TW201641580A - Active energy ray-curable composition, cured product, optical component and method for producing active energy ray-curable composition - Google Patents
Active energy ray-curable composition, cured product, optical component and method for producing active energy ray-curable composition Download PDFInfo
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- TW201641580A TW201641580A TW105110845A TW105110845A TW201641580A TW 201641580 A TW201641580 A TW 201641580A TW 105110845 A TW105110845 A TW 105110845A TW 105110845 A TW105110845 A TW 105110845A TW 201641580 A TW201641580 A TW 201641580A
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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 110
- 230000003287 optical effect Effects 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 48
- 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 12
- -1 titanium alkoxide Chemical class 0.000 claims description 56
- 150000004703 alkoxides Chemical class 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 25
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
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- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 230000035876 healing Effects 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 18
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 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 9
- 239000000758 substrate Substances 0.000 description 9
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- 238000000034 method Methods 0.000 description 8
- 238000011084 recovery Methods 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
- 229920002799 BoPET Polymers 0.000 description 6
- 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 6
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- 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
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
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- 239000001301 oxygen Substances 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
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- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- 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
- 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
- C08F2/46—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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
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 components obtained from a cured product, and a method for producing the active energy ray-curable composition. Specifically, it relates to an active energy ray-curable composition having 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。 Conventionally, a cymbal used for a liquid crystal display or an optical lens such as a Fresnel lens or a lenticular lens for projecting a TV is provided with a resin base by flowing an active energy ray-curable composition to the inner surface. The mold is made of a material and irradiated with an active energy ray to cure 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 the display, the brightness of the optical lens has been attempted. For this purpose, for example, a technique of dispersing fine particles of a metal oxide in a high refractive index resin has been 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 of dispersing fine particles of metal oxide in Patent Document 1, it is necessary to contain a dispersing agent and an organic solvent in the high refractive index resin, and to solidify the cured product produced by hardening the high refractive index resin produced by the method. Solvent. When the organic solvent remains in the cured product, there is a problem that scratches occur due to contact with other members during assembly and transportation. Further, when the fine particles of the metal oxide are contained, the transparency of the cured product is impaired, so that 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 Laid-Open Patent Publication 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 high refractive index and excellent transparency, which is excellent in recovery of scratches and high in adhesion to a plastic substrate. Hardened matter.
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 conducted research in order to achieve the above object, and as a result, have achieved 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 having an aromatic ring skeleton (B), and a photopolymerization initiator (C) The active energy ray-curable composition (D) characterized in that the active energy ray-curable composition (D) has a refractive index of 1.56 to 1.70 at 25 ° C, and the active energy ray-curable composition (D) The total light transmittance is 90% or more; (2) a cured product obtained by hardening the active energy ray-curable composition of the present invention; and (3) an optical component using the above-described present invention a cured product; (4) and a method for producing an active energy ray-curable composition, which is manufactured as described above The active energy ray-curable composition characterized by comprising the following steps: a reaction liquid preparation step of: metal alkoxide (a1) and water molar ratio to metal alkoxide (a1) / water = 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 liquid; and the reaction step: the above metal alkoxide in the above reaction liquid ( A1) reacting with the above water to form a metal oxide (A); and a photopolymerization initiator adding step: adding a photopolymerization initiator (C) to the above reaction liquid.
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 has an effect of high refractive index, excellent transparency, and excellent recovery of scratches of a cured product, and high adhesion to a plastic substrate.
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 contains 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 active energy ray-curable composition (D) has a refractive index of 1.56 to 1.70 at 25 ° C, 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 the present specification, the refractive index means the refractive index of light at 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 term "total light transmittance" means the total 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 excellent in 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) is excellent in 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 the refractive index, examples of the metal oxide (A) include oxides of zirconium, titanium, hafnium, zinc, aluminum, gallium, indium, antimony, 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。 Further, 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 a titanium alkoxide, a zirconium alkoxide, a decane oxide, a zinc alkoxide, an aluminoxane, a gallium alkoxide, an indium alkoxide, and a decane. Oxides, tin alkoxides, and the like.
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 alkoxide include zirconium tetra-n-butyl oxide, and examples of the titanium alkoxide include titanium tetra-n-butyl oxide.
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 obtained by making a metal alkoxide (a1) and water a molar ratio to a metal alkoxide. (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) is 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。 Further, if the molar ratio exceeds 200, the refractive index of the active energy ray-curable composition (D) The rate is getting lower.
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, 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 total light transmittance is increased.
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 the present 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 the dynamic light scattering method. The analysis is a value below 10 nm; or in the measurement by dynamic light scattering, the average particle diameter of the metal oxide (A) is analyzed to be less than 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. The refractive index of the active energy ray-curable composition (D) of the present invention is appropriately increased by using the (meth) acrylate (B) having an aromatic ring skeleton.
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. Further, it is more preferred that the above oxygen alkyl group is an oxyethylene group. Examples of such a (meth) acrylate (B) having an aromatic ring skeleton include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-, m- or p-phenylphenol. Mono (meth) acrylate, 3,3'-diphenyl-4,4'-dihydroxybiphenyl mono (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate And a di(meth)acrylate of an ethylene oxide adduct of bisphenol A, a di(meth)acrylate of an ethylene oxide adduct of hydrazine, 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 the (meth) acrylates (B) having an aromatic ring skeleton, more preferred are phenoxyethyl (meth) acrylate, mono(meth) acrylate of o-, m- or p-phenylphenol, O-, m- or p-phenylphenoxy (oxyalkyl) adducts of (meth) acrylate, oxime ethylene oxide The (meth) acrylate of the adduct of the (meth) acrylate and the ethylene oxide adduct of ruthenium.
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。 Among these, further preferred are phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, oxime acrylate with addition of 6 moles of ethylene oxide, and hydrazine acrylic acid having an addition of 10 moles of ethylene oxide. 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)、1,3α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 a phosphine oxide compound (C1), a benzamidine compound (C2), and 9-oxosulfuric acid. Compound (C3), oxime ester compound (C4), hydroxybenzimidyl compound (C5), benzophenone compound (C6), ketal compound (C7), 1,3α aminoalkyl group A benzophenone compound (C8) or 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-trimethylbenzhydryldiphenyl oxide. Phosphine and the like.
作為苯甲醯甲酸酯系化合物(C2)，可舉苯甲醯甲酸甲酯等。 The benzamidine compound (C2) may, for example, be methyl benzoate.
作為9-氧硫系化合物(C3)，可舉異丙基-9-氧硫等。 9-oxosulfur Compound (C3), which can be isopropyl-9-oxosulfur Wait.
作為肟酯系化合物(C4)，可列舉1,2-辛烷二酮，1-[4-(苯硫基)-,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)-, 2-(O-benzamide), ethyl ketone, 1-[ 9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetyl) 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 hydroxybenzimidyl compound (C5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl 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 and the like.
作為縮酮系化合物(C7)，可舉苄基二甲基縮酮等。 The ketal compound (C7) may, for example, be a benzyldimethylketal or the like.
作為1,3α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。 The 1,3α-aminoalkylphenone compound (C8) is exemplified by 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)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 the photopolymerization initiators (C), the curable property of the active energy ray-curable composition of the present invention and the cured product obtained by curing the active energy ray-curable composition of the present invention by an active energy ray From the viewpoint of coloring, a phosphine oxide compound (C1) is preferred, and bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6- is further preferred. Trimethylbenzimidyldiphenylphosphine 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 the aromatic ring skeleton. It is 5 to 50% by weight, 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) is 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, it is preferred that the content of the (meth) acrylate (B) having an aromatic ring skeleton is based on the metal oxide (A) and the (meth) group having the aromatic ring skeleton described above. The total weight of the acrylate (B) is 50 to 95% by weight, 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, it is preferred that the content of the photopolymerization initiator (C) is based on the metal oxide (A) and the above (meth) having an aromatic ring skeleton. The total weight of the acrylate (B) is from 0.1 to 10% by weight, more preferably from 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) is good, and the transparency of the active energy ray-curable composition (D) is 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 within a range not inhibiting the effects of the present invention.
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, an antifoaming agent, a shake imparting 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, which is a method for producing a cured product of a cured product by curing the active energy ray-curable composition of the present invention by an active energy ray, 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 method for producing a cured product includes an active energy ray irradiation step of irradiating an active energy ray-curable composition of the present invention with an active energy ray to be cured to form a cured product.
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, visible rays, and the like.
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, from the viewpoints of hardenability and resin deterioration, ultraviolet rays and electron beams are preferable.
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]]。 When ultraviolet rays are used as the active energy ray, various ultraviolet ray irradiation devices can be used [for example, an ultraviolet ray irradiation device [Model "VPS/I600", manufactured by Radiation Ultraviolet Systems Co., Ltd.]].
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 or a metal halide lamp. The irradiation amount of the ultraviolet ray 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 cured product produced in this manner is also a cured 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。 As a method of producing the cured product, the following steps may be additionally included.
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 arrangement step of disposing the active energy ray-curable composition of the present invention in a flat mold having a fine uneven structure may be included before the active energy ray irradiation step.
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 hardened by the 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 arrangement step, it is preferred that the active energy ray-curable composition of the present invention is adjusted to a temperature of 20 to 50 ° C in advance 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-described arrangement, the active energy ray-curable composition is preferably placed at a temperature of 20 to 50 ° C in advance, and more preferably, the active energy ray-curable composition is placed at 25 to 40 ° C.
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。 Further, in the above-mentioned arrangement step, the active energy ray-curable composition may be applied or filled in the mold so that the thickness after hardening is 20 to 150 μm, and the air is not applied from the coating film. The method of entering is to pressurize a transparent substrate such as a laminated transparent film.
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 disposed in this manner is subjected to an active energy ray irradiation step to become a cured product, and an optical lens sheet can be produced by demolding 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 those composed of a resin such as methyl methacrylate (co)polymer, polyethylene terephthalate, polycarbonate, polytrimethylene 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 an optical component such as an optical lens or an optical lens sheet using the cured product of the present invention is also an optical component 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, a method for producing the active energy ray-curable composition of the present invention will be described.
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 comprising the steps of: a reaction liquid preparation step of: a metal alkoxide (a1)/water = a molar ratio of a metal alkoxide (a1) to water; 2.0 to 200, the metal alkoxide (a1) and the water are added to the (meth) acrylate (B) having an aromatic ring skeleton to prepare a reaction liquid; and the reaction step: the above metal in the reaction liquid The alkoxide (a1) is reacted with the above water to form a metal oxide (A); and a photopolymerization initiator is added: a photopolymerization initiator (C) is added to the above reaction liquid.
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 reaction liquid preparation step, the metal alkoxide (a1) and the water are added in such a manner that the molar ratio of the metal alkoxide (a1) to water is metal alkoxide (a1) / water = 2.0 to 200. To the (meth) acrylate (B) having an aromatic ring skeleton. The metal alkoxide (a1) and the water molar are preferably metal alkoxide (a1) / water = 5.0 to 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。 Further, when the molar ratio exceeds 200, the refractive index of the active energy ray-curable composition produced through the subsequent step 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 liquid production step include a titanium alkoxide, a zirconium alkoxide, a decane oxide, a zinc alkoxide, an aluminoxane, and a gallium alkoxide. Indium alkoxide, decane oxide, 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。 The (meth) acrylate (B) having an aromatic ring skeleton used in the reaction liquid production step may, for example, be benzyl (meth) acrylate, phenoxyethyl (meth) acrylate or the like. Or mono(meth)acrylate of p-phenylphenol, mono(meth)acrylate of 3,3'-diphenyl-4,4'-dihydroxybiphenyl and mercaptophenoxy polyethylene glycol (Meth) acrylate, bis(meth) acrylate of ethylene oxide adduct of bisphenol A, and di(meth) acrylate of ethylene oxide adduct of hydrazine.
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 preferred to add an organic amine as a catalyst (a2) to the reaction liquid in the reaction liquid preparation step.
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。 The organic amine may, for example, be an aliphatic amine, an alicyclic amine, an aromatic amine or 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, dimethyl laurylamine, and dimethyl whale. A mono-, di-, and tri-alkylamine having 1 to 18 carbon atoms of an alkyl group such as a waxy amine, a trimethylamine or a 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 alicyclic amine include a carbon number of a cycloalkyl group such as cyclobutylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, N-methylcyclohexylamine, and N-ethylcyclohexylamine. It is a 4 to 12 cycloalkylamine and the alkyl (carbon number 1 to 6) substituents and the like.
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 amine 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, A heterocyclic amine having a carbon number of 4 to 10, such as a porphyrin.
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 above photopolymerization initiator addition step can be carried out at any time. For example, the photopolymerization initiator (C) may be added during the preparation of the reaction liquid in the reaction liquid preparation step, or the photopolymerization initiator (C) may be added to the reaction liquid after the reaction step.
實施例 Example
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 by way of Examples and Comparative Examples, but the present invention is not limited thereto.
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, water 0.01 was added. And 0.3 parts of triethylamine (a2-2) and stirred for 30 minutes, after which 20.0 parts of zirconium tetra-n-butoxide (a1-1) [trade name: TBZR; manufactured by Nippon Soda Co., Ltd.] was added to make it The reaction was carried out at 65 ° C for 2 hours. Thereafter, 2.0 parts of 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (C1-1) [trade name "Lucirin TPO"; manufactured by BASF Corporation) was added, and the mixture was stirred at 65 ° C until it became changed. It was made uniform to obtain an active energy ray-curable composition (D-1).
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)。 To a reaction vessel equipped with a stirrer, a condenser, and a thermometer, phenoxyethyl acrylate (B-2) [trade name: Light acrylate POA; manufactured by Kyoeisha Chemical Co., Ltd.] 45.0 parts, addition of 10 mole epoxy Ethyl acrylate (B-4) [trade name: KOMERATE-D104; manufactured by KPX Green Chemical Co., Ltd.] 40.0 parts, 0.1 parts of water and 0.03 parts of triethylamine (a2-2) and stirred 30 Minutes, after that, 15.0 parts of titanium tetra-n-butoxide (a1-2) [trade name: B-1; manufactured by Nippon Soda Co., Ltd.] was added, and it was allowed to react at 65 ° C for 2 hours, after which bis (2, 4) was added. , 6-trimethylbenzimidyl)-phenylphosphine oxide (C1-2) [trade name "Irgacure-819"; manufactured by BASF Corporation] 2.0 parts, and mixed and stirred at 65 ° C until uniform, 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 moles of epoxy were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer. Ethyl 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, after which 2,4,6-trimethylbenzimidyldiphenylphosphine oxide was added. (C1-1) 2.0 parts and mixed and stirred at 65 ° C until uniform, and an active energy ray-curable composition (D-3) was obtained.
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)。 Adding 70.0 parts of o-phenylphenoxyethyl acrylate (B-1) to a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and adding 10.0 parts of oxime acrylate (B-3) of 6 mol of ethylene oxide, 0.05 parts of water and 0.05 parts of trimethylamine (a2-1) and stirred for 30 minutes, after which 20.0 parts of titanium tetra-n-butoxide (a1-2) was added and allowed to react at 65 ° C for 2 hours, after which 1 was added. 2-hydroxycyclohexyl phenyl ketone (C5-1) [trade name "Irgacure 184"; manufactured by BASF Corporation) 2.0 parts, and mixed and stirred at 65 ° C until uniform, 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 added. 40.0 parts of zirconium tetra-n-butoxide (a1-1), which was allowed to react at 65 ° C for 2 hours, after which bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (C1- 2) 2.0 parts, and mixing and stirring at 65 ° C until it became uniform, and the active energy ray hardening composition (D-5) was obtained.
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)。 Adding 45.0 parts of phenoxyethyl acrylate (B-2) to a reaction vessel equipped with a stirrer, a condenser and a thermometer, and adding 100.0 parts of oxime acrylate (B-4) of 10 moles of ethylene oxide, double (2) , 4,6-trimethylbenzhydryl)-phenylphosphine oxide (C1-2) 3.0 parts, and mixed at 65 ° C The mixture was stirred until it became uniform, and an active energy ray-curable composition (D'-1) was obtained.
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)。 45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of oxime acrylate (B-4) added with 10 moles of ethylene oxide, and titanium oxide fine particles were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer. (A-1) [trade name: MT-01; manufactured by Dihua Co., Ltd.] 2.0 parts, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (C1-2) 2.0 The mixture was mixed and stirred at 65 ° C until it became uniform, 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)。 45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of oxime acrylate (B-4) added with 10 moles of ethylene oxide, and titanium oxide fine particles were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer. (A-1) 5.0 parts of 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (C1-1) 2.0 parts, and mixed and stirred at 65 ° C until uniform, to obtain active energy Linear 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)。 Adding 70.0 parts of o-phenylphenoxyethyl acrylate (B-1) to a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and adding 10.0 parts of oxime acrylate (B-3) of 6 mol of ethylene oxide, 5.0 parts of water and 0.05 parts of triethylamine (a2-2) and stirred for 30 minutes, after which 20.0 parts of zirconium tetra-n-butoxide (a1-1) was added and allowed to react at 65 ° C for 2 hours, after which 2 was added. , 4,6-trimethylbenzimidyldiphenylphosphine oxide (C1-1), 2.0 parts, and mixed and stirred at 65 ° C until uniform, to obtain an active energy ray hardening 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)。 Adding o-phenylphenoxy acrylate to a reaction vessel equipped with a stirrer, a condenser and a thermometer 70.0 parts of ethyl ester (B-1), addition of 10.0 parts of oxime acrylate (B-3) of 6 moles of 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, after which 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (C1) was added. -1) 2.0 parts, and mixed and stirred at 65 ° C until uniform, and an active energy ray-curable composition (D'-5) was obtained.
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, after which 2,4,6-trimethylbenzimidyldiphenylphosphine oxide was added. (C1-1) 2.0 parts and mixed and stirred at 65 ° C until uniform, and an active energy ray-curable composition (D'-6) was obtained.
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 composition of Examples 1 to 5 and Comparative Examples 1 to 6 at 25 ° C by the methods described below, and Examples 1 to 5 and Comparative Example 1 The adhesion of the cured product of the active energy ray-curable composition of ~6 and the recovery of the flaw 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。 Further, in the examples and comparative examples containing the organic solvent, the organic solvent was sufficiently volatilized by an evaporator and then evaluated.
[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。 The refractive index of the active energy ray-curable composition of Examples 1 to 5 and Comparative Examples 1 to 6 was carried out under the environment of 25 ° C using a refractometer [trade name: Abbe refractometer 4T; manufactured by Aiwa Co., Ltd.]. 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 2 cm square of ruthenium rubber having a thickness of 100 μm was placed on a glass slide having a thickness of 1 mm, and the active energy ray-curable composition of each of the examples and the comparative examples was poured into the excavated portion. Then, another slide having a thickness of 1 mm was placed on the active energy ray-curable composition that had flowed in, and both ends of each slide were fixed by a jig. Thereafter, the total light transmittance (%) was measured in accordance with JIS-K7105 using a total light transmittance measuring device [trade name "haze-garddual"; manufactured by BYK Gardner Co., Ltd.).
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。 Further, 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。 The active energy ray-curable composition was applied to one surface of a glass plate so as to have a thickness of 20 μm by an applicator, and then a PET film having a thickness of 100 μm [trade name "COSMOSHINE A4300"; manufactured by Toyobo Co., Ltd.] The film was bonded to the side of the active energy ray-curable composition, and the air was extruded from above to extrude the air. The active energy ray-curable composition was cured by irradiating ultraviolet rays from the PET film side at 1000 mJ/cm 2 by an ultraviolet irradiation device. The cured product adhered to the PET film was peeled off from the glass plate to prepare a test piece.
[密接性之評價] [Evaluation of adhesion]
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 test piece was allowed to stand in an environment of 23° C. and a relative humidity of 50% for 24 hours, a checkerboard (10×10 pieces) was prepared by cutting a slit of 1 mm width by a cutting knife according to JIS K5600-5-6. A cellophane adhesive tape was attached to the checkerboard and peeled off at 90 degrees to visually observe the peeling state of the cured product from the PET film, and was evaluated by 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: More than 90 of the 100 checkerboards are not peeled off and remain on the substrate.
B：100個棋盤格之中10~89個未剝離而殘留於基材 B: 10 to 89 of the 100 checkerboards are not peeled off and remain on the substrate.
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 the 100 checkerboards are not peeled off and remain on the substrate.
[傷痕之恢復性之評價] [Evaluation of the recovery of scars]
(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 having a groove depth of 50 μm and a pitch width of 20 μm engraved with parallel lines and finely embossed was prepared.
(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) The active energy ray-curable composition is applied to one side of the mold so as to have a thickness of 100 μm by an applicator, and then a PET film having a thickness of 100 μm [trade name "COSMOSHINE A4300"; Toyo Textile Co., Ltd. The company manufactured] is attached to the side of the active energy ray-curable composition, and rolls the air from above to extrude the air. Ultraviolet irradiation apparatus [Model "VPS/I600"; manufactured by Fusion Ultraviolet Systems Co., Ltd.] was irradiated with ultraviolet rays from the PET film side at 1000 mJ/cm 2 to be cured, thereby producing a film-like cured product.
(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) Using a pencil with a chrome cap, a film-like cured product according to 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 cured product after the scratch test was visually observed and judged by the following criteria.
A：劃傷於3秒以內完全消失 A: Scratch completely disappears within 3 seconds
B：劃傷即便經過3秒亦有一部分殘留 B: Scratch has a part of residue even after 3 seconds.
C：劃傷即便經過3秒亦全部殘留 C: Scratch all remains 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。 In any of the active energy ray-curable compositions of Examples 1 to 5, the refractive index is sufficiently high, the transparency is excellent, the adhesion to the plastic substrate is high, and the recovery of the flaw is excellent.
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 active energy ray-curable composition of Comparative Example 1 containing no metal oxide (A) had a refractive index of less than 1.56, and the adhesion was poor, and the recovery property of the flaw was also 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 active energy ray-curable composition of Comparative Example 6 using an aromatic ring-free (meth) acrylate had a refractive index of 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 is preferably used as an optical component because it has a high refractive index and is excellent in transparency, and has excellent recovery from scratches of a cured product and high adhesion to a plastic substrate. 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, and a film. More specifically, for example, a plastic lens (a lens, a lenticular lens, and a micro-transparent lens) Mirror, Fresnel lens, viewing angle lifting lens, etc.), optical compensation film, retardation film, germanium, optical fiber, solder resist for flexible printed wiring, plating resist, interlayer insulating film for multilayer printed wiring board, and photosensitive Optical waveguides, etc.
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| 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 |
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2016
- 2016-04-06 KR KR1020177027768A patent/KR20170125076A/en not_active Application Discontinuation
- 2016-04-06 WO PCT/JP2016/061214 patent/WO2016163381A1/en active Application Filing
- 2016-04-06 CN CN201680020396.3A patent/CN107428858B/en active Active
- 2016-04-06 JP JP2017511005A patent/JP6714581B2/en active Active
- 2016-04-07 TW TW105110845A patent/TWI647271B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107428858A (en) | 2017-12-01 |
| JPWO2016163381A1 (en) | 2018-02-01 |
| KR20170125076A (en) | 2017-11-13 |
| JP6714581B2 (en) | 2020-06-24 |
| CN107428858B (en) | 2020-02-07 |
| WO2016163381A1 (en) | 2016-10-13 |
| TWI647271B (en) | 2019-01-11 |
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