WO2017169838A1 - 光学物品用活性エネルギー線硬化型樹脂組成物、硬化物及び光学シート - Google Patents
光学物品用活性エネルギー線硬化型樹脂組成物、硬化物及び光学シート Download PDFInfo
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- WO2017169838A1 WO2017169838A1 PCT/JP2017/010628 JP2017010628W WO2017169838A1 WO 2017169838 A1 WO2017169838 A1 WO 2017169838A1 JP 2017010628 W JP2017010628 W JP 2017010628W WO 2017169838 A1 WO2017169838 A1 WO 2017169838A1
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- WIPO (PCT)
- Prior art keywords
- active energy
- meth
- energy ray
- acrylate
- ethylene oxide
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- 125000001741 organic sulfur group Chemical group 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical class CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 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
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the present invention relates to an active energy ray-curable resin composition for optical articles used for cast polymerization applying a curing reaction by irradiation with active energy rays, and an optical sheet obtained by curing the composition.
- the light casting polymerization method is, for example, filling (batch injection) an active energy ray-curable resin composition into a mother mold having a fine shape, interposing it in the mother mold, and then applying the resin composition by ultraviolet rays or the like. This is a method of curing the mold, and a replica of the master mold can be precisely manufactured in large quantities.
- Active energy ray curable resin composition containing, for example, epoxy (meth) acrylate or urethane (meth) acrylate, as an active energy ray curable resin composition for optical articles that has excellent curability and excellent mold reproducibility of the resulting cured product
- a polymer component such as bisphenol A type epoxy (meth) acrylate, monofunctional (meth) acrylate, bifunctional (meth) acrylate, and an acrylic resin having a weight average molecular weight of 95,000.
- an ionizing radiation curable resin composition for a Fresnel lens having a refractive index after curing of 1.55 or more for example, see Patent Document 1
- a polymerizable non-polymerizing compound containing a compound represented by formula (1) A weight average molecular weight obtained by polymerizing a monomer having a saturated double bond and a polymerizable unsaturated monomer is 2,000 to 100,000, and a polymerizable unsaturated double bond is formed in the polymer structure.
- An active energy ray-curable resin composition for optical articles containing a polymer containing, a photopolymerization initiator, and containing the monomer and polymer in a specific ratio is known (for example, (See Patent Document 2).
- the polymer component is not bonded to a crosslinked structure caused by a curing reaction. For this reason, when the content of the polymer component is large, the curability tends to deteriorate.
- the active energy ray-curable resin composition for optical articles described in Patent Document 2 is excellent in mold reproducibility, but sometimes inferior in dimensional stability and curling property.
- a flexible ethylene oxide group is effectively introduced into the main chain of the cured product, and internal stress generated during curing That is, as a result of being able to reduce curing shrinkage, it was found that a cured product in which curling property is suppressed while maintaining scratch resistance can be obtained.
- the present invention also provides an optical sheet obtained by curing the active energy ray-curable composition for optical articles described above with active energy rays.
- an optical sheet having excellent surface reproducibility, scratch resistance, dimensional stability and curl resistance, and having a fine surface shape such as a prism lens sheet and a Fresnel lens sheet.
- the active energy ray polymerizable compound used in the present invention includes (1) a polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group as an essential component, and (2) active energy.
- a polymerizable compound having two or more linear polymerizable groups is contained in an amount of 30 to 70% by weight based on the total amount of the active energy linear polymerizable compound.
- ethylene oxide groups such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, etc.
- Ethylene oxide group-modified di (meth) acrylate obtained by reacting (meth) acrylic acid with diol
- Bisphenol A-type epoxy resin bisphenol F-type epoxy resin, partially halogen-substituted bisphenol A-type epoxy resin, partially halogen-substituted bisphenol F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, and mixtures thereof
- Bisphenol type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy obtained by reaction of one or more epoxy resins selected from the group and plural moles of (meth) acrylic acid (Meth) acrylates, naphthalene skeleton epoxy (meth) acrylates or mixtures thereof,
- urethane (meth) acrylate obtained by reaction of polyol, organic polyisocyanate having a cyclic structure and plural moles of hydroxyl group-containing (meth) acrylate, diol having cyclic structure, organic polyisocyanate and plural moles of hydroxyl group-containing (meth) acrylate
- examples thereof include urethane (meth) acrylate obtained by reaction, urethane (meth) acrylate obtained by reaction of organic polyisocyanate having a cyclic structure and plural moles of hydroxyl group-containing (meth) acrylate.
- the polymerizable compound having two or more active energy ray polymerizable groups may be used alone or in combination of two or more.
- the polymerizable compound having two or more active energy ray polymerizable groups is 30 to 70% by weight based on the total amount of the active energy ray polymerizable compound. Within this range, a cured product having an excellent balance of mechanical properties such as curl resistance and scratch resistance can be obtained.
- the polymerizable compound having two or more active energy ray polymerizable groups is preferably 40 to 60% by weight.
- a polymerizable compound having an aromatic group In the present invention, a polymerizable compound having an aromatic group, a polymerizable compound having a cycloaliphatic structure, a polymerizable compound having a heterocyclic structure, a styrene compound, a polymerizable compound having a linear aliphatic structure, etc.
- the use is preferable because scratch resistance and a high refractive index, which is an essential performance for optical sheets, can be obtained.
- the content of the polymerizable compound having an aromatic group is preferably such that the weight concentration of the aromatic group is 30 to 60% by weight with respect to the total amount of the active energy ray polymerizable compound. 50% by weight is preferred.
- Examples of the polymerizable compound having an aromatic group include (meth) acrylic acid esters having an aromatic ring.
- (meth) acrylic acid esters having an aromatic ring include benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate.
- 2-hydroxy-3-phenoxypropyl (meth) acrylate 2-phenyl-2- (4-acryloyloxyphenyl) propane, 2-phenyl-2- (4-acryloyloxyalkoxyphenyl) propane, 2,4,6 -Trichlorophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-trichlorobenzyl (meth) acrylate, 2,4,6-tribromobenzyl (meth) acrylate, 2, , 4,6-tric Lorophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, o-phenylphenol (poly) ethoxy (meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate, etc. Can be mentioned.
- Examples of the polymerizable compound having a cycloaliphatic structure include (meth) acrylic acid esters having a cycloaliphatic group.
- Examples of (meth) acrylic acid esters having a cycloaliphatic group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and tetrahydroflurane.
- Examples include furyl (meth) acrylate, glycidyl cyclocarbonate (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate.
- styrene compound examples include styrene, ⁇ -methylstyrene, chlorostyrene and the like.
- heterocyclic compound examples include N-vinylpyrrolidone, N-vinylcaprolactone, acryloylformoline, tris (2-hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, and 1 to 20 mol of them.
- examples include compounds having an isocyanuric acid structure in which (meth) acrylic acid is ester-bonded to a compound having a hydroxyl group such as a hydroxyl group-containing compound obtained by ring-opening addition of alkylene oxide or ⁇ -caprolactone.
- Polymerizable compound having two or more active energy ray polymerizable groups, an ethylene oxide group, and an aromatic group a polymerizable compound having two or more active energy ray polymerizable groups, an ethylene oxide group, and an aromatic group.
- examples of such polymerizable compounds include ethylene oxide group-modified epoxy poly (meth) acrylate, ethylene oxide modified bisphenol A epoxy poly (meth) acrylate, ethylene oxide modified bisphenol F epoxy poly (meth) acrylate, and ethylene oxide modified bisphenol. S epoxy poly (meth) acrylate and the like.
- the ethylene oxide group contained in these ethylene oxide group-modified epoxy poly (meth) acrylates preferably has an average value of 1 to 30 repeating units per molecule.
- the polymerizable compound having two or more ethylene oxide groups and active energy ray polymerizable groups may be used singly or in combination.
- a mixture of a plurality of types for example, a combination of an ethylene oxide addition diacrylate of bisphenol A and an acrylate of an ethylene oxide addition product of dipentaerythritol, an ethylene oxide addition diacrylate of bisphenol A, and trimethylolpropane A combination with an acrylate of an ethylene oxide adduct is often preferred.
- a polymerizable compound having one active energy ray polymerizable group (sometimes referred to as a monofunctional monomer) may be used in combination.
- a known monomer can be used as the monofunctional monomer without any particular limitation.
- Silyl group-containing (meth) acrylates such as ⁇ -methacryloxypropyltrimethoxysilane; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylamino N, N-dialkylaminoalkyl (meth) acrylates such as propyl (meth) acrylate;
- R 1 is a hydrogen atom
- R 2 is a hydrogen atom or a methyl group
- the average value of n is a number of 1 to 5.
- the compound represented by the formula (1) can be obtained, for example, by reacting (meth) acrylic acid with a reaction product of p-phenylphenol or o-phenylphenol and ethylene oxide or propylene oxide.
- a reaction product of p-phenylphenol or o-phenylphenol and ethylene oxide or propylene oxide can be easily obtained from the market.
- New Pole OPE-20 manufactured by Sanyo Chemical Co., Ltd. (1 mol of o-phenylphenol reacted with 2 mol of ethylene oxide)
- New Pole OPE-40 (1 mol of o-phenylphenol with 4 mol of ethylene oxide) And the like can be used.
- Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; thioxanthones; acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;
- the photopolymerization initiator may be used alone or in combination of two or more.
- the amount used is not particularly limited, but in order to maintain good sensitivity and prevent precipitation of crystals, physical properties of the coating film, etc., to 100 parts by weight of the active energy ray-curable resin composition for optical articles of the present invention. 0.05 to 20 parts by weight is preferably used, and 0.1 to 10 parts by weight is particularly preferable.
- various photosensitizers can be used in combination with the photopolymerization initiator.
- the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
- the photopolymerization initiator is preferably an initiator having a light-absorbing ability in the long wavelength region.
- a photopolymerization initiator that exhibits the photoinitiating ability in the range of 360 to 450 nm is preferable.
- the active energy ray-curable resin composition for optical articles of the present invention can be used in combination with a resin or the like for the purpose of improving viscosity or adhesion to a transparent substrate.
- a resin or the like for the purpose of improving viscosity or adhesion to a transparent substrate.
- acrylic resin such as methyl methacrylate resin and methyl methacrylate copolymer
- polyester resin polyurethane resin
- polybutadiene resin such as polybutadiene and butadiene-acrylonitrile copolymer
- bisphenol type examples thereof include epoxy resins such as epoxy resins, phenoxy resins, and novolac-type epoxy resins.
- antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.
- tan ⁇ max in dynamic viscoelasticity can also be mentioned.
- the peak value of Tan ⁇ max indicates the distribution of molecular weight between cross-linking points in the cross-linked structure, and when the peak value is low and broad, the distribution of molecular weight between cross-linking points is wide and the curling property is good because the curing shrinkage is dispersed.
- the peak value is high and sharp, the distribution of molecular weight between cross-linking points is uniform, and shrinkage occurs at the time of curing.
- the scratch resistance can be increased by broadening the distribution of the molecular weight between the cross-linking points, so that the toughness of the cured resin can be increased. It is more preferable to design low.
- Table 2 shows the results of Examples and Comparative Examples.
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- Polymers & Plastics (AREA)
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
このうち、光注型重合法は、例えば、微細な形状を賦した母型に活性エネルギー線硬化型樹脂組成物を充填(一括注入)し、母型に介在させ、紫外線などによって該樹脂組成物を硬化させる方法であり、母型の複製を精密に大量に製造することができる。
エチレンオキサイド骨格を構造に有する活性エネルギー線重合性基を2つ以上有する重合性化合物を用いることで、硬化物の主鎖に柔軟なエチレンオキサイド基を効果的に導入し、硬化時に発生する内部応力即ち硬化収縮を低減することが出来た結果、耐スクラッチ性を維持した上でカール性の抑制された硬化物を得られることを見出した。
(1)活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物を含有し、該エチレンオキサイド基の重量濃度が前記活性エネルギー線重合性化合物全量に対し6.0~15.0重量%であり、
(2)活性エネルギー線重合性基を2つ以上有する重合性化合物を前記活性エネルギー線重合性化合物全量に対し30~70重量%含有する光学物品用活性エネルギー線硬化性組成物を提供する。
本発明で使用する活性エネルギー線重合性化合物は、(1)活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物を必須成分として含有し、且つ(2)活性エネルギー線重合性基を2つ以上有する重合性化合物を前記活性エネルギー線重合性化合物全量に対し30~70重量%含有する。
本発明で使用する活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物としては、特に限定なく公知のものを使用できる。
(なお本発明において、ジ(メタ)アクリレートは(メタ)アクリロイル基を2個有する化合物を表し、トリ(メタ)アクリレートは(メタ)アクリロイル基を3個有する化合物を表し、ポリ(メタ)アクリレートは(メタ)アクリロイル基を2個以上有する化合物を表し、(メタ)アクリレートはアクリレート及びメタクリレートの総称を表し、(メタ)アクリロイル基はアクリロイル基及びメタクリロイル基の総称を表す。またエチレンオキサイドはEOと略す場合がある)
本発明で使用する活性エネルギー線重合性基を2つ以上有する重合性化合物としては、特に限定されることはなく公知の化合物を使用することができる。
例えば、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、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、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(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)アクリレートや、
本発明においては、芳香族基を有する重合性化合物、環状脂肪族構造を有する重合性化合物、複素環構造を有する重合性化合物、スチレン系化合物、直鎖状脂肪族構造を有する重合性化合物等を使用することは、耐スクラッチ性や、光学シートに必須性能である高屈折率を得ることができ好ましい。例えば、前記芳香族基を有する重合性化合物の含有量は、芳香族基の重量濃度が前記活性エネルギー線重合性化合物全量に対し30~60重量%となるようにすることが好ましく、中でも30~50重量%が好ましい。
また、前記活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有し、且つ芳香族基を有する重合性化合物を使用することももちろん好ましい。このような重合性化合物としては、エチレンオキサイド基変性エポキシポリ(メタ)アクリレートである、エチレンオキサイド変性ビスフェノールAエポキシポリ(メタ)アクリレート、エチレンオキサイド変性ビスフェノールFエポキシポリ(メタ)アクリレート、エチレンオキサイド変性ビスフェノールSエポキシポリ(メタ)アクリレート等が挙げられる。これらのエチレンオキサイド基変性エポキシポリ(メタ)アクリレートが有するエチレンオキサイド基は、1分子中平均値で1~30個の繰り返し単位数を有することが好ましい。
このことから、活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物は、複数の活性エネルギー線重合性基の間にエチレンオキサイド鎖が存在するような構造であることが好ましい。
本発明においては、活性エネルギー線重合性基を1つ有する重合性化合物(単官能モノマーと称する場合がある)を併用してもよく好ましい。単官能モノマーとしては特に限定なく公知のモノマーを使用することができる。
式(1)で表される化合物は、例えばp-フェニルフェノール或いは、o-フェニルフェノールとエチレンオキサイド或いは、プロピレンオキサイドとの反応物と(メタ)アクリル酸を反応させることにより得ることができる。p-フェニルフェノール或いはo-フェニルフェノールとエチレンオキサイド或いは、プロピレンオキサイドの反応物は、市場より容易に入手できる。例えば、三洋化成(株)製、ニューポールOPE-20(o-フェニルフェノール1モルにエチレンオキサイド2モルを反応させたもの。)ニューポールOPE-40(o-フェニルフェノール1モルにエチレンオキサイド4モルを反応させたもの。)等を使用することができる。
本発明で用いる光重合開始剤としては、例えば、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類;
本発明の硬化物は本発明の光学物品用活性エネルギー線硬化型樹脂組成物を硬化させてなるものである。該硬化物は、微細形状を賦した樹脂硬化層に加わる圧力が小さい場合は変形しない程度の硬さを有し、また一時的に強い圧力が加わった場合にも形状が崩れない(硬脆くない)ためには、25℃における動的粘弾性での弾性率が2500MPa~3000であることが好ましく、2700~2900MPaがより好ましい。
同様にカールに関しても、弾性率が高いほど硬化収縮による影響が発現し易いので、物性バランスを考えて上記範囲内で設計することが好ましい。
本発明の光学物品用活性エネルギー線硬化型樹脂組成物を硬化させる活性エネルギー線は、電磁波または荷電粒子線のうち、分子を重合、架橋しうるエネルギー量子を有するものを意味し、例えば、可視光線、紫外線、X線等の電磁波、または電子線等の荷電粒子線が挙げられる。これらの内で実用上良く用いられるのは、可視光線、紫外線である。紫外線の場合には、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク、ブラックライトランプ、メタルハライドランプ等の光源を用いることができる。
本発明の光学シートを製造する方法としては、本発明の光学物品用活性エネルギー線硬化型樹脂組成物を、必要とされる微細形状を有する母型上に充填した後、充填された該樹脂組成物上にプラスチック基材を空気が混入しないように加圧積層して密着させ、プラスチック基材側から紫外線等の活性エネルギー線を照射して該樹脂組成物を硬化させた後、母型から離型する方法などが挙げられる。また例えば、ロール状の母型に該樹脂組成物を連続的に充填した後、充填された該樹脂組成物上にプラスチック基材を空気が混入しないように連続的に密着させ、プラスチック基材側から紫外線等の活性エネルギー線を照射して該樹脂組成物を硬化させた後、ロール状の母型から離型する連続製造方法などが挙げられる。
下記表1に示すような配合で組成物を調整した。また、各成分の該エチレンオキサイド基の重量濃度や芳香族基の重量濃度は、各構造成分の構造式より算出した。
ユニディック V-5500 (DIC社製、BPA型エポキシアクリレート)
芳香環量:33.7%、EO鎖含有量:0%
TMP3EO-3A:トリメチロールプロパンのEO変性(n=3)トリアクリレート
芳香環量:0%、EO鎖含有量:18%
BPA4EO-2A:BPAのEO変性(n=4)ジアクリレート
芳香環量:30.5%、EO鎖含有量:31.2%
オルソフェノキシフェニルエチルアクリレート
芳香環量:58.2%、EO鎖含有量:16.4%
フェノキシエチルアクリレート
芳香環量:40.6%、EO鎖含有量:20.8%
ベンジルアクリレート
芳香環量:48.1%、EO鎖含有量:0%
DP6A/DP5A=6/4:ジペンタエリスリトールヘキサアクリレート/ジペンタエリスリトールペンタアクリレート=6/4
芳香環量:0%、EO鎖含有量:0%
h)DP-EO-6A/DP-EO-5A=6/4:ジペンタエリスリトールのEO変性ヘキサアクリレート/ジペンタエリスリトールのEO変性ペンタアクリレート=6/4 (EO重合度:0.85)
芳香環量:0%、EO鎖含有量:26.7%
i)I-184:1-ヒドロキシ-シクロヘキシルーフェニルーケトン(光開始剤)イルガキュア184[BASF社製]
硬化物の作成方法、及び評価方法は以下のように行った。
(硬化物の作成方法)
ガラス板に実施例または比較例の樹脂組成物を滴下し、スピンコーターにて膜厚100μmとなるように塗装した後、窒素雰囲気下でUV照射を行い硬化塗膜を作成した。照射条件は、アイグラフィックス社製のメタルハライドランプにて積算光量1000mJ/cm2で行った。その後、ガラス板より硬化物である樹脂フィルムを剥がし、3mm×50mmに裁断して試験片とした。
樹脂フィルムのTg、貯蔵弾性率、及びtanδmax(ピーク高さ)の測定には、粘弾性測定装置としてRheometoric Scientific社製の「RSAII」を用い、測定条件は昇温スピード:3℃/Min、周波数:3.5Hzで行った。
75μmのPETフィルム(東洋紡社製:コスモシャインA4300)を基材として、実施例または比較例の樹脂組成物を塗装し、窒素雰囲気下、窒素雰囲気下でUV照射を行い(照射条件は、アイグラフィックス社製のメタルハライドランプにて積算光量1000mJ/cm2)、プリズムシート(ピッチ間隔20μm)を作成した。
作成したプリズムシートを5cm角に裁断し、1日室温で放置した後、4隅の反り(カール)の程度をメージャーにてミリ単位で計測し、4隅の合計値をカール性の指標とした。値が低いほど、カールしていないことを示す。本評価においては10mm以下であれば合格とした。
上記と同様の条件で作成したプリズムシートの上に、偏光フィルムを重ね合わせ、その上に錘を乗せた。この状態でプリズムシートのみを引っ張り、プリズムシート表面にできた傷の程度を目視にて観察した。
錘の重さを変えて試験し、傷がつかなかった最大の重量(g)を耐スクラッチ性の値とした。値が高いほど、耐スクラッチに優れる。本評価においては、100g以上であれば合格とした。
Claims (5)
- 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する光学物品用活性エネルギー線硬化性組成物であって、
(1)活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物を含有し、該エチレンオキサイド基の重量濃度が前記活性エネルギー線重合性化合物全量に対し6.0~15.0重量%であり、
(2)活性エネルギー線重合性基を2つ以上有する重合性化合物を前記活性エネルギー線重合性化合物全量に対し30~70重量%含有することを特徴とする光学物品用活性エネルギー線硬化性組成物。 - 前記活性エネルギー線重合性基を2つ以上有し且つエチレンオキサイド基を有する重合性化合物がジペンタエリスリトールのエチレンオキサイド変性ポリ(メタ)アクリレートである請求項1に記載の光学物品用活性エネルギー線硬化性組成物。
- 芳香族基の重量濃度が前記活性エネルギー線重合性化合物全量に対し30~60重量%である請求項1または2に記載の光学物品用活性エネルギー線硬化性組成物。
- 請求項1~3のいずれかに記載の光学物品用活性エネルギー線硬化性組成物を活性エネルギー線で硬化させた硬化物。
- 請求項1~3のいずれかに記載の光学物品用活性エネルギー線硬化性組成物を活性エネルギー線で硬化させた光学シート。
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