％未満である。
Ｄ：残面積比率が１０％未満である。
[Adhesion evaluation]
The surface of the cured coating film of the COP film of each example was cut vertically and horizontally at intervals of 1 mm to form 100 squares. Next, a cellophane tape (“Cellotape (registered trademark) CT-18” manufactured by Nichiban Co., Ltd.) was adhered to the surface, and then peeled off at once, which was repeated twice. The initial adhesion was evaluated according to the following criteria from the ratio of the remaining area without peeling. A grade or higher was determined to be acceptable.
A: The remaining area ratio is 100%.
B: The remaining area ratio is 95% or more and less than 100%.
C: The remaining area ratio is 10% or more and less than 95%.
D: The residual area ratio is less than 10%.
［硬度評価］
各例のＣＯＰフィルムの硬化塗膜の表面について、ＪＩＳ Ｋ５６００－５－４（１９９９）に準拠して鉛筆硬度を７５０ｇ荷重条件下で測定した。１つの硬度につき５回測定を行い、傷が付かなかった測定が４回以上あった硬度を積層フィルムの表面硬度とした。
なお、鉛筆の硬度は、硬度が高い順から２Ｈ、Ｈ、Ｆである。
[Hardness evaluation]
The surface of the cured coating film of the COP film of each example was measured for pencil hardness under a load of 750 g according to JIS K5600-5-4 (1999). Each hardness was measured 5 times, and the surface hardness of the laminated film was defined as the hardness at which 4 or more measurements did not cause damage.
The hardness of the pencil is 2H, H, and F in descending order of hardness.
［耐擦傷性評価］
各例のＣＯＰフィルムの硬化塗膜の表面について、クロックメーター形摩擦試験器（直径１．０ｃｍ円形摩擦子、スチールウール＃００００、荷重５００ｇ、１０往復）を用いて試験を行い、試験後の硬化塗膜表面を目視で観察し、下記の基準により耐擦傷性を評価した。
５：傷が無い。
４：浅い傷が５本以下である。
３：傷が５本以下である。
２：傷が多数ある。
１：顕著に深い傷が多数ある。
[Scratch resistance evaluation]
The surface of the cured coating film of the COP film of each example was tested using a crockmeter type friction tester (circular friction element with a diameter of 1.0 cm, steel wool #0000, load of 500 g, 10 reciprocations), and cured after the test. The coating film surface was visually observed, and the scratch resistance was evaluated according to the following criteria.
5: No damage.
4: 5 or less shallow scratches.
3: There are 5 or less scratches.
2: There are many scratches.
1: There are many remarkably deep scratches.
表１～２中に示す略語は下記の化合物を示す。
「ＵＡ１」：ヘキサメチレンジイソシアネート（ＨＤＩ）とジペンタエリスリトールペンタアクリレート（ＤＰＰＡ）との反応物、固形分１００質量％
「ＵＡ２」：イソホロンジイソシアネート（ＩＰＤＩ）とペンタエリスリトールトリアクリレート（ＰＥＴＡ）との反応物、固形分１００質量％
「ＵＡ３」：トリレンジイソシアネート（ＴＤＩ）とＰＥＴＡとの反応物、固形分１００質量％
「ＰＥＴＴＡ」：ペンタエリスリトールテトラアクリレート
「ＤＰＨＡ」：ジペンタエリスリールヘキサアクリレート
「ポリエステルＡｃ」：１，２，３，６－テトラヒドロフタル酸（ＴＨＰＡ）とＰＥＴＡとの反応物、固形分１００質量％
「イソシアヌレート」：イソシアヌル酸ＥＯ変性トリアクリレート
「ＴＭＰＴＡ」：トリメチロールプロパントリアクリレート
「ＰＧＭＥ」：プロピレングリコールモノメチルエーテル
The abbreviations shown in Tables 1-2 refer to the following compounds.
"UA1": reaction product of hexamethylene diisocyanate (HDI) and dipentaerythritol pentaacrylate (DPPA), solid content 100% by mass
"UA2": reaction product of isophorone diisocyanate (IPDI) and pentaerythritol triacrylate (PETA), solid content 100% by mass
"UA3": reaction product of tolylene diisocyanate (TDI) and PETA, solid content 100% by mass
"PETTA": pentaerythritol tetraacrylate "DPHA": dipentaerythryl hexaacrylate "Polyester Ac": reaction product of 1,2,3,6-tetrahydrophthalic acid (THPA) and PETA, solid content 100% by mass
"Isocyanurate": isocyanuric acid EO-modified triacrylate "TMPTA": trimethylolpropane triacrylate "PGME": propylene glycol monomethyl ether
本発明の活性エネルギー線硬化性組成物の硬化塗膜は、ＣＯＰフィルムとの優れた密着性を有し、且つ、硬度及び耐擦傷性に優れることが確認できた。
一方、（Ａ）成分を含有せず、樹脂として（Ｂ）成分のみを含有する比較例１は、基材密着性に劣ることが確認できた。また、（Ａ）成分を含有せず、代わりに他の樹脂を含有する比較例３～６も同様に、基材密着性に劣っていた。
加えて、（Ｂ）成分を含有しない比較例２は基材密着性及び耐擦傷性に劣ることが確認できた。
It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention has excellent adhesion to the COP film and is excellent in hardness and scratch resistance.
On the other hand, it was confirmed that Comparative Example 1, which does not contain the (A) component and contains only the (B) component as the resin, is inferior in adhesion to the substrate. Also, Comparative Examples 3 to 6, which did not contain component (A) and contained other resins instead, were similarly inferior in adhesion to the substrate.
In addition, it was confirmed that Comparative Example 2, which does not contain component (B), is inferior in substrate adhesion and scratch resistance.
Claims (5)
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| TW111118127A TW202311445A (en) | 2021-05-25 | 2022-05-13 | Active energy ray curable composition cured product and film |
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| JP2021087491A Pending JP2022180796A (en) | 2021-05-25 | 2021-05-25 | Active energy ray-curable composition, cured product and film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2022180796A (en) |
| KR (1) | KR20220159292A (en) |
| CN (1) | CN115386253A (en) |
| TW (1) | TW202311445A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004284158A (en) | 2003-03-20 | 2004-10-14 | Dainippon Printing Co Ltd | Hard coating film |
| JP6294999B1 (en) | 2017-06-05 | 2018-03-14 | 日本化工塗料株式会社 | Active energy ray-curable composition for forming a cured film on a cyclic olefin-based resin substrate, and method for producing a hard coat film |
-
2021
- 2021-05-25 JP JP2021087491A patent/JP2022180796A/en active Pending
-
2022
- 2022-05-10 CN CN202210502359.3A patent/CN115386253A/en active Pending
- 2022-05-13 TW TW111118127A patent/TW202311445A/en unknown
- 2022-05-25 KR KR1020220063982A patent/KR20220159292A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220159292A (en) | 2022-12-02 |
| TW202311445A (en) | 2023-03-16 |
| CN115386253A (en) | 2022-11-25 |
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| A621 | Written request for application examination |
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