TWI647271B - Active energy ray-curable composition, hardened product, optical part, and method for producing active energy ray-curable composition - Google Patents
Active energy ray-curable composition, hardened product, optical part, and method for producing active energy ray-curable composition Download PDFInfo
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- TWI647271B TWI647271B TW105110845A TW105110845A TWI647271B TW I647271 B TWI647271 B TW I647271B TW 105110845 A TW105110845 A TW 105110845A TW 105110845 A TW105110845 A TW 105110845A TW I647271 B TWI647271 B TW I647271B
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- Prior art keywords
- active energy
- energy ray
- curable composition
- acrylate
- alkoxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 230000003287 optical effect Effects 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 238000002834 transmittance Methods 0.000 claims abstract description 13
- -1 titanium alkoxide Chemical class 0.000 claims description 45
- 150000004703 alkoxides Chemical class 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 14
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- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 125000006353 oxyethylene group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 10
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- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 14
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- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 11
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 11
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 7
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 6
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- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 3
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- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 3
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- OJNNAJJFLWBPRS-UHFFFAOYSA-N phenyl-[(2,4,6-trimethylphenyl)methyl]-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=CC2=C(C=C(C=C2C)C)C)C(=CC(=C1)C)C OJNNAJJFLWBPRS-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 2
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
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- 238000010894 electron beam technology Methods 0.000 description 2
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- ITKPCHYKBRFJPV-UHFFFAOYSA-N (2-phenylphenyl) prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1C1=CC=CC=C1 ITKPCHYKBRFJPV-UHFFFAOYSA-N 0.000 description 1
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- YRRAEYCMWVQGAG-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-phenylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)C1=CC=CC=C1 YRRAEYCMWVQGAG-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000002390 adhesive tape Substances 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- UBPIRRORRFGPNE-UHFFFAOYSA-N benzoic acid;formic acid Chemical compound OC=O.OC(=O)C1=CC=CC=C1 UBPIRRORRFGPNE-UHFFFAOYSA-N 0.000 description 1
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 description 1
- HSOHBWMXECKEKV-UHFFFAOYSA-N cyclooctanamine Chemical compound NC1CCCCCCC1 HSOHBWMXECKEKV-UHFFFAOYSA-N 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 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 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical compound CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- SEGJNMCIMOLEDM-UHFFFAOYSA-N n-methyloctan-1-amine Chemical compound CCCCCCCCNC SEGJNMCIMOLEDM-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本發明之目的在於提供一種活性能量線硬化性組成物，其係高折射率且透明性優異之活性能量線硬化性組成物，可製造傷痕之恢復性優異，且與塑膠基材的密接性高之硬化物。 An object of the present invention is to provide an active energy ray-curable composition, which is an active energy ray-curable composition having a high refractive index and excellent transparency, which is excellent in recovering wounds, and has high adhesion to a plastic substrate. Of hardened.
本發明之活性能量線硬化性組成物係含有金屬氧化物(A)、具有芳香環骨架之(甲基)丙烯酸酯(B)及光聚合起始劑(C)之活性能量線硬化性組成物(D)，其特徵在於：上述活性能量線硬化性組成物(D)於25℃之折射率為1.56~1.70，且上述活性能量線硬化性組成物(D)之總光線透射率為90%以上。 The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton, and a photopolymerization initiator (C). (D), characterized in that the refractive index of the active energy ray-curable composition (D) at 25 ° C is 1.56 to 1.70, and the total light transmittance of the active energy ray-curable composition (D) is 90% the above.
Description
本發明係關於一種活性能量線硬化性組成物、其硬化物、由硬化物而獲得之各種光學零件及該活性能量線硬化性組成物之製造方法。詳細而言，係關於一種高折射率且透明性優異之活性能量線硬化性組成物。 The present invention relates to an active energy ray-curable composition, a cured product thereof, various optical parts obtained from the cured product, and a method for manufacturing the active energy ray-curable composition. More specifically, it relates to an active energy ray-curable composition having a high refractive index and excellent transparency.
以往，使用於液晶顯示器之稜鏡片或使用於投影TV之菲涅耳透鏡、柱狀透鏡(lenticular lens)等光學透鏡，係藉由將活性能量線硬化性組成物流入至內面設置有樹脂基材之模具內，並照射活性能量線使其硬化而製造。 In the past, optical lenses such as Fresnel lenses for liquid crystal displays, Fresnel lenses, and lenticular lenses used for projection TVs have resin-based materials that flow into the inner surface of the active energy ray-hardening composition. It is manufactured by irradiating an active energy ray in a metal mold to harden it.
近年來，隨著顯示器之高亮度化，正在嘗試提昇光學透鏡之亮度，為了該目的，例如正研究使金屬氧化物之微粒子分散於高折射率樹脂之技術(專利文獻1)。 In recent years, with the increase in the brightness of displays, attempts have been made to increase the brightness of optical lenses. For this purpose, for example, a technique of dispersing fine particles of metal oxide in a high refractive index resin is being studied (Patent Document 1).
專利文獻1之使金屬氧化物的微粒子分散之方法必須使高折射率樹脂中含有分散劑及有機溶劑，使利用該方法所製造之高折射率樹脂進行硬化而製造之硬化物之中會殘留有機溶劑。若於硬化物之中殘留有機溶劑，則存在因於組裝時、搬送時與其他構件接觸而產生傷痕之問題。 又，若含有金屬氧化物之微粒子則硬化物之透明性受損，故而難以同時實現高折射率及透明性。 In the method for dispersing fine particles of metal oxides in Patent Document 1, it is necessary to contain a dispersant and an organic solvent in the high refractive index resin, and organic matter will remain in the hardened product manufactured by curing the high refractive index resin manufactured by this method. Solvent. If an organic solvent remains in the hardened material, there is a problem that a flaw occurs due to contact with other members during assembly and during transportation. Moreover, if the fine particles containing metal oxides impair the transparency of the hardened material, it is difficult to achieve high refractive index and transparency at the same time.
專利文獻1：日本特開2010-248505號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2010-248505
本發明之目的在於提供一種活性能量線硬化性組成物，其係高折射率且透明性優異之活性能量線硬化性組成物，可製造傷痕之恢復性優異，且與塑膠基材之密接性高之硬化物。 An object of the present invention is to provide an active energy ray-curable composition, which is an active energy ray-curable composition having a high refractive index and excellent transparency, which is excellent in recovering wounds and has high adhesion to a plastic substrate. Of hardened.
本發明人等為了達成上述目的進行了研究，結果達成了本發明。 The present inventors have conducted studies in order to achieve the above-mentioned object, and as a result, have reached the present invention.
即，本發明係：(1)一種活性能量線硬化性組成物，其係含有金屬氧化物(A)、具有芳香環骨架之(甲基)丙烯酸酯(B)及光聚合起始劑(C)之活性能量線硬化性組成物(D)，其特徵在於：上述活性能量線硬化性組成物(D)於25℃之折射率為1.56~1.70，上述活性能量線硬化性組成物(D)之總光線透射率為90%以上；(2)一種硬化物，其係使上述本發明之活性能量線硬化性組成物進行硬化而成；(3)一種光學零件，其使用有上述本發明之硬化物；(4)以及一種活性能量線硬化性組成物之製造方法，其製造上述本發 明之活性能量線硬化性組成物，其特徵在於含有如下步驟：反應液製作步驟：以金屬烷氧化物(a1)與水之莫耳比成為金屬烷氧化物(a1)/水=2.0~200之方式將上述金屬烷氧化物(a1)及上述水加入至具有芳香環骨架之(甲基)丙烯酸酯(B)而製成反應液；反應步驟：使上述反應液中之上述金屬烷氧化物(a1)與上述水進行反應而製成金屬氧化物(A)；及光聚合起始劑添加步驟：於上述反應液加入光聚合起始劑(C)。 That is, the present invention is: (1) an active energy ray-curable composition containing a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton, and a photopolymerization initiator (C ) Of the active energy ray-curable composition (D), characterized in that the refractive index of the active energy ray-curable composition (D) at 25 ° C is 1.56 to 1.70, and the active energy ray-curable composition (D) The total light transmittance is 90% or more; (2) a hardened product which is obtained by hardening the active energy ray-curable composition of the present invention; (3) an optical part using the above-mentioned invention of the present invention; Hardened material; (4) and a method for producing an active energy ray-curable composition, which manufactures the present invention Ming's active energy ray-curable composition is characterized in that it contains the following steps: a reaction solution production step: the molar ratio of the metal alkoxide (a1) to water becomes metal alkoxide (a1) / water = 2.0 to 200 The method comprises adding the above-mentioned metal alkoxide (a1) and the above-mentioned water to the (meth) acrylate (B) having an aromatic ring skeleton to prepare a reaction solution; a reaction step: making the above-mentioned metal alkoxide ( a1) reacting with the water to prepare a metal oxide (A); and a photopolymerization initiator adding step: adding a photopolymerization initiator (C) to the reaction solution.
本發明之活性能量線硬化性組成物發揮如下效果：其折射率高，透明性優異，又，其硬化物之傷痕之恢復性優異，與塑膠基材之密接性高。 The active energy ray-curable composition of the present invention exhibits the following effects: its refractive index is high, its transparency is excellent, and its cured material has excellent recoverability of scars, and its adhesiveness to plastic substrates is high.
本發明之活性能量線硬化性組成物係含有金屬氧化物(A)、具有芳香環骨架之(甲基)丙烯酸酯(B)及光聚合起始劑(C)之活性能量線硬化性組成物(D)，其特徵在於：上述活性能量線硬化性組成物(D)於25℃之折射率為1.56~1.70，上述活性能量線硬化性組成物(D)之總光線透射率為90%以上。 The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton, and a photopolymerization initiator (C). (D), characterized in that the refractive index of the active energy ray-curable composition (D) at 25 ° C is 1.56 to 1.70, and the total light transmittance of the active energy ray-curable composition (D) is 90% or more .
於本說明書中，所謂折射率，意指於25℃之波長589nm之光的折射率。 In this specification, the refractive index means the refractive index of light having a wavelength of 589 nm at 25 ° C.
於本說明書中，所謂總光線透射率，意指依據JIS-K7105所測得之總 光線透射率。 In this specification, the total light transmittance means the total light transmittance measured according to JIS-K7105. Light transmittance.
本發明之活性能量線硬化性組成物所含有之金屬氧化物(A)，較佳為與具有芳香環骨架之(甲基)丙烯酸酯(B)的相溶性優異之金屬氧化物。 The metal oxide (A) contained in the active energy ray-curable composition of the present invention is preferably a metal oxide having excellent compatibility with the (meth) acrylate (B) having an aromatic ring skeleton.
若金屬氧化物(A)與具有芳香環骨架之(甲基)丙烯酸酯(B)之相溶性優異，則活性能量線硬化性組成物(D)的折射率變高。 When the metal oxide (A) has excellent compatibility with the (meth) acrylate (B) having an aromatic ring skeleton, the refractive index of the active energy ray-curable composition (D) becomes high.
就折射率之觀點而言，作為金屬氧化物(A)，例如可列舉鋯、鈦、鉿、鋅、鋁、鎵、銦、鍺及錫之氧化物。 From the viewpoint of refractive index, examples of the metal oxide (A) include oxides of zirconium, titanium, hafnium, zinc, aluminum, gallium, indium, germanium, and tin.
又，金屬氧化物(A)較佳為金屬烷氧化物(a1)與水反應所獲得者。 The metal oxide (A) is preferably obtained by reacting a metal alkoxide (a1) with water.
作為金屬烷氧化物(a1)，例如可列舉：鈦烷氧化物、鋯烷氧化物、鉿烷氧化物、鋅烷氧化物、鋁烷氧化物、鎵烷氧化物、銦烷氧化物、鍺烷氧化物、錫烷氧化物等。 Examples of the metal alkoxide (a1) include titanium alkoxide, zirconium oxide, hafnium oxide, zinc alkoxide, aluminoxide, gallium alkoxide, indium alkoxide, and germane Oxides, tin oxides, etc.
作為鋯烷氧化物，例如可列舉鋯四正丁氧化物，作為鈦烷氧化物，例如可列舉鈦四正丁氧化物。 Examples of the zirconium oxide include zirconium tetra-n-butoxide, and examples of the titanium alkoxide include titanium tetra-n-butoxide.
又，本發明之活性能量線硬化性組成物中，金屬氧化物(A)較佳為下述金屬氧化物：藉由使金屬烷氧化物(a1)與水以莫耳比成為金屬烷氧化物(a1)/水=2.0~200之方式，於具有芳香環骨架之(甲基)丙烯酸酯(B)中進行反應而生成之金屬氧化物。 Further, in the active energy ray-curable composition of the present invention, the metal oxide (A) is preferably a metal oxide which becomes a metal alkoxide by a molar ratio of the metal alkoxide (a1) and water. (a1) /water=2.0 to 200. A metal oxide formed by a reaction in a (meth) acrylate (B) having an aromatic ring skeleton.
若上述莫耳比未達2.0，則活性能量線硬化性組成物(D)之透明性變得不充分。 When the molar ratio is less than 2.0, the transparency of the active energy ray-curable composition (D) becomes insufficient.
又，若上述莫耳比超過200，則活性能量線硬化性組成物(D)之折射 率變低。 When the Mohr ratio is more than 200, refraction of the active energy ray-curable composition (D) The rate becomes low.
本發明之活性能量線硬化性組成物中，上述金屬氧化物(A)之平均粒徑較佳為10nm以下，更佳為1~5nm。 In the active energy ray-curable composition of the present invention, the average particle diameter of the metal oxide (A) is preferably 10 nm or less, and more preferably 1 to 5 nm.
若金屬氧化物(A)之平均粒徑為10nm以下，則發揮總光線透射率變高之效果。 When the average particle diameter of the metal oxide (A) is 10 nm or less, the effect of increasing the total light transmittance is exhibited.
再者，於本說明書中，所謂「金屬氧化物(A)之平均粒徑為10nm以下」，意指於藉由動態光散射法進行之測量中，金屬氧化物(A)之平均粒徑被分析為10nm以下之數值；或於藉由動態光散射法進行之測量中，金屬氧化物(A)之平均粒徑被分析為未達檢測極限之大小。 In addition, in this specification, "the average particle diameter of the metal oxide (A) is 10 nm or less" means that the average particle diameter of the metal oxide (A) is measured by a dynamic light scattering method. The analysis is a value of 10 nm or less; or in the measurement by the dynamic light scattering method, the average particle diameter of the metal oxide (A) is analyzed to a size that does not reach the detection limit.
本發明之活性能量線硬化性組成物含有具有芳香環骨架之(甲基)丙烯酸酯(B)。藉由使用具有芳香環骨架之(甲基)丙烯酸酯(B)，本發明之活性能量線硬化性組成物(D)之折射率適當地變高。 The active energy ray-curable composition of the present invention contains a (meth) acrylate (B) having an aromatic ring skeleton. By using the (meth) acrylate (B) having an aromatic ring skeleton, the refractive index of the active energy ray-curable composition (D) of the present invention is appropriately increased.
作為具有芳香環骨架之(甲基)丙烯酸酯(B)，較理想為分子內具有氧伸烷基(oxyalkylene group)之(甲基)丙烯酸酯。又，更理想為上述氧伸烷基為氧伸乙基(oxyethylene group)。作為此種具有芳香環骨架之(甲基)丙烯酸酯(B)，例如可列舉：(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、鄰、間或對苯基苯酚之單(甲基)丙烯酸酯、3,3'-二苯基-4,4'-二羥基聯苯之單(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、雙酚A之環氧乙烷加成物之二(甲基)丙烯酸酯、茀之環氧乙烷加成物之二(甲基)丙烯酸酯等。 The (meth) acrylate (B) having an aromatic ring skeleton is preferably a (meth) acrylate having an oxyalkylene group in the molecule. The oxyalkylene group is more preferably an oxyethylene group. Examples of such a (meth) acrylate (B) having an aromatic ring skeleton include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and o-, m-, or p-phenylphenol. Mono (meth) acrylate, 3,3'-diphenyl-4,4'-dihydroxy biphenyl mono (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate , Bisphenol A ethylene oxide adduct di (meth) acrylate, tritium ethylene oxide adduct di (meth) acrylate, and the like.
該等具有芳香環骨架之(甲基)丙烯酸酯(B)之中，更佳為(甲基)丙烯酸苯氧基乙酯、鄰、間或對苯基苯酚之單(甲基)丙烯酸酯、鄰、間或對苯基苯氧基(氧烷基(oxyalkyl))加成物之(甲基)丙烯酸酯、茀之環氧乙烷 加成物之(甲基)丙烯酸酯及茀之環氧乙烷加成物之二(甲基)丙烯酸酯。 Among these (meth) acrylates (B) having an aromatic ring skeleton, phenoxyethyl (meth) acrylate, mono (meth) acrylate of o-, m-, or p-phenylphenol, (Meth) acrylic acid esters of ortho-, m- or p-phenylphenoxy (oxyalkyl) adducts (Meth) acrylates of adducts and di (meth) acrylates of adducts of ethylene oxide.
該等之中，進而較佳為丙烯酸苯氧基乙酯、丙烯酸鄰苯基苯氧基乙酯、加成6莫耳環氧乙烷之茀丙烯酸酯、加成10莫耳環氧乙烷之茀丙烯酸酯。 Of these, phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, fluorene acrylate with 6 mol ethylene oxide, and fluorene acrylate with 10 mol ethylene oxide are more preferred. ester.
若具有芳香環骨架之(甲基)丙烯酸酯(B)為該等化合物，則活性能量線硬化性組成物(D)之折射率適當地變高。 When the (meth) acrylate (B) having an aromatic ring skeleton is such a compound, the refractive index of the active energy ray-curable composition (D) is appropriately increased.
本發明之活性能量線硬化性組成物含有光聚合起始劑(C)。作為光聚合起始劑(C)，例如可列舉：氧化膦(phosphine oxide)系化合物(C1)、苯甲醯甲酸酯系化合物(C2)、9-氧硫系化合物(C3)、肟酯系化合物(C4)、羥基苯甲醯基系化合物(C5)、二苯甲酮系化合物(C6)、縮酮系化合物(C7)、1,3-α胺基烷基苯酮系化合物(C8)等。 The active energy ray-curable composition of the present invention contains a photopolymerization initiator (C). Examples of the photopolymerization initiator (C) include phosphine oxide-based compounds (C1), benzoic acid formate-based compounds (C2), and 9-oxysulfur. Compound (C3), oxime ester compound (C4), hydroxybenzyl compound (C5), benzophenone compound (C6), ketal compound (C7), 1,3-α amino group Alkyl phenone compounds (C8) and the like.
作為氧化膦系化合物(C1)，可列舉雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等。 Examples of the phosphine oxide-based compound (C1) include bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, and 2,4,6-trimethylbenzylidene diphenyl oxide. Phosphine, etc.
作為苯甲醯甲酸酯系化合物(C2)，可舉苯甲醯甲酸甲酯等。 Examples of the benzoic acid formate compound (C2) include methyl benzoic acid and the like.
作為9-氧硫系化合物(C3)，可舉異丙基-9-氧硫等。 As 9-oxysulfur Compounds (C3), such as isopropyl-9-oxysulfur Wait.
作為肟酯系化合物(C4)，可列舉1,2-辛烷二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)等。 Examples of the oxime ester compound (C4) include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzidine oxime), and ethyl ketone, 1 -[9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime) and the like.
作為羥基苯甲醯基系化合物(C5)，可列舉：2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、安息香烷基醚等。 Examples of the hydroxybenzyl group-based compound (C5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, and benzoin alkyl ether.
作為二苯甲酮系化合物(C6)，可舉二苯甲酮等。 Examples of the benzophenone-based compound (C6) include benzophenone.
作為縮酮系化合物(C7)，可舉苄基二甲基縮酮等。 Examples of the ketal-based compound (C7) include benzyldimethyl ketal and the like.
作為1,3-α胺基烷基苯酮系化合物(C8)，可列舉：2-甲基-1-(4-甲硫基苯基)-2-啉基丙烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]-1-丁酮等。 Examples of the 1,3-αaminoalkyl phenone compound (C8) include 2-methyl-1- (4-methylthiophenyl) -2- Phenylpropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] -1-butanone and the like.
該等光聚合起始劑(C)之中，就本發明之活性能量線硬化性組成物之硬化性及藉由活性能量線使本發明之活性能量線硬化性組成物硬化而製造的硬化物之著色的觀點而言，較佳為氧化膦系化合物(C1)，進而較佳為雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦。 Among these photopolymerization initiators (C), a hardened product produced by curing the active energy ray-curable composition of the present invention and hardening the active energy ray-curable composition of the present invention by the active energy ray From the viewpoint of coloring, a phosphine oxide-based compound (C1) is preferred, and bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide is more preferred, and 2,4,6- Trimethylbenzylidene diphenylphosphine oxide.
本發明之活性能量線硬化性組成物中，較佳上述金屬氧化物(A)之含量基於上述金屬氧化物(A)與上述具有芳香環骨架之(甲基)丙烯酸酯(B)的合計重量為5~50重量%，更佳為10~40重量%。若金屬氧化物(A)之含量為5重量%以上，則活性能量線硬化性組成物(D)之折射率充分地變高。 In the active energy ray-curable composition of the present invention, the content of the metal oxide (A) is preferably based on the total weight of the metal oxide (A) and the (meth) acrylate (B) having an aromatic ring skeleton. It is 5 to 50% by weight, and more preferably 10 to 40% by weight. When the content of the metal oxide (A) is 5% by weight or more, the refractive index of the active energy ray-curable composition (D) becomes sufficiently high.
若金屬氧化物(A)之含量為50重量%以下，則活性能量線硬化性組成物(D)之透明性變得充分。 When the content of the metal oxide (A) is 50% by weight or less, the transparency of the active energy ray-curable composition (D) becomes sufficient.
本發明之活性能量線硬化性組成物中，較佳上述具有芳香環骨架之(甲基)丙烯酸酯(B)之含量基於上述金屬氧化物(A)與上述具有芳香環骨架之(甲基)丙烯酸酯(B)的合計重量為50~95重量%，更佳為60~85重量%。若具有芳香環骨架之(甲基)丙烯酸酯(B)之含量為上述範圍，則活性能量線硬化性組成物(D)之折射率充分地變高。 In the active energy ray-curable composition of the present invention, the content of the (meth) acrylate (B) having an aromatic ring skeleton is preferably based on the metal oxide (A) and the (meth) having an aromatic ring skeleton. The total weight of the acrylate (B) is 50 to 95% by weight, and more preferably 60 to 85% by weight. When the content of the (meth) acrylate (B) having an aromatic ring skeleton is in the above range, the refractive index of the active energy ray-curable composition (D) is sufficiently high.
本發明之活性能量線硬化性組成物中，較佳上述光聚合起始劑(C)之含量基於上述金屬氧化物(A)與上述具有芳香環骨架之(甲基) 丙烯酸酯(B)的合計重量為0.1~10重量%，更佳為0.2~7重量%。 In the active energy ray-curable composition of the present invention, the content of the photopolymerization initiator (C) is preferably based on the metal oxide (A) and the (methyl) group having an aromatic ring skeleton. The total weight of the acrylate (B) is 0.1 to 10% by weight, and more preferably 0.2 to 7% by weight.
若光聚合起始劑(C)之含量為上述範圍，則活性能量線硬化性組成物(D)之硬化性變得良好，且活性能量線硬化性組成物(D)之透明性變得良好。 When the content of the photopolymerization initiator (C) is in the above range, the curability of the active energy ray-curable composition (D) becomes good, and the transparency of the active energy ray-curable composition (D) becomes good. .
本發明之活性能量線硬化性組成物可於不阻礙本發明之效果之範圍內視需要含有各種添加劑。 The active energy ray-curable composition of the present invention may contain various additives as needed, as long as the effect of the present invention is not inhibited.
作為添加劑，例如可列舉：塑化劑、有機溶劑、分散劑、消泡劑、搖變性賦予劑(增黏劑)、滑劑(slipping agent)、抗氧化劑、受阻胺系光穩定劑及紫外線吸收劑。 Examples of the additive include a plasticizer, an organic solvent, a dispersant, a defoamer, a shake-giving agent (tackifier), a slipping agent, an antioxidant, a hindered amine light stabilizer, and ultraviolet absorption. Agent.
繼而，針對本發明之活性能量線硬化性組成物之使用方法之一例，即藉由活性能量線使本發明之活性能量線硬化性組成物硬化而製作硬化物之硬化物之製造方法進行說明。 Next, an example of a method of using the active energy ray-curable composition of the present invention, that is, a method for producing a cured product of hardened product by hardening the active energy ray-curable composition of the present invention with active energy rays will be described.
上述硬化物之製造方法含有活性能量線照射步驟，其對本發明之活性能量線硬化性組成物照射活性能量線使其硬化而製作硬化物。 The manufacturing method of the said hardened | cured material contains an active energy ray irradiation process which irradiates an active energy ray hardening composition of this invention, and hardens | cures an active energy ray, and produces a hardened | cured material.
作為上述活性能量線照射步驟中使用之活性能量線，例如可列舉：紫外線、電子束、X射線、紅外線、可見光線等。 Examples of the active energy ray used in the active energy ray irradiation step include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays.
該等活性能量線之中，就硬化性及樹脂劣化之觀點而言，較佳為紫外線及電子束。 Among these active energy rays, in terms of hardenability and resin deterioration, ultraviolet rays and electron beams are preferred.
於使用紫外線作為活性能量線之情形時，可使用各種紫外線照射裝置[例如，紫外線照射裝置[型號「VPS/I600」，輻深紫外線系統股份有限公司製造]]。 In the case of using ultraviolet rays as the active energy rays, various ultraviolet irradiation devices [for example, ultraviolet irradiation devices [model "VPS / I600", manufactured by Radiation Ultraviolet System Co., Ltd.]] can be used.
作為使用之燈，例如可列舉高壓水銀燈或金屬鹵素燈等。關於紫外線 之照射量，就活性能量線硬化性組成物之硬化性及硬化物的可撓性之觀點而言，較佳為10~10,000mJ/cm2，進而較佳為100~5,000mJ/cm2。 Examples of the lamp to be used include a high-pressure mercury lamp and a metal halide lamp. The amount of ultraviolet radiation is preferably from 10 to 10,000 mJ / cm 2 , and more preferably from 100 to 5,000 mJ / cm from the viewpoint of the curability of the active energy ray-curable composition and the flexibility of the cured product. 2 .
以此方式所製造之硬化物亦為本發明之硬化物。 The hardened product produced in this way is also a hardened product of the present invention.
作為上述硬化物之製造方法，可另外含有以下步驟。 The manufacturing method of the said hardened | cured material may contain the following processes separately.
即，可於活性能量線照射步驟之前含有將本發明之活性能量線硬化性組成物配置於具有微細之凹凸構造的平坦模具之配置步驟。 That is, the step of arranging the active energy ray-curable composition of the present invention in a flat mold having a fine uneven structure before the active energy ray irradiation step may be included.
於該步驟之後，藉由進行活性能量線照射步驟使活性能量線硬化性組成物硬化，並使硬化物自模具脫模，藉此可製造光學透鏡。 After this step, the active energy ray-curable composition is cured by performing an active energy ray irradiation step, and the cured product is released from the mold, whereby an optical lens can be manufactured.
上述配置步驟中，較佳預先將本發明之活性能量線硬化性組成物調溫至20~50℃而配置於模具。 In the above-mentioned arrangement step, the active energy ray-curable composition of the present invention is preferably adjusted to a temperature of 20 to 50 ° C. and placed in a mold.
上述配置步驟中，較佳預先將模具之溫度設為20~50℃而配置活性能量線硬化性組成物，更佳設為25~40℃而配置活性能量線硬化性組成物。 In the above-mentioned arrangement step, it is preferable to set the temperature of the mold in advance to 20 to 50 ° C to arrange the active energy ray-curable composition, and more preferably set to 25 to 40 ° C to arrange the active energy ray-curable composition.
又，上述配置步驟中，亦可使用分注器等，以硬化後之厚度成為20~150μm之方式將活性能量線硬化性組成物塗佈或填充於模具，並自塗膜上以空氣不會進入之方式加壓積層透明膜等透明基材。 Also, in the above arrangement step, a dispenser or the like may be used to coat or fill the active energy ray-curable composition into a mold so that the thickness after curing becomes 20 to 150 μm, and air is not applied from the coating film. The entry method is to laminate a transparent substrate such as a transparent film by pressure.
以此方式所配置之活性能量線硬化性組成物經過之後之活性能量線照射步驟成為硬化物，藉由使該硬化物自模具脫模可製作光學透鏡片。 The active-energy-ray-curable composition configured in this way becomes a cured product after the subsequent active-energy-ray irradiation step, and the optical lens sheet can be produced by releasing the cured product from the mold.
作為上述透明基材，可列舉由甲基丙烯酸甲酯(共)聚合物、聚對酞酸乙二酯、聚碳酸酯、聚三乙醯纖維素及聚環烯烴等樹脂構成者。 Examples of the transparent substrate include resins such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriethyl cellulose, and polycycloolefin.
此種使用有本發明之硬化物之光學透鏡或光學透鏡片等光學零件亦為本發明之光學零件。 Such optical components such as an optical lens or an optical lens sheet using the hardened material of the present invention are also optical components of the present invention.
即，本發明之活性能量線硬化性組成物可作為光學零件用之材料而使 用。 That is, the active energy ray-curable composition of the present invention can be used as a material for optical parts. use.
繼而，針對本發明之活性能量線硬化性組成物之製造方法進行說明。 Next, the manufacturing method of the active-energy-ray-curable composition of this invention is demonstrated.
本發明之活性能量線硬化性組成物之製造方法之特徵在於含有如下步驟：反應液製作步驟：以金屬烷氧化物(a1)與水之莫耳比成為金屬烷氧化物(a1)/水=2.0~200之方式將上述金屬烷氧化物(a1)及上述水加入至具有芳香環骨架之(甲基)丙烯酸酯(B)而製成反應液；反應步驟：使上述反應液中之上述金屬烷氧化物(a1)與上述水進行反應而製成金屬氧化物(A)；及光聚合起始劑添加步驟：於上述反應液加入光聚合起始劑(C)。 The method for producing an active energy ray-curable composition of the present invention is characterized by including the following steps: a reaction solution production step: forming a metal alkoxide (a1) with water in a molar ratio of metal alkoxide (a1) / water = In a method of 2.0 to 200, the above metal alkoxide (a1) and the above water are added to the (meth) acrylate (B) having an aromatic ring skeleton to prepare a reaction solution. The reaction step is to make the above metal in the above reaction solution. The alkoxide (a1) reacts with the water to form a metal oxide (A); and a photopolymerization initiator adding step: adding a photopolymerization initiator (C) to the reaction solution.
上述反應液製作步驟中，以金屬烷氧化物(a1)與水之莫耳比成為金屬烷氧化物(a1)/水=2.0~200之方式將上述金屬烷氧化物(a1)及上述水加入至具有芳香環骨架之(甲基)丙烯酸酯(B)。金屬烷氧化物(a1)與水之莫耳比較佳為金屬烷氧化物(a1)/水=5.0~100。 In the step of preparing the reaction solution, the metal alkoxide (a1) and the water are added so that the molar ratio of the metal alkoxide (a1) to water becomes metal alkoxide (a1) /water=2.0 to 200. To (meth) acrylate (B) having an aromatic ring skeleton. The molarity of the metal alkoxide (a1) and water is better. The metal alkoxide (a1) /water=5.0~100.
若上述莫耳比未達2.0，則經過後續步驟所製造之活性能量線硬化性組成物之透明性變得不充分。 If the molar ratio is less than 2.0, the transparency of the active energy ray-curable composition produced through the subsequent steps becomes insufficient.
又，若上述莫耳比超過200，則經過後續步驟所製造之活性能量線硬化性組成物之折射率變低。 In addition, if the above-mentioned molar ratio exceeds 200, the refractive index of the active energy ray-curable composition produced through the subsequent steps becomes low.
作為上述反應液製作步驟中使用之金屬烷氧化物(a1)，例如可列舉：鈦烷氧化物、鋯烷氧化物、鉿烷氧化物、鋅烷氧化物、鋁烷氧化物、鎵烷氧化物、銦烷氧化物、鍺烷氧化物、錫烷氧化物等。 Examples of the metal alkoxide (a1) used in the reaction solution production step include a titanium alkoxide, a zirconium oxide, a hafnium oxide, a zinc alkoxide, an aluminum alkoxide, and a gallium alkoxide. , Indium alkoxide, germane alkoxide, tin alkoxide, and the like.
作為上述反應液製作步驟中使用之具有芳香環骨架之(甲基)丙烯酸酯(B)，例如可列舉：(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、鄰、間 或對苯基苯酚之單(甲基)丙烯酸酯、3,3'-二苯基-4,4'-二羥基聯苯之單(甲基)丙烯酸酯及壬基苯氧基聚乙二醇(甲基)丙烯酸酯、雙酚A之環氧乙烷加成物之二(甲基)丙烯酸酯、茀之環氧乙烷加成物之二(甲基)丙烯酸酯。 Examples of the (meth) acrylate (B) having an aromatic ring skeleton used in the step of preparing the reaction solution include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ortho, meta Or mono (meth) acrylate of p-phenylphenol, mono (meth) acrylate of 3,3'-diphenyl-4,4'-dihydroxybiphenyl and nonylphenoxy polyethylene glycol (Meth) acrylate, di (meth) acrylate of the ethylene oxide adduct of bisphenol A, and di (meth) acrylate of the ethylene oxide adduct of fluorene.
本發明之活性能量線硬化性組成物之製造方法中，較佳於上述反應液製作步驟中，於上述反應液中加入有機胺作為觸媒(a2)。 In the method for producing an active energy ray-curable composition of the present invention, it is preferable to add an organic amine as a catalyst (a2) to the reaction solution in the step of preparing the reaction solution.
作為有機胺，可列舉：脂肪族胺、脂環族胺、芳香族胺或者雜環胺等。 Examples of the organic amine include an aliphatic amine, an alicyclic amine, an aromatic amine, and a heterocyclic amine.
作為脂肪族胺，可列舉：己基胺、辛基胺、甲基己基胺、甲基辛基胺、二甲基己基胺、二甲基辛基胺、二甲基月桂基胺、二甲基鯨蠟基胺、三甲基胺及三乙基胺等烷基之碳數為1~18之單-、二-及三-烷基胺等。 Examples of the aliphatic amine include hexylamine, octylamine, methylhexylamine, methyloctylamine, dimethylhexylamine, dimethyloctylamine, dimethyllaurylamine, and dimethylwhale Mono-, di-, and tri-alkylamines having 1 to 18 carbon atoms in alkyl groups such as waxylamine, trimethylamine, and triethylamine.
作為脂環族胺，可列舉：環丁基胺、環己基胺、環戊基胺、環辛基胺、N-甲基環己基胺及N-乙基環己基胺等環烷基之碳數為4~12之環烷基胺及該等之烷基(碳數1~6)取代物等。 Examples of the cycloaliphatic amine include the number of carbon atoms of cycloalkyl such as cyclobutylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, N-methylcyclohexylamine, and N-ethylcyclohexylamine. It is a cycloalkylamine of 4 to 12 and the alkyl (carbon number of 1 to 6) substitutes.
作為芳香族胺，可列舉：苯胺、二苯基胺等碳數為6~18之芳香族胺等。 Examples of the aromatic amines include aromatic amines having 6 to 18 carbon atoms, such as aniline and diphenylamine.
作為雜環胺，可舉啉等碳數為4~10之雜環胺等。 As a heterocyclic amine, Heterocyclic amines having 4 to 10 carbon atoms such as phthaloline.
上述光聚合起始劑添加步驟於任何時間進行均可。例如，可於反應液製作步驟中製作反應液時加入光聚合起始劑(C)，亦可於反應步驟後之反應液加入光聚合起始劑(C)。 The photopolymerization initiator addition step may be performed at any time. For example, the photopolymerization initiator (C) may be added when the reaction solution is prepared in the reaction solution production step, or the photopolymerization initiator (C) may be added to the reaction solution after the reaction step.
實施例 Examples
以下，藉由實施例及比較例進一步對本發明進行說明，但本發明並不限定於該等。 Hereinafter, the present invention will be further described using examples and comparative examples, but the present invention is not limited to these.
實施例1 Example 1
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸鄰苯基苯氧基乙酯(B-1)[商品名：KOMERATE-A011；KPX Green Chemical Co.,Ltd.製造]80.0份、水0.01份及三乙基胺(a2-2)0.05份並攪拌30分鐘，之後，加入鋯四正丁氧化物(a1-1)[商品名：TBZR；日本曹達股份有限公司製造]20.0份，使其於65℃反應2小時。之後，加入2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)[商品名「Lucirin TPO」；BASF公司製造]2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D-1)。 To a reaction vessel equipped with a stirrer, a condenser, and a thermometer, o-phenylphenoxyethyl acrylate (B-1) [trade name: KOMERATE-A011; manufactured by KPX Green Chemical Co., Ltd.] 80.0 parts of water and 0.01 of water Parts and 0.05 parts of triethylamine (a2-2) and stirring for 30 minutes, and then 20.0 parts of zirconium tetra-n-butoxide (a1-1) [trade name: TBZR; manufactured by Soda Co., Ltd.] was added to The reaction was carried out at 65 ° C for 2 hours. Thereafter, 2.0 parts of 2,4,6-trimethylbenzylidene diphenylphosphine oxide (C1-1) [trade name "Lucirin TPO"; manufactured by BASF Corporation] was added, and the mixture was stirred at 65 ° C until the It was made uniform, and the active-energy-ray-curable composition (D-1) was obtained.
實施例2 Example 2
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸苯氧基乙酯(B-2)[商品名：Light acrylate POA；共榮社化學股份有限公司製造]45.0份、加成10莫耳環氧乙烷之茀丙烯酸酯(B-4)[商品名：KOMERATE-D104；KPX Green Chemical Co.,Ltd.製造]40.0份、水0.1份及三乙基胺(a2-2)0.03份並攪拌30分鐘，之後，加入鈦四正丁氧化物(a1-2)[商品名：B-1；日本曹達股份有限公司製造]15.0份，使其於65℃反應2小時，之後加入雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(C1-2)[商品名「Irgacure-819」；BASF公司製造]2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D-2)。 Add a phenoxyethyl acrylate (B-2) [trade name: Light acrylate POA; manufactured by Kyoeisha Chemical Co., Ltd.] to a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and add 10 mol epoxy Ethane fluorene acrylate (B-4) [trade name: KOMERATE-D104; manufactured by KPX Green Chemical Co., Ltd.] 40.0 parts, water 0.1 parts, and triethylamine (a2-2) 0.03 parts and stirred for 30 After 1 minute, 15.0 parts of titanium tetra-n-butoxide (a1-2) [trade name: B-1; manufactured by Soda Co., Ltd.] was added and allowed to react at 65 ° C for 2 hours, and then bis (2,4 , 6-trimethylbenzyl) -phenylphosphine oxide (C1-2) [trade name "Irgacure-819"; manufactured by BASF Corporation] 2.0 parts, and stirred at 65 ° C until uniform, and An active energy ray-curable composition (D-2) was obtained.
實施例3 Example 3
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸鄰苯基苯氧基乙酯(B-1)40.0份、丙烯酸苯氧基乙酯(B-2)10.0份、加成6莫耳環氧乙烷之茀丙烯酸酯(B-3)[商品名：KOMERATE-D064；KPX Green Chemical Co.,Ltd.製造]20.0份、水0.05份及三甲基胺(a2-1)0.05份並攪拌 30分鐘，之後，加入鋯四正丁氧化物(a1-1)30.0份，使其於65℃反應2小時，之後，加入2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D-3)。 40.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of phenoxyethyl acrylate (B-2), and 6 mol epoxy were added to a reaction vessel equipped with a stirrer, a condenser, and a thermometer. Ethane fluorene acrylate (B-3) [trade name: KOMERATE-D064; manufactured by KPX Green Chemical Co., Ltd.] 20.0 parts, 0.05 parts of water, and 0.05 parts of trimethylamine (a2-1) and stirred After 30 minutes, 30.0 parts of zirconium tetra-n-butoxide (a1-1) was added and allowed to react at 65 ° C for 2 hours, and then 2,4,6-trimethylbenzylidene diphenylphosphine oxide was added. (C1-1) 2.0 parts, and it stirred at 65 degreeC until it became uniform, and obtained the active-energy-ray-curable composition (D-3).
實施例4 Example 4
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸鄰苯基苯氧基乙酯(B-1)70.0份、加成6莫耳環氧乙烷之茀丙烯酸酯(B-3)10.0份、水0.05份及三甲基胺(a2-1)0.05份並攪拌30分鐘，之後，加入鈦四正丁氧化物(a1-2)20.0份，使其於65℃反應2小時，之後，加入1-羥基環己基苯基酮(C5-1)[商品名「Irgacure 184」；BASF公司製造]2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D-4)。 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 70.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of fluorene acrylate (B-3) added with 6 mol ethylene oxide, 0.05 parts of water and 0.05 parts of trimethylamine (a2-1) were stirred for 30 minutes, and then 20.0 parts of titanium tetra-n-butoxide (a1-2) was added to react at 65 ° C for 2 hours, and then 1 -2.0 parts of hydroxycyclohexylphenyl ketone (C5-1) [trade name "Irgacure 184"; manufactured by BASF Co., Ltd.], and stirred at 65 ° C until homogeneous to obtain an active energy ray-curable composition (D -4).
實施例5 Example 5
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸苯氧基乙酯(B-2)70.0份、水0.1份及三甲基胺(a2-1)0.05份並攪拌30分鐘，之後，加入鋯四正丁氧化物(a1-1)40.0份，使其於65℃反應2小時，之後，加入雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(C1-2)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D-5)。 70.0 parts of phenoxyethyl acrylate (B-2), 0.1 parts of water, and 0.05 parts of trimethylamine (a2-1) were added to a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and stirred for 30 minutes, and then 40.0 parts of zirconium tetra-n-butoxide (a1-1) was allowed to react at 65 ° C for 2 hours, and then bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide (C1- 2) 2.0 parts, and mixing and stirring at 65 ° C. until uniform, to obtain an active energy ray-curable composition (D-5).
比較例1 Comparative Example 1
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸苯氧基乙酯(B-2)45.0份、加成10莫耳環氧乙烷之茀丙烯酸酯(B-4)40.0份、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(C1-2)3.0份，並於65℃進行混合 攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-1)。 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, add 45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) with 10 mol ethylene oxide, and double (2 3.0 parts of 4,4,6-trimethylbenzyl) -phenylphosphine oxide (C1-2), and mixed at 65 ° C It stirred until it became uniform, and obtained the active-energy-ray-curable composition (D'-1).
比較例2 Comparative Example 2
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸苯氧基乙酯(B-2)45.0份、加成10莫耳環氧乙烷之茀丙烯酸酯(B-4)40.0份、氧化鈦微粒子(A-1)[商品名：MT-01；帝化股份有限公司製造]2.0份、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(C1-2)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-2)。 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) added with 10 mol ethylene oxide, and titanium oxide fine particles were added. (A-1) [Trade name: MT-01; manufactured by Imperial Chemical Co., Ltd.] 2.0 parts, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide (C1-2) 2.0 The mixture was stirred at 65 ° C. until homogeneous, and an active energy ray-curable composition (D′-2) was obtained.
比較例3 Comparative Example 3
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸苯氧基乙酯(B-2)45.0份、加成10莫耳環氧乙烷之茀丙烯酸酯(B-4)40.0份、氧化鈦微粒子(A-1)5.0份、2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-3)。 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) added with 10 mol ethylene oxide, and titanium oxide fine particles were added. (A-1) 5.0 parts, 2.0 parts of 2,4,6-trimethylbenzylidene diphenylphosphine oxide (C1-1), and stirred at 65 ° C until homogeneous to obtain active energy Wire-curable composition (D'-3).
比較例4 Comparative Example 4
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸鄰苯基苯氧基乙酯(B-1)70.0份、加成6莫耳環氧乙烷之茀丙烯酸酯(B-3)10.0份、水5.0份及三乙基胺(a2-2)0.05份並攪拌30分鐘，之後，加入鋯四正丁氧化物(a1-1)20.0份，使其於65℃反應2小時，之後，加入2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-4)。 In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 70.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of fluorene acrylate (B-3) added with 6 mol ethylene oxide, 5.0 parts of water and 0.05 parts of triethylamine (a2-2) were stirred for 30 minutes, and then 20.0 parts of zirconium tetra-n-butoxide (a1-1) was added to react at 65 ° C for 2 hours, and then 2 was added 2.0 parts of 4,4,6-trimethylbenzylidene diphenylphosphine oxide (C1-1), and stirred at 65 ° C until homogeneous, thereby obtaining an active energy ray-curable composition (D'- 4).
比較例5 Comparative Example 5
於具備攪拌機、冷凝管及溫度計之反應容器中加入丙烯酸鄰苯基苯氧 基乙酯(B-1)70.0份、加成6莫耳環氧乙烷之茀丙烯酸酯(B-3)10.0份、水0.003份及三乙基胺(a2-2)0.05份並攪拌30分鐘，之後，加入鋯四正丁氧化物(a1-1)20.0份，使其於65℃反應2小時，之後，加入2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-5)。 Add o-phenylphenoxy acrylate to a reaction vessel equipped with a stirrer, a condenser, and a thermometer 70.0 parts of methyl ethyl ester (B-1), 10.0 parts of fluorene acrylate (B-3) added with 6 mol ethylene oxide, 0.003 parts of water and 0.05 parts of triethylamine (a2-2) and stirred for 30 minutes Then, 20.0 parts of zirconium tetra-n-butoxide (a1-1) was added and allowed to react at 65 ° C for 2 hours, and then 2,4,6-trimethylbenzylidene diphenylphosphine oxide (C1 -1) 2.0 parts, and mixing and stirring at 65 ° C. until uniform, to obtain an active energy ray-curable composition (D′-5).
比較例6 Comparative Example 6
於具備攪拌機、冷凝管及溫度計之反應容器中加入二羥甲基三環癸烷二丙烯酸酯(B'-1)80.0份、水0.05份及三乙基胺(a2-2)0.05份並攪拌30分鐘，之後，加入鈦四正丁氧化物(a1-2)20.0份，使其於65℃反應2小時，之後，加入2,4,6-三甲基苯甲醯基二苯基氧化膦(C1-1)2.0份，並於65℃進行混合攪拌直至變得均勻，而獲得活性能量線硬化性組成物(D'-6)。 Add 80.0 parts of dimethylol tricyclodecane diacrylate (B'-1), 0.05 parts of water, and 0.05 parts of triethylamine (a2-2) to a reaction vessel equipped with a stirrer, a condenser, and a thermometer and stir. After 30 minutes, 20.0 parts of titanium tetra-n-butoxide (a1-2) was added and allowed to react at 65 ° C for 2 hours, and then 2,4,6-trimethylbenzylidene diphenylphosphine oxide was added. (C1-1) 2.0 parts, and it stirred at 65 degreeC until it became uniform, and obtained the active energy ray hardening composition (D'-6).
利用以下記載之方法對實施例1~5及比較例1~6之活性能量線硬化性組成物於25℃的折射率、總光線透射率(%)，以及實施例1~5及比較例1~6之活性能量線硬化性組成物之硬化物的密接性、傷痕之恢復性進行測量並進行評價。將結果示於表1。 The refractive index and total light transmittance (%) of the active energy ray-curable compositions of Examples 1 to 5 and Comparative Examples 1 to 6 at 25 ° C, and Examples 1 to 5 and Comparative Example 1 were measured by the methods described below. The adhesion of the cured product of the active energy ray-curable composition of ~ 6 and the recoverability of the scar were measured and evaluated. The results are shown in Table 1.
再者，關於含有有機溶劑之實施例及比較例，於利用蒸發器使有機溶劑充分地揮發之後進行評價。 The examples and comparative examples containing organic solvents were evaluated after the organic solvents were sufficiently evaporated using an evaporator.
[折射率之評價] [Evaluation of refractive index]
使用折射計[商品名：阿貝折射計4T；愛宕股份有限公司製造]，於25℃之環境下對實施例1~5及比較例1~6之活性能量線硬化性組成物的折射率進行測量。 Using a refractometer [trade name: Abbe Refractometer 4T; manufactured by Atago Co., Ltd.], the refractive indices of the active energy ray-curable compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were measured at 25 ° C. measuring.
[總光線透射率之評價] [Evaluation of total light transmittance]
於厚度1mm之載玻片上放置挖出2cm見方之厚度100μm之矽橡膠，於所挖出之部分流入各實施例及各比較例之活性能量線硬化性組成物。繼而，將另一厚度1mm之載玻片放置於所流入之活性能量線硬化性組成物上，將各載玻片之兩端利用夾具進行固定。之後，依據JIS-K7105，使用總光線透射率測量裝置[商品名「haze-garddual」；BYK gardner股份有限公司製造]對總光線透射率(%)進行測量。 A silicon rubber with a thickness of 2 μm and a thickness of 100 μm was placed on a glass slide having a thickness of 1 mm, and the excavated portion flowed into the active energy ray-curable composition of each example and each comparative example. Then, another glass slide having a thickness of 1 mm was placed on the flowing active energy ray-curable composition, and both ends of each glass slide were fixed with a jig. After that, the total light transmittance (%) was measured using a total light transmittance measuring device [trade name "haze-garddual"; manufactured by BYK Gardner Co., Ltd.] in accordance with JIS-K7105.
再者，本發明之活性能量線硬化性組成物之總光線透射率必須為90%以上。 Furthermore, the total light transmittance of the active energy ray-curable composition of the present invention must be 90% or more.
[試片之製作] [Production of test piece]
利用敷貼器將活性能量線硬化性組成物以厚度成為20μm之方式塗佈於玻璃板之單面，之後，將厚度100μm之PET膜[商品名「COSMOSHINE A4300」；東洋紡績股份有限公司製造]貼合於活性能量線硬化性組成物側，自上方轉動輥而將空氣擠出。藉由紫外線照射裝置以1000mJ/cm2自PET膜側照射紫外線，而使活性能量線硬化性組成物硬化。將密接於PET膜之硬化物自玻璃板剝離，而製作試片。 An applicator was used to apply an active energy ray-curable composition to a thickness of 20 μm on one side of a glass plate, and then a 100 μm-thick PET film [trade name “COSMOSHINE A4300”; manufactured by Toyobo Corporation] It adheres to the active-energy-ray-curable composition side, and rotates a roller from above to squeeze out air. The active energy ray-curable composition was cured by irradiating ultraviolet rays from the PET film side with an ultraviolet irradiation device at 1000 mJ / cm 2 . The hardened | cured material which adhered to the PET film was peeled from the glass plate, and the test piece was produced.
[密接性之評價] [Evaluation of tightness]
將上述試片於23℃、相對濕度50%之環境下靜置24小時後，依據JIS K5600-5-6，利用截切刀切出1mm寬之切口而製作棋盤格(10×10個)，於該棋盤格上貼附賽珞凡(cellophane)黏著帶並進行90度剝離，以目視觀察硬化物之自PET膜之剝離狀態，並利用以下基準進行評價。 After the above test piece was left to stand in an environment of 23 ° C. and a relative humidity of 50% for 24 hours, a 1 mm wide incision was cut out using a cutter according to JIS K5600-5-6 to make a checkerboard (10 × 10 pieces). A cellophane adhesive tape was affixed to this checkerboard and peeled at 90 degrees, and the peeling state of the cured product from the PET film was visually observed, and evaluated using the following criteria.
A：100個棋盤格之中90個以上未剝離而殘留於基材 A: 90 or more of the 100 checkerboards remain on the substrate without peeling
B：100個棋盤格之中10~89個未剝離而殘留於基材 B: 10 to 89 out of 100 checkerboards remain on the substrate without peeling
C：100個棋盤格之中9個以下未剝離而殘留於基材 C: 9 or less of 100 checkerboards remain on the substrate without peeling
[傷痕之恢復性之評價] [Evaluation of the recoverability of the scar]
(1)準備以槽深50μm且間距寬度20μm刻上平行線而微細地實施過凹凸處理之不鏽鋼製模具。 (1) A stainless steel mold was prepared by engraving parallel lines with a groove depth of 50 μm and a pitch width of 20 μm and finely performing unevenness treatment.
(2)利用敷貼器將活性能量線硬化性組成物以厚度成為100μm之方式塗佈於該模具之單面，之後，將厚度100μm之PET膜[商品名「COSMOSHINE A4300」；東洋紡績股份有限公司製造]貼合於活性能量線硬化性組成物側，自上方轉動輥而將空氣擠出。藉由紫外線照射裝置[型號「VPS/I600」；輻深紫外線系統股份有限公司製造]以1000mJ/cm2自PET膜側照射紫外線使其硬化，而製作膜狀之硬化物。 (2) Apply an active energy ray-curable composition to a single surface of the mold with a thickness of 100 μm using an applicator, and then apply a 100 μm-thick PET film [trade name “COSMOSHINE A4300”; Toyo Textile Co., Ltd. Co., Ltd.] It is attached to the active energy ray-curable composition side, and the roller is rotated from above to squeeze air out. An ultraviolet irradiation device [model "VPS / I600"; manufactured by Radiation Ultraviolet System Co., Ltd.] was irradiated with ultraviolet light from the PET film side at 1000 mJ / cm 2 to harden it to produce a film-like hardened body.
(3)使用安裝有鉻帽之鉛筆，依據JIS K 5600-5-4對膜狀之硬化物 的表面進行刮痕試驗。 (3) Use a pencil with a chrome cap to apply film-like hardened material in accordance with JIS K 5600-5-4 The surface was subjected to a scratch test.
(4)以目視觀察刮痕試驗後之膜狀之硬化物的表面，並利用下述基準進行判定。 (4) The surface of the film-like hardened | cured material after the scratch test was visually observed, and it judged by the following reference | standard.
A：劃傷於3秒以內完全消失 A: The scratch disappears completely within 3 seconds
B：劃傷即便經過3秒亦有一部分殘留 B: Some scratches remain even after 3 seconds
C：劃傷即便經過3秒亦全部殘留 C: Scratches remain even after 3 seconds
實施例1~5之活性能量線硬化性組成物之任一者均折射率充分高，透明性優異，與塑膠基材之密接性高，且傷痕之恢復性優異。 Each of the active energy ray-curable compositions of Examples 1 to 5 had a sufficiently high refractive index, excellent transparency, high adhesion to a plastic substrate, and excellent recoverability of scars.
另一方面，不含金屬氧化物(A)之比較例1之活性能量線硬化性組成物之折射率未達1.56，密接性不良，且傷痕之恢復性亦不充分。 On the other hand, the refractive index of the active energy ray-curable composition of Comparative Example 1 containing no metal oxide (A) was less than 1.56, the adhesion was poor, and the recoverability of the scar was insufficient.
比較例2之活性能量線硬化性組成物之折射率未達1.56。 The refractive index of the active energy ray-curable composition of Comparative Example 2 was less than 1.56.
比較例3之活性能量線硬化性組成物之透明性未達90%。 The transparency of the active energy ray-curable composition of Comparative Example 3 was less than 90%.
比較例4之活性能量線硬化性組成物之透明性未達90%。 The transparency of the active energy ray-curable composition of Comparative Example 4 was less than 90%.
比較例5之活性能量線硬化性組成物之折射率未達1.56。 The refractive index of the active energy ray-curable composition of Comparative Example 5 was less than 1.56.
使用不含芳香環之(甲基)丙烯酸酯之比較例6的活性能量線硬化性組成物之折射率未達1.56。 The refractive index of the active energy ray-curable composition of Comparative Example 6 using a (meth) acrylate containing no aromatic ring was less than 1.56.
[產業上之可利用性] [Industrial availability]
本發明之活性能量線硬化性組成物由於為高折射率且透明性優異，並且其硬化物之傷痕之恢復性優異且與塑膠基材之密接性高，故而可較佳地用作光學零件、電氣-電子零件。 The active energy ray-curable composition of the present invention has a high refractive index and excellent transparency, and has excellent recoverability of scars of the cured material and high adhesion to a plastic substrate, so it can be preferably used as an optical part, Electrical-electronic parts.
作為使用本發明之硬化物之光學零件，可列舉光學透鏡、光學透鏡片或膜，更詳細而言，例如可列舉：塑膠透鏡(稜鏡透鏡、柱狀透鏡、微透 鏡、菲涅耳透鏡、視野角提昇透鏡等)、光學補償膜、相位差膜、稜鏡、光纖、可撓性印刷配線用阻焊劑、電鍍阻劑、多層印刷配線板用層間絕緣膜、感光性光波導等。 Examples of the optical component using the cured product of the present invention include an optical lens, an optical lens sheet, or a film. More specifically, for example, a plastic lens (e.g., a lenticular lens, a lenticular lens, or a micro lens) Mirrors, Fresnel lenses, viewing angle-enhancing lenses, etc.), optical compensation films, retardation films, chirps, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and photosensitive Optical waveguides.
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP2015-079966 | 2015-04-09 | ||
| JP2015079966 | 2015-04-09 |
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| TW201641580A TW201641580A (en) | 2016-12-01 |
| TWI647271B true TWI647271B (en) | 2019-01-11 |
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| TW105110845A TWI647271B (en) | 2015-04-09 | 2016-04-07 | Active energy ray-curable composition, hardened product, optical part, and method for producing active energy ray-curable composition |
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| JP (1) | JP6714581B2 (en) |
| KR (1) | KR20170125076A (en) |
| CN (1) | CN107428858B (en) |
| TW (1) | TWI647271B (en) |
| WO (1) | WO2016163381A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342308A (en) * | 2002-05-24 | 2003-12-03 | Nippon Shokubai Co Ltd | Curable resin composition and its manufacturing process |
| JP2012184318A (en) * | 2011-03-04 | 2012-09-27 | Nippon Steel Chem Co Ltd | Curable composition |
| TW201625480A (en) * | 2014-12-12 | 2016-07-16 | Dainippon Ink & Chemicals | Process for producing dispersion of fine inorganic particles, curable composition containing said dispersion, and cured object obtained therefrom |
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| JP4234406B2 (en) * | 2002-11-29 | 2009-03-04 | 住友精化株式会社 | Photocurable composition |
| JP2005314661A (en) * | 2004-03-30 | 2005-11-10 | Mitsubishi Chemicals Corp | Resin molded product |
| CN102985483B (en) * | 2010-06-23 | 2015-06-10 | 日本化成株式会社 | Inorganic-organic hybrid material, optical material using same, and inorganic-organic composite composition |
| JP5760522B2 (en) * | 2011-03-07 | 2015-08-12 | 帝人株式会社 | PHOTOCURABLE RESIN COMPOSITION, ARTICLE HAVING CURED CURTAIN THEREOF, AND PRODUCTION METHOD THEREFOR |
| JP5922341B2 (en) * | 2011-05-09 | 2016-05-24 | 大阪ガスケミカル株式会社 | Composition comprising fluorene compound and metal oxide |
| JP2013227395A (en) * | 2012-04-25 | 2013-11-07 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition for optical lens sheet and cured product of the same |
| JP6368240B2 (en) * | 2012-04-27 | 2018-08-01 | 地方独立行政法人大阪産業技術研究所 | Metal oxide dispersion, polymerizable composition containing metal oxide dispersion, and polymer thereof |
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- 2016-04-06 WO PCT/JP2016/061214 patent/WO2016163381A1/en active Application Filing
- 2016-04-06 CN CN201680020396.3A patent/CN107428858B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342308A (en) * | 2002-05-24 | 2003-12-03 | Nippon Shokubai Co Ltd | Curable resin composition and its manufacturing process |
| JP2012184318A (en) * | 2011-03-04 | 2012-09-27 | Nippon Steel Chem Co Ltd | Curable composition |
| TW201625480A (en) * | 2014-12-12 | 2016-07-16 | Dainippon Ink & Chemicals | Process for producing dispersion of fine inorganic particles, curable composition containing said dispersion, and cured object obtained therefrom |
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| Publication number | Publication date |
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| CN107428858A (en) | 2017-12-01 |
| JPWO2016163381A1 (en) | 2018-02-01 |
| TW201641580A (en) | 2016-12-01 |
| KR20170125076A (en) | 2017-11-13 |
| JP6714581B2 (en) | 2020-06-24 |
| CN107428858B (en) | 2020-02-07 |
| WO2016163381A1 (en) | 2016-10-13 |
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