JPWO2009075287A1 - High refractive resin composition, film-shaped optical member using the same, and method for producing high refractive resin composition - Google Patents
High refractive resin composition, film-shaped optical member using the same, and method for producing high refractive resin composition Download PDFInfo
- Publication number
- JPWO2009075287A1 JPWO2009075287A1 JP2009545429A JP2009545429A JPWO2009075287A1 JP WO2009075287 A1 JPWO2009075287 A1 JP WO2009075287A1 JP 2009545429 A JP2009545429 A JP 2009545429A JP 2009545429 A JP2009545429 A JP 2009545429A JP WO2009075287 A1 JPWO2009075287 A1 JP WO2009075287A1
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- Prior art keywords
- resin composition
- titanium
- high refractive
- diethanolamine
- water
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 87
- 230000003287 optical effect Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 4
- 239000010408 film Substances 0.000 description 28
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 28
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 239000010409 thin film Substances 0.000 description 18
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- 238000002835 absorbance Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
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- 238000011156 evaluation Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
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- 239000004065 semiconductor Substances 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 241000220317 Rosa Species 0.000 description 3
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- 125000003545 alkoxy group Chemical group 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
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- 239000010419 fine particle Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
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- 239000004611 light stabiliser Substances 0.000 description 2
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- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
透明、高屈折率でかつ膜状の光学部材を形成することが可能な高屈折樹脂組成物及びこれを用いた膜状光学部材並びに高屈折樹脂組成物の製造方法を提供する。チタンアルコキシド、ジエタノールアミン及び水を混合して加熱し、加水分解により生成する副生成物のアルコールを留去して得られる含金属高屈折中間体を含む高屈折樹脂組成物であって、前記アルコールを留去した後、さらにジエタノールアミンと水とを加えてなることを特徴とする高屈折樹脂組成物である。Provided are a high refractive resin composition capable of forming a transparent, high refractive index and film-shaped optical member, a film-shaped optical member using the same, and a method for producing the high refractive resin composition. A high refractive resin composition comprising a metal-containing high refractive intermediate obtained by mixing and heating titanium alkoxide, diethanolamine and water, and distilling off an alcohol as a by-product produced by hydrolysis, After distilling off, a high refractive resin composition characterized by further adding diethanolamine and water.
Description
本発明は、高屈折樹脂組成物及びこれを用いた膜状光学部材並びに高屈折樹脂組成物の製造方法に関する。
さらに、詳しくは、プラスチックレンズ、プリズム、光ファイバー、情報記録基板（光ディスク）、フィルター、液晶ディスプレイ用部材、プラズマディスプレイ用部材、プリズムシート、ディフューザ、光散乱フィルム、視野角向上フィルム、輝度向上フィルム、偏光子、太陽電池用ライトトラッピングフィルム等に代表される膜状光学部材及びその樹脂材料に関し、特に、高い屈折率を有する薄膜状光学部材及び薄膜状光学部材を提供するための高屈折樹脂組成物並びに高屈折樹脂組成物製造方法に関する。The present invention relates to a high refractive resin composition, a film-like optical member using the same, and a method for producing the high refractive resin composition.
More specifically, plastic lenses, prisms, optical fibers, information recording substrates (optical disks), filters, liquid crystal display members, plasma display members, prism sheets, diffusers, light scattering films, viewing angle enhancement films, brightness enhancement films, polarization In particular, the present invention relates to a film-like optical member typified by a light trapping film for a solar cell and a resin material thereof, and particularly to a thin-film optical member having a high refractive index and a high-refractive resin composition for providing a thin-film optical member, and The present invention relates to a method for producing a highly refractive resin composition.
近年、軽量でかつ加工性に富み、各種の光学部材として好適な樹脂材料として、１．６〜２．２程度の高い屈折率を有する透明樹脂材料（以下、適宜、高屈折性樹脂材料という）が要求されている。 In recent years, a transparent resin material having a high refractive index of about 1.6 to 2.2 (hereinafter, appropriately referred to as a high refractive resin material) as a resin material that is lightweight and rich in workability and is suitable as various optical members. Is required.
従来技術における高屈折率樹脂材料は、ポリチオール化合物とポリイソシアネート化合物から得られるチオウレタン（例えば、特許文献１参照）、エポキシ樹脂又はエピスルフィド樹脂から得られる重合体（例えば、特許文献２参照）などが挙げられるが、これらイオウ系の高屈折樹脂材料は、屈折率の限界が１．７２程度であるのに加え、硬化前の臭気が激しく、工程上の制約を受ける。 The high refractive index resin material in the prior art includes a thiourethane obtained from a polythiol compound and a polyisocyanate compound (for example, see Patent Document 1), a polymer obtained from an epoxy resin or an episulfide resin (for example, see Patent Document 2), and the like. These sulfur-based high-refractive resin materials have a refractive index limit of about 1.72 and a strong odor before curing, which is subject to process restrictions.
また、ベンゼン環に臭素を導入したポリマが既に市販化されているが、その屈折率は１．６程度である。
さらに、含臭素化合物は、ダイオキシンを発生させる可能性があることから、近年は、その使用が制限されている。Moreover, although the polymer which introduce | transduced the bromine into the benzene ring is already marketed, the refractive index is about 1.6.
Furthermore, since bromine-containing compounds may generate dioxins, their use has been limited in recent years.
また、樹脂中に酸化チタン、酸化亜鉛等の高屈折率金属酸化物微粒子を分散させる技術が提案されているが（例えば、特許文献３参照）、光散乱を引き起こさないようにこれらの微粒子を分散させるのは極めて難しい。 Further, a technique for dispersing high refractive index metal oxide fine particles such as titanium oxide and zinc oxide in a resin has been proposed (for example, see Patent Document 3), but these fine particles are dispersed so as not to cause light scattering. It is extremely difficult to do.
また、チタンアルコキシドのゾルゲル反応を樹脂マトリクス中で行う有機−無機ハイブリッド系も多々報告されているが（例えば、特許文献４、５参照）、光散乱を引き起こしてしまうため、光学用途としての実用化には至っていない。 In addition, many organic-inorganic hybrid systems in which a sol-gel reaction of titanium alkoxide is performed in a resin matrix have been reported (see, for example, Patent Documents 4 and 5). It has not reached.
また、本発明と比較的近いものとして、例えば、特許文献６や特許文献７に記載の発明が挙げられるが、特許文献６の発明では、粘度が低すぎて１〜１０００μｍ程度の厚膜を形成することはできない。 In addition, the invention described in Patent Document 6 and Patent Document 7 can be cited as comparatively close to the present invention. In the invention of Patent Document 6, the viscosity is too low to form a thick film of about 1 to 1000 μm. I can't do it.
また、特許文献７にある有機・無機ポリマー複合体及びその製造方法では、反応性の高い金属アルコキシドを用いる場合、その反応性制御と均一分散が困難である。例えば、チタンアルコキシドのゾルゲル反応は、非常に反応性が高いため、酸化チタン粒子が光を散乱させる程度以上の粒子サイズ（＞１００ｎｍ）になり易い。 In addition, in the organic / inorganic polymer composite and the production method thereof disclosed in Patent Document 7, when a highly reactive metal alkoxide is used, it is difficult to control the reactivity and uniformly disperse it. For example, since the sol-gel reaction of titanium alkoxide is very reactive, it tends to have a particle size (> 100 nm) larger than the titanium oxide particles scatter light.
また、酸化チタンには、光触媒活性があるので、分散媒であるポリマーを侵してしまう恐れがある。 Further, since titanium oxide has photocatalytic activity, there is a possibility that the polymer which is a dispersion medium is affected.
本発明は、透明、高屈折率でかつ膜状の光学部材を形成することが可能な高屈折樹脂組成物及びこれを用いた膜状光学部材並びに高屈折樹脂組成物の製造方法を提供することを目的とする。 The present invention provides a high refractive resin composition capable of forming a transparent, high refractive index and film-like optical member, a film-like optical member using the same, and a method for producing the high refractive resin composition. With the goal.
本発明者らは、高屈折樹脂組成物中の金属アルコキシドの反応性を抑制し、その粒子成長を抑えることで、透明、高屈折率かつ所望膜厚の膜状光学部材を得ることが可能であることを見出し、本発明を完成するに至った。 By suppressing the reactivity of metal alkoxide in the high refractive resin composition and suppressing the particle growth, the present inventors can obtain a film-like optical member having a transparent, high refractive index and a desired film thickness. As a result, the present invention has been completed.
（１）チタンアルコキシド、ジエタノールアミン及び水を混合して加熱し、加水分解により生成する副生成物のアルコールを留去して得られる含金属高屈折中間体を含む高屈折樹脂組成物であって、
前記アルコールを留去した後、さらにジエタノールアミンと水とを加えてなることを特徴とする高屈折樹脂組成物。(1) A high-refractive resin composition comprising a metal-containing high-refractive intermediate obtained by mixing and heating titanium alkoxide, diethanolamine and water, and distilling off a by-product alcohol produced by hydrolysis,
A high refractive resin composition comprising diethanolamine and water added after the alcohol is distilled off.
（２）前記アルコールを留去した後、前記ジエタノールアミンを先に加え、水を後に加えることを特徴とする前記（１）に記載の高屈折樹脂組成物。 (2) The highly refractive resin composition as described in (1) above, wherein after distilling off the alcohol, the diethanolamine is added first, and water is added later.
（３）前記アルコールを留去した後、水とジエタノールアミンとを、あらかじめ混合した混合物の状態で加えることを特徴とする前記（１）に記載の高屈折樹脂組成物。 (3) The highly refractive resin composition as described in (1) above, wherein after the alcohol is distilled off, water and diethanolamine are added in the form of a premixed mixture.
（４）前記アルコールを留去する前におけるチタンアルコキシド、ジエタノールアミン、及び水の混合モル比をｎ：ｍ：ｌとした場合、ｌ＜ｎ≦ｍであることを特徴とする前記（１）から（３）のいずれかに記載の高屈折樹脂組成物。 (4) When the mixing molar ratio of titanium alkoxide, diethanolamine, and water before distilling off the alcohol is n: m: l, l <n ≦ m. The highly refractive resin composition according to any one of 3).
（５）前記アルコールを留去する前に、さらに溶媒を含有してなることを特徴とする前記（１）から（４）のいずれかに記載の高屈折樹脂組成物。 (5) The high refractive resin composition as described in any one of (1) to (4) above, further comprising a solvent before distilling off the alcohol.
（６）前記（１）から（５）のいずれかに記載の高屈折樹脂組成物を用いて形成されることを特徴とする膜状光学部材。 (6) A film-shaped optical member formed using the high refractive resin composition according to any one of (1) to (5).
（７）膜厚が１〜１０００μｍの範囲である前記（６）に記載の膜状光学部材。 (7) The film-shaped optical member according to (6), wherein the film thickness is in the range of 1 to 1000 μm.
（８）チタンアルコキシドとジエタノールアミンと水とを混合し加熱し、加水分解により生成する副生成物のアルコールを留去して含金属高屈折中間体を得る第１の工程と、
前記含金属高屈折中間体を得た後、ジエタノールアミンと水とをさらに加える第２の工程と、
を有することを特徴とする高屈折樹脂組成物の製造方法。(8) a first step of mixing titanium alkoxide, diethanolamine, and water, heating and distilling off by-product alcohol produced by hydrolysis to obtain a metal-containing highly refractive intermediate;
A second step of further adding diethanolamine and water after obtaining the metal-containing highly refractive intermediate;
A process for producing a highly refractive resin composition, comprising:
（９）前記第２の工程において、ジエタノールアミンを先に加え、水を後に加えることを特徴とする前記（８）に記載の高屈折樹脂組成物の製造方法。 (9) The method for producing a highly refractive resin composition as described in (8) above, wherein in the second step, diethanolamine is added first and water is added later.
（１０）前記第２の工程において、ジエタノールアミンと水とを、あらかじめ混合した混合物の状態で加えることを特徴とする前記（８）に記載の高屈折樹脂組成物の製造方法。 (10) The method for producing a highly refractive resin composition as described in (8) above, wherein in the second step, diethanolamine and water are added in the form of a premixed mixture.
（１１）前記第１の工程において、前記アルコールを留去する前におけるチタンアルコキシド、ジエタノールアミン、水の混合モル比をｎ：ｍ：ｌとした場合、ｌ＜ｎ≦ｍの混合比で前記チタンアルコキシド、前記ジエタノールアミン及び前記水を混合し加熱することを特徴とする前記（８）から（１０）のいずれかに記載の高屈折樹脂組成物の製造方法。 (11) In the first step, when the mixing molar ratio of titanium alkoxide, diethanolamine and water before distilling off the alcohol is n: m: l, the titanium alkoxide has a mixing ratio of l <n ≦ m. The method for producing a highly refractive resin composition according to any one of (8) to (10), wherein the diethanolamine and the water are mixed and heated.
（１２）前記第１の工程におけるアルコール留去前に、さらに溶媒を含有させることを特徴とする前記（８）から（１１）のいずれかに記載の高屈折樹脂組成物の製造方法。 (12) The method for producing a highly refractive resin composition as described in any one of (8) to (11) above, further comprising a solvent before the alcohol is distilled off in the first step.
上記のような構成にすることにより、プラスチックレンズ、プリズム、光ファイバー、情報記録基板、フィルター、液晶ディスプレイ用部材、プラズマディスプレイ用部材、プリズムシート、ディフューザ、光散乱フィルム、視野角向上フィルム、輝度向上フィルム、偏光子、太陽電池用ライトトラッピングフィルム等に代表される膜状光学部材及びその樹脂材料に適用できる。特に、高い屈折率を有する薄膜状光学部材及び高屈折樹脂組成物に適用できる。 By adopting the above configuration, plastic lenses, prisms, optical fibers, information recording substrates, filters, liquid crystal display members, plasma display members, prism sheets, diffusers, light scattering films, viewing angle enhancement films, brightness enhancement films It can be applied to a film-like optical member typified by a polarizer, a light trapping film for solar cells, and the like, and a resin material thereof. In particular, the present invention can be applied to a thin film optical member having a high refractive index and a high refractive resin composition.
本発明によれば、従来よりも透明、高屈折率でかつ所望の膜厚が得られる光学部材を形成することが可能な高屈折樹脂組成物及び該高屈折樹脂組成物を製造し得る高屈折樹脂組成物の製造方法を提供することができる。
また、本発明によれば、従来よりも透明、高屈折率でかつ所望の膜厚が得られる膜状光学部材を提供することが可能である。According to the present invention, a highly refractive resin composition capable of forming an optical member that is more transparent and has a higher refractive index and a desired film thickness than the conventional one, and a high refractive index that can produce the highly refractive resin composition. A method for producing a resin composition can be provided.
In addition, according to the present invention, it is possible to provide a film-like optical member that is transparent, has a higher refractive index, and has a desired film thickness.
以下にまず、本発明の高屈折樹脂組成物、及び本発明の高屈折樹脂組成物の製造方法の実施の形態について双方交えて説明する。 First, the embodiment of the high refractive resin composition of the present invention and the method for producing the high refractive resin composition of the present invention will be described together.
本発明の高屈折樹脂組成物は、チタンアルコキシド、ジエタノールアミン及び水を混合して加熱し、加水分解により生成する副生成物のアルコールを留去して得られる含金属高屈折中間体を含む高屈折樹脂組成物であって、前記アルコールを留去した後、さらに水とジエタノールアミンとを加えてなることを特徴としている。
本発明の高屈折樹脂組成物の製造方法は、チタンアルコキシドとジエタノールアミンと水とを混合し加熱し、加水分解により生成する副生成物のアルコールを留去して含金属高屈折中間体を得る第１の工程と、前記含金属高屈折中間体を得た後、水とジエタノールアミンとをさらに加える第２の工程と、を有することを特徴としている。The high-refractive resin composition of the present invention comprises a metal-containing high-refractive intermediate obtained by mixing and heating titanium alkoxide, diethanolamine, and water, and distilling off by-product alcohol produced by hydrolysis. The resin composition is characterized in that after the alcohol is distilled off, water and diethanolamine are further added.
The method for producing a highly refractive resin composition according to the present invention comprises a step of mixing a titanium alkoxide, diethanolamine and water, heating, distilling off by-product alcohol produced by hydrolysis, and obtaining a metal-containing highly refractive intermediate. And a second step of further adding water and diethanolamine after the metal-containing highly refractive intermediate is obtained.
［含金属高屈折中間体］
含金属高屈折中間体は、上述の通り、チタンアルコキシド、ジエタノールアミン及び水を混合して加熱し、加水分解により生成する副生成物のアルコールを留去して得られる。なお、この含金属高屈折中間体を得る工程は、本発明の製造方法における第１の工程である。
前記ジエタノールアミンは、チタンアルコキシドに配位し、加水分解反応の進行を制御し、酸化チタン粒子の成長を抑制する役割を果たす。
このように、本発明の高屈折樹脂組成物は、加水分解による副生成物のアルコールを積極的に留去することにより含金属高屈折中間体が得られ、よって酸化チタン粒子の成長が抑制されるので、必要以上に大きな粒子とならず、硬化物の光散乱を引き起こさないようにすることが可能となる。[Metal-containing highly refractive intermediates]
As described above, the metal-containing highly refractive intermediate is obtained by mixing and heating titanium alkoxide, diethanolamine and water, and distilling off the alcohol as a by-product generated by hydrolysis. The step of obtaining the metal-containing highly refractive intermediate is the first step in the production method of the present invention.
The diethanolamine functions to coordinate with titanium alkoxide, control the progress of hydrolysis reaction, and suppress the growth of titanium oxide particles.
As described above, the high refractive resin composition of the present invention can obtain a metal-containing high refractive intermediate by positively distilling off the alcohol as a by-product by hydrolysis, thereby suppressing the growth of titanium oxide particles. Therefore, the particles are not larger than necessary, and it is possible not to cause light scattering of the cured product.
（チタンアルコキシド）
前記チタンアルコキシドは、目的に応じて他の金属アルコキシドを部分的に用いることもできる。その金属としては、特に限定されないが、Ｚｎ、Ｚｒ、Ｌａ、Ｔｈ、Ｔａ、Ｓｉ、Ｇｅなどが挙げられる。(Titanium alkoxide)
As the titanium alkoxide, other metal alkoxides can be partially used depending on the purpose. The metal is not particularly limited, and examples thereof include Zn, Zr, La, Th, Ta, Si, and Ge.
前記高屈折樹脂組成物に使用されるチタンアルコキシドの加水分解性アルコキシ基としては、特に制限はないが、例えば、炭素数１〜６のアルコキシ基、具体的には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等が挙げられる。炭素数が３〜６であるとゾルゲル反応が十分に進行することから、好ましくはプロポキシ基、イソプロポキシ基、ブトキシ基であり、特に好ましくはイソプロポキシ基である。金属上のこれらアルコキシ基の種類はすべて同一であっても、違っていても差し支えない。 The hydrolyzable alkoxy group of the titanium alkoxide used in the high refractive resin composition is not particularly limited. For example, the alkoxy group having 1 to 6 carbon atoms, specifically, methoxy group, ethoxy group, propoxy Group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group, hexyloxy group and the like. Since the sol-gel reaction proceeds sufficiently when the carbon number is 3 to 6, a propoxy group, an isopropoxy group, and a butoxy group are preferable, and an isopropoxy group is particularly preferable. The types of these alkoxy groups on the metal can be the same or different.
前記高屈折樹脂組成物に使用されるチタンアルコキシドとしては、例えば、チタニウムテトラメトキシ、チタニウムテトラエトキシ、チタニウムテトラ−ｎ−プロポキシ、チタニウムテトラ−ｉｓｏ−プロポキシ、チタニウムテトラ−ｎ−ブトキシ、チタニウムテトラ−ｓｅｃ−ブトキシ、チタニウムテトラ−ｔｅｒｔ−ブトキシ、チタニウムテトラフェノキシ等のテトラアルコキシ、チタニウムトリメトキシ、チタニウムトリエトキシ、チタニウムトリプロポキシ、チタニウムフルオロトリメトキシ、チタニウムフルオロトリエトキシ、チタニウムメチルトリメトキシ、チタニウムメチルトリエトキシ、チタニウムメチルトリ−ｎ−プロポキシ、チタニウムメチルトリ−ｉｓｏ−プロポキシ、チタニウムメチルトリ−ｎ−ブトキシ、チタニウムメチルトリ−ｉｓｏ−ブトキシ、チタニウムメチルトリ−ｔｅｒｔ−ブトキシ、チタニウムメチルトリフェノキシ、チタニウムエチルトリメトキシ、チタニウムエチルトリエトキシ、チタニウムエチルトリ−ｎ−プロポキシ、チタニウムエチルトリ−ｉｓｏ−プロポキシ、チタニウムエチルトリ−ｎ−ブトキシ、チタニウムエチルトリ−ｉｓｏ−ブトキシ、チタニウムエチルトリ−ｔｅｒｔ−ブトキシ、チタニウムエチルトリフェノキシ、チタニウムｎ−プロピルトリメトキシ、チタニウムｎ−プロピルトリエトキシ、チタニウムｎ−プロピルトリ−ｎ−プロポキシ、チタニウムｎ−プロピルトリ−ｉｓｏ−プロポキシ、チタニウムｎ−プロピルトリ−ｎ−ブトキシ、チタニウムｎ−プロピルトリ−ｉｓｏ−ブトキシ、チタニウムｎ−プロピルトリ−ｔｅｒｔ−ブトキシ、チタニウムｎ−プロピルトリフェノキシ、チタニウムｉｓｏ−プロピルトリメトキシ、チタニウムｉｓｏ−プロピルトリエトキシ、チタニウムｉｓｏ−プロピルトリ−ｎ−プロポキシ、チタニウムｉｓｏ−プロピルトリ−ｉｓｏ−プロポキシ、チタニウムｉｓｏ−プロピルトリ−ｎ−ブトキシ、チタニウムｉｓｏ−プロピルトリ−ｉｓｏ−ブトキシ、チタニウムｉｓｏ−プロピルトリ−ｔｅｒｔ−ブトキシ、チタニウムｉｓｏ−プロピルトリフェノキシ、チタニウムｎ−ブチルトリメトキシ、チタニウムｎ−ブチルトリエトキシ、チタニウムｎ−ブチルトリ−ｎ−プロポキシ、チタニウムｎ−ブチルトリ−ｉｓｏ−プロポキシ、チタニウムｎ−ブチルトリ−ｎ−ブトキシ、チタニウムｎ−ブチルトリ−ｉｓｏ−ブトキシ、チタニウムｎ−ブチルトリ−ｔｅｒｔ−ブトキシ、チタニウムｎ−ブチルトリフェノキシ、チタニウムｓｅｃ−ブチルトリメトキシ、チタニウムｓｅｃ−ブチルトリエトキシ、チタニウムｓｅｃ−ブチルトリ−ｎ−プロポキシ、チタニウムｓｅｃ−ブチルトリ−ｉｓｏ−プロポキシ、チタニウムｓｅｃ−ブチルトリ−ｎ−ブトキシ、チタニウムｓｅｃ−ブチルトリ−ｉｓｏ−ブトキシ、チタニウムｓｅｃ−ブチルトリ−ｔｅｒｔ−ブトキシ、チタニウムｓｅｃ−ブチルトリフェノキシ、チタニウムｔｅｒｔ−ブチルトリメトキシ、チタニウムｔｅｒｔ−ブチルトリエトキシ、チタニウムｔｅｒｔ−ブチルトリ−ｎ−プロポキシ、チタニウムｔｅｒｔ−ブチルトリ−ｉｓｏ−プロポキシ、チタニウムｔｅｒｔ−ブチルトリ−ｎ−ブトキシ、チタニウムｔｅｒｔ−ブチルトリ−ｉｓｏ−ブトキシ、チタニウムｔｅｒｔ−ブチルトリ−ｔｅｒｔ−ブトキシ、チタニウムｔ−ブチルトリフェノキシ、チタニウムフェニルトリメトキシ、チタニウムフェニルトリエトキシ、チタニウムフェニルトリ−ｎ−プロポキシ、チタニウムフェニルトリ−ｉｓｏ−プロポキシ、チタニウムフェニルトリ−ｎ−ブトキシ、チタニウムフェニルトリ−ｉｓｏ−ブトキシ、チタニウムフェニルトリ−ｔｅｒｔ−ブトキシ、チタニウムフェニルトリフェノキシ、チタニウムトリフルオロメチルトリメトキシ、チタニウムペンタフルオロエチルトリメトキシ、チタニウム３，３，３−トリフルオロプロピルトリメトキシ、チタニウム３，３，３−トリフルオロプロピルトリエトキシ等のトリアルコキシ、チタニウムジメチルジメトキシ、チタニウムジメチルジエトキシ、チタニウムジメチルジ−ｎ−プロポキシ、チタニウムジメチルジ−ｉｓｏ−プロポキシ、チタニウムジメチルジ−ｎ−ブトキシ、チタニウムジメチルジ−ｓｅｃ−ブトキシ、チタニウムジメチルジ−ｔｅｒｔ−ブトキシ、チタニウムジメチルジフェノキシ、チタニウムジエチルジメトキシ、チタニウムジエチルジエトキシ、チタニウムジエチルジ−ｎ−プロポキシ、チタニウムジエチルジ−ｉｓｏ−プロポキシ、チタニウムジエチルジ−ｎ−ブトキシ、チタニウムジエチルジ−ｓｅｃ−ブトキシ、チタニウムジエチルジ−ｔｅｒｔ−ブトキシ、チタニウムジエチルジフェノキシ、チタニウムジ−ｎ−プロピルジメトキシ、チタニウムジ−ｎ−プロピルジエトキシ、チタニウムジ−ｎ−プロピルジ−ｎ−プロポキシ、チタニウムジ−ｎ−プロピルジ−ｉｓｏ−プロポキシ、チタニウムジ−ｎ−プロピルジ−ｎ−ブトキシ、チタニウムジ−ｎ−プロピルジ−ｓｅｃ−ブトキシ、チタニウムジ−ｎ−プロピルジ−ｔｅｒｔ−ブトキシ、チタニウムジ−ｎ−プロピルジフェノキシ、チタニウムジ−ｉｓｏ−プロピルジメトキシ、チタニウムジ−ｉｓｏ−プロピルジエトキシ、チタニウムジ−ｉｓｏ−プロピルジ−ｎ−プロポキシ、チタニウムジ−ｉｓｏ−プロピルジ−ｉｓｏ−プロポキシ、チタニウムジ−ｉｓｏ−プロピルジ−ｎ−ブトキシ、チタニウムジ−ｉｓｏ−プロピルジ−ｓｅｃ−ブトキシ、チタニウムジ−ｉｓｏ−プロピルジ−ｔｅｒｔ−ブトキシ、チタニウムジ−ｉｓｏ−プロピルジフェノキシ、チタニウムジ−ｎ−ブチルジメトキシ、チタニウムジ−ｎ−ブチルジエトキシ、チタニウムジ−ｎ−ブチルジ−ｎ−プロポキシ、チタニウムジ−ｎ−ブチルジ−ｉｓｏ−プロポキシ、チタニウムジ−ｎ−ブチルジ−ｎ−ブトキシ、チタニウムジ−ｎ−ブチルジ−ｓｅｃ−ブトキシ、チタニウムジ−ｎ−ブチルジ−ｔｅｒｔ−ブトキシ、チタニウムジ−ｎ−ブチルジフェノキシ、チタニウムジ−ｓｅｃ−ブチルジメトキシ、チタニウムジ−ｓｅｃ−ブチルジエトキシ、チタニウムジ−ｓｅｃ−ブチルジ−ｎ−プロポキシ、チタニウムジ−ｓｅｃ−ブチルジ−ｉｓｏ−プロポキシ、チタニウムジ−ｓｅｃ−ブチルジ−ｎ−ブトキシ、チタニウムジ−ｓｅｃ−ブチルジ−ｓｅｃ−ブトキシ、チタニウムジ−ｓｅｃ−ブチルジ−ｔｅｒｔ−ブトキシ、チタニウムジ−ｓｅｃ−ブチルジフェノキシ、チタニウムジ−ｔｅｒｔ−ブチルジメトキシ、チタニウムジ−ｔｅｒｔ−ブチルジエトキシ、チタニウムジ−ｔｅｒｔ−ブチルジ−ｎ−プロポキシ、チタニウムジ−ｔｅｒｔ−ブチルジ−ｉｓｏ−プロポキシ、チタニウムジ−ｔｅｒｔ−ブチルジ−ｎ−ブトキシ、チタニウムジ−ｔｅｒｔ−ブチルジ−ｓｅｃ−ブトキシ、チタニウムジ−ｔｅｒｔ−ブチルジ−ｔｅｒｔ−ブトキシ、チタニウムジ−ｔｅｒｔ−ブチルジフェノキシ、チタニウムジフェニルジメトキシ、チタニウムジフェニルジエトキシ、チタニウムジフェニルジ−ｎ−プロポキシ、チタニウムジフェニルジ−ｉｓｏ−プロポキシ、チタニウムジフェニルジ−ｎ−ブトキシ、チタニウムジフェニルジ−ｓｅｃ−ブトキシ、チタニウムジフェニルジ−ｔｅｒｔ−ブトキシ、チタニウムジフェニルジフェノキシ、チタニウムビス（３，３，３−トリフルオロプロピル）ジメトキシ、チタニウムメチル（３，３，３−トリフルオロプロピル）ジメトキシ等のジオルガノジアルコキシ等が挙げられ、中でも、プロポキシ基、イソプロポキシ基、ブトキシ基を含むものが好ましく、特に好ましくはイソプロポキシ基である。 Examples of the titanium alkoxide used in the high refractive resin composition include titanium tetramethoxy, titanium tetraethoxy, titanium tetra-n-propoxy, titanium tetra-iso-propoxy, titanium tetra-n-butoxy, and titanium tetra-sec. Tetraalkoxy such as butoxy, titanium tetra-tert-butoxy, titanium tetraphenoxy, titanium trimethoxy, titanium triethoxy, titanium tripropoxy, titanium fluorotrimethoxy, titanium fluorotriethoxy, titanium methyltrimethoxy, titanium methyltriethoxy, Titanium methyl tri-n-propoxy, titanium methyl tri-iso-propoxy, titanium methyl tri-n-butoxy, titani Mumethyltri-iso-butoxy, titaniummethyltri-tert-butoxy, titaniummethyltriphenoxy, titaniumethyltrimethoxy, titaniumethyltriethoxy, titaniumethyltri-n-propoxy, titaniumethyltri-iso-propoxy, titaniumethyltri-n -Butoxy, titanium ethyl tri-iso-butoxy, titanium ethyl tri-tert-butoxy, titanium ethyl triphenoxy, titanium n-propyl trimethoxy, titanium n-propyl triethoxy, titanium n-propyl tri-n-propoxy, titanium n -Propyltri-iso-propoxy, titanium n-propyltri-n-butoxy, titanium n-propyltri-iso-butoxy, titanium n-propyl Pyrtri-tert-butoxy, titanium n-propyltriphenoxy, titanium iso-propyltrimethoxy, titanium iso-propyltriethoxy, titanium iso-propyltri-n-propoxy, titanium iso-propyltri-iso-propoxy, titanium iso- Propyltri-n-butoxy, titanium iso-propyltri-iso-butoxy, titanium iso-propyltri-tert-butoxy, titanium iso-propyltriphenoxy, titanium n-butyltrimethoxy, titanium n-butyltriethoxy, titanium n -Butyltri-n-propoxy, titanium n-butyltri-iso-propoxy, titanium n-butyltri-n-butoxy, titanium n-butyltri-iso -Butoxy, titanium n-butyltri-tert-butoxy, titanium n-butyltriphenoxy, titanium sec-butyltrimethoxy, titanium sec-butyltriethoxy, titanium sec-butyltri-n-propoxy, titanium sec-butyltri-iso-propoxy Titanium sec-butyltri-n-butoxy, titanium sec-butyltri-iso-butoxy, titanium sec-butyltri-tert-butoxy, titanium sec-butyltriphenoxy, titanium tert-butyltrimethoxy, titanium tert-butyltriethoxy, titanium tert-butyltri-n-propoxy, titanium tert-butyltri-iso-propoxy, titanium tert-butyltri-n-butyl Xy, titanium tert-butyltri-iso-butoxy, titanium tert-butyltri-tert-butoxy, titanium tert-butyltriphenoxy, titaniumphenyltrimethoxy, titaniumphenyltriethoxy, titaniumphenyltri-n-propoxy, titaniumphenyltri-iso -Propoxy, titanium phenyl tri-n-butoxy, titanium phenyl tri-iso-butoxy, titanium phenyl tri-tert-butoxy, titanium phenyl triphenoxy, titanium trifluoromethyl trimethoxy, titanium pentafluoroethyl trimethoxy, titanium 3,3 , 3-trifluoropropyltrimethoxy, trialkoxy such as titanium 3,3,3-trifluoropropyltriethoxy Titanium dimethyldimethoxy, titanium dimethyldiethoxy, titanium dimethyldi-n-propoxy, titanium dimethyldi-iso-propoxy, titanium dimethyldi-n-butoxy, titanium dimethyldi-sec-butoxy, titanium dimethyldi-tert-butoxy, titanium Dimethyldiphenoxy, titaniumdiethyldimethoxy, titaniumdiethyldiethoxy, titaniumdiethyldi-n-propoxy, titaniumdiethyldi-iso-propoxy, titaniumdiethyldi-n-butoxy, titaniumdiethyldi-sec-butoxy, titaniumdiethyldi-tert -Butoxy, titanium diethyldiphenoxy, titanium di-n-propyldimethoxy, titanium di-n-propyldiethoxy, titanium Di-n-propyldi-n-propoxy, titanium di-n-propyldi-iso-propoxy, titanium di-n-propyldi-n-butoxy, titanium di-n-propyldi-sec-butoxy, titanium di-n-propyldi- tert-butoxy, titanium di-n-propyldiphenoxy, titanium di-iso-propyldimethoxy, titanium di-iso-propyldiethoxy, titanium di-iso-propyldi-n-propoxy, titanium di-iso-propyldi-iso- Propoxy, titanium di-iso-propyl di-n-butoxy, titanium di-iso-propyl di-sec-butoxy, titanium di-iso-propyl di-tert-butoxy, titanium di-iso-propyl diphenoxy, titanium di n-butyldimethoxy, titanium di-n-butyldiethoxy, titanium di-n-butyldi-n-propoxy, titanium di-n-butyldi-iso-propoxy, titanium di-n-butyldi-n-butoxy, titanium di- n-butyldi-sec-butoxy, titanium di-n-butyldi-tert-butoxy, titanium di-n-butyldiphenoxy, titanium di-sec-butyldimethoxy, titanium di-sec-butyldiethoxy, titanium di-sec- Butyl di-n-propoxy, titanium di-sec-butyl di-iso-propoxy, titanium di-sec-butyl di-n-butoxy, titanium di-sec-butyl di-sec-butoxy, titanium di-sec-butyl di-tert-butoxy, Titanium Di sec-butyldiphenoxy, titanium di-tert-butyldimethoxy, titanium di-tert-butyldiethoxy, titanium di-tert-butyldi-n-propoxy, titanium di-tert-butyldi-iso-propoxy, titanium di-tert- Butyl di-n-butoxy, titanium di-tert-butyl di-sec-butoxy, titanium di-tert-butyl di-tert-butoxy, titanium di-tert-butyl diphenoxy, titanium diphenyl dimethoxy, titanium diphenyl diethoxy, titanium diphenyl di- n-propoxy, titanium diphenyl di-iso-propoxy, titanium diphenyl di-n-butoxy, titanium diphenyl di-sec-butoxy, titanium diphenyl di- Examples include diorganodialkoxy, such as tert-butoxy, titanium diphenyldiphenoxy, titanium bis (3,3,3-trifluoropropyl) dimethoxy, titaniummethyl (3,3,3-trifluoropropyl) dimethoxy, and the like. , A propoxy group, an isopropoxy group and a butoxy group are preferable, and an isopropoxy group is particularly preferable.
また、本発明の高屈折樹脂組成物は、アルコール留去前のチタンアルコキシド、ジエタノールアミン、及び水の混合モル比をｎ：ｍ：ｌとした場合、ｌ＜ｎ≦ｍとすることが好ましい。水が多い場合やジエタノールアミンが少ない場合には、チタン粒子の析出やゲル化が発生するため、この不等式を満足することで、透明で均質な樹脂組成物ができる。より具体的には、ｌ＝２〜６、ｍ＝５〜９、ｎ＝３〜７あることが好ましい。 In the high refractive resin composition of the present invention, it is preferable that l <n ≦ m when the mixing molar ratio of titanium alkoxide, diethanolamine and water before distilling off alcohol is n: m: 1. When water is abundant or diethanolamine is abundant, precipitation and gelation of titanium particles occur. Therefore, by satisfying this inequality, a transparent and homogeneous resin composition can be obtained. More specifically, it is preferable that l = 2-6, m = 5-9, and n = 3-7.
（ポリマ、オリゴマ、反応性モノマ）
本発明の高屈折樹脂組成物は、ポリマ若しくはオリゴマ及び／又は反応性モノマを含んでいてもよく、ポリマ又はオリゴマとしては、特に制限はないが、光透過率や屈折率が高く、可塑性があり、耐候性の良いものが好ましく、例えば、エポキシ樹脂、ポリアミド、ポリウレタン、ポリ尿素、ポリイミン、ポリイミド、ポリアミドイミド、ポリビニル、ポリアクリル、ポリエーテル、ポリスルフィド、ポリエステル、ポリカーボネート、ポリケトン等が挙げられる。前記ポリマ又はオリゴマの成分を配合させる場合、その配合量は、前記高屈折樹脂組成物成分１００重量部に対して、１〜１００重量部であることが好ましい。(Polymer, oligomer, reactive monomer)
The high refractive resin composition of the present invention may contain a polymer or oligomer and / or a reactive monomer, and the polymer or oligomer is not particularly limited, but has high light transmittance and refractive index and is plastic. Those having good weather resistance are preferable, and examples thereof include epoxy resin, polyamide, polyurethane, polyurea, polyimine, polyimide, polyamideimide, polyvinyl, polyacryl, polyether, polysulfide, polyester, polycarbonate, and polyketone. When the polymer or oligomer component is blended, the blending amount is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the high refractive resin composition component.
反応性モノマとしては、熱や光により重合、硬化する高屈折樹脂組成物において成分となる。反応性モノマ成分の重合形態には、例えば、イオン重合やラジカル重合がよく知られているが、本発明は、それら重合形態を制限するものではない。反応性モノマとしては、具体的には、エポキシ誘導体、イソシアネート、（メタ）アクリレート、ジカルボン酸、ジオール、ジアミン、スチレン、イソプレン、ブタジエン、アクリロニトリル、プロピレン、エチレンが挙げられ、中でも、エポキシ誘導体、イソシアネート、（メタ）アクリレート、ジカルボン酸、ジオール、ジアミン、スチレンが好ましい。
上記反応性モノマを配合させる場合、その配合量は、前記高屈折樹脂組成物成分１００重量部に対して、１〜１００重量部であることが好ましい。The reactive monomer is a component in a highly refractive resin composition that is polymerized and cured by heat or light. For example, ionic polymerization or radical polymerization is well known as a polymerization form of the reactive monomer component, but the present invention does not limit the polymerization form. Specific examples of the reactive monomer include epoxy derivatives, isocyanates, (meth) acrylates, dicarboxylic acids, diols, diamines, styrene, isoprene, butadiene, acrylonitrile, propylene, and ethylene. (Meth) acrylate, dicarboxylic acid, diol, diamine and styrene are preferred.
When the reactive monomer is blended, the blending amount is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the high refractive resin composition component.
（溶媒）
前記アルコールを留去する前に、すなわち本発明の製造方法の第１の工程におけるアルコール留去前に、さらに溶媒を含有させることが好ましい。
前記溶媒としては、極性溶媒であることが好ましく、具体的には、アルコール類、Ｎ−メチルピロリドンなどであることが好ましく、これらは１種類又は２種類以上を組み合わせて使用することができる。中でも、窒素原子を有する溶媒は、窒素原子がチタンアルコキシドを安定化させるという観点から特に好ましい。窒素原子を有する溶媒としては、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルアセトアミドが挙げられ、Ｎ−メチルピロリドンが好適に使用することができる。
前記溶媒を配合させる場合、その配合量は、高屈折樹脂組成物１００重量部に対して、１〜１０００重量部であることが好ましい。(solvent)
It is preferable to further contain a solvent before distilling off the alcohol, that is, before distilling off the alcohol in the first step of the production method of the present invention.
The solvent is preferably a polar solvent, specifically, alcohols, N-methylpyrrolidone and the like, and these can be used alone or in combination of two or more. Among these, a solvent having a nitrogen atom is particularly preferable from the viewpoint that the nitrogen atom stabilizes the titanium alkoxide. Examples of the solvent having a nitrogen atom include N-methylpyrrolidone and N, N-dimethylacetamide, and N-methylpyrrolidone can be preferably used.
When the solvent is blended, the blending amount is preferably 1-1000 parts by weight with respect to 100 parts by weight of the high refractive resin composition.
アルコール類の溶媒としては、メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、セカンダリーブチルアルコール、１−ペンタノール、２−ペンタノール、３−ペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、４−ヘプタノール、１−オクタノール、２−オクタノール、３−オクタノール、４−オクタノール、エチレングリコールモノメチルエーテル等多数あるが、特に制限はない。中でも特に、１−ペンタノール、エチレングリコールモノメチルエーテル、１−ヘプタノールが好ましい。 As alcohol solvents, methanol, ethanol, propanol, isopropyl alcohol, butanol, secondary butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1 -Heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, ethylene glycol monomethyl ether, etc. are not particularly limited. Of these, 1-pentanol, ethylene glycol monomethyl ether, and 1-heptanol are particularly preferable.
（添加剤）
また、本発明の高屈折樹脂組成物は、添加剤を含有させることができる。前記添加剤としては、必要な場合には、光ラジカル重合開始剤、熱ラジカル重合開始剤等の重合開始剤を用い、さらに必要に応じて、紫外線吸収剤、光安定化剤、酸化防止剤等の安定化剤、カップリング剤、難燃剤等を挙げることができる。(Additive)
Moreover, the high refractive resin composition of this invention can contain an additive. As the additive, if necessary, a polymerization initiator such as a photo radical polymerization initiator or a thermal radical polymerization initiator is used, and if necessary, an ultraviolet absorber, a light stabilizer, an antioxidant, or the like. And stabilizers, coupling agents, flame retardants, and the like.
これらラジカル重合開始剤の配合量は、ポリマ又はオリゴマ成分と反応性モノマ成分の総量１００重量部に対して０．０１〜１０重量部の範囲であることが好ましく、０．１〜５重量部の範囲であることがより好ましい。 The blending amount of these radical polymerization initiators is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polymer or oligomer component and the reactive monomer component, and 0.1 to 5 parts by weight. A range is more preferable.
前記紫外線吸収剤や光安定化剤は、通常、ポリマ又はオリゴマ成分と反応性モノマ成分の総量１００重量部に対し０．０５〜２０重量部の範囲で添加される。 The ultraviolet absorber and light stabilizer are usually added in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymer or oligomer component and the reactive monomer component.
前記酸化防止剤は、充填材との相性や目的とする成形作業性及び樹脂保存安定性などの条件により種類、量を変えて添加する。通常、ポリマ又はオリゴマ成分と反応性モノマ成分の総量１００重量部に対し１０〜１０，０００ｐｐｍである。 The antioxidant is added in various kinds and amounts depending on conditions such as compatibility with the filler, desired molding workability and resin storage stability. Usually, it is 10 to 10,000 ppm with respect to 100 parts by weight of the total amount of the polymer or oligomer component and the reactive monomer component.
カップリング剤は、通常、ポリマ又はオリゴマ成分と反応性モノマ成分の総量１００重量部に対し、０．００１〜２０重量部添加する。
前記難燃剤の添加量は、ポリマ又はオリゴマ成分と反応性モノマ成分の総量１００重量部に対し１０〜３００重量部の範囲で用いることが好ましい。The coupling agent is usually added in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the total amount of the polymer or oligomer component and the reactive monomer component.
The amount of the flame retardant added is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the total amount of the polymer or oligomer component and the reactive monomer component.
《加熱〜加水分解》
本発明において、含金属高屈折率中間体は、以上のチタンアルコキシド、ジエタノールアミン、水、及び必要に応じて溶媒、添加剤を混合して、加熱し、加水分解することにより合成される。加水分解による副生成物としてアルコールが生成するが、既述の通り、当該アルコールは加熱により揮発し留去する。
本工程における加熱温度としては、副生成物のアルコールの沸点付近が好ましく、４０〜１５０℃とすることが好ましく、例えば、副生成物がイソプロピルアルコールの場合には６０〜１００℃とすることが好ましい。また、加熱時間としては、チタンアルコキシド量から計算されるアルコールの留去量から決定することが好ましい。<Heating to hydrolysis>
In the present invention, the metal-containing high refractive index intermediate is synthesized by mixing the above titanium alkoxide, diethanolamine, water, and, if necessary, a solvent and an additive, heating and hydrolyzing. Alcohol is generated as a by-product by hydrolysis, and as described above, the alcohol is volatilized and distilled by heating.
The heating temperature in this step is preferably near the boiling point of the by-product alcohol, preferably 40 to 150 ° C. For example, when the by-product is isopropyl alcohol, it is preferably 60 to 100 ° C. . Further, the heating time is preferably determined from the amount of alcohol distilled off calculated from the amount of titanium alkoxide.
《水及びジエタノールアミンの混合物の添加（第２の工程）》
また、本発明の高屈折樹脂組成物は、加熱・加水分解で生じたアルコールを留去した後に、すなわち本発明の製造方法においては第２の工程で、さらにジエタノールアミンと水とを加える。
本発明の高屈折樹脂組成物は、膜状に加工した後に、最終的に加熱処理により硬化させるが、その際に、Ｔｉ原子に配位していたジエタノールアミンの一部が系外に揮発あるいは遊離する。このとき水が存在すると、さらにＴｉＯ構造が成長し、高屈折率化に寄与する。つまり、水の添加により最終硬化物が高屈折率化する。これは、Ｔｉ原子に配位していたジエタノールアミンの加熱による揮発あるいは遊離で空いた配座がさらに縮合反応を起こし、ＴｉＯ構造を成長させるためである。また、同時に添加するジエタノールアミンは系の安定化に寄与し、急激な酸化チタン粒子の生成を制御することができる。
なお、先に水を添加すると、添加量が多いと反応が急速に進行し、ゲル化や粒子の析出の問題が起こることがあるため、水とジエタノールアミンを添加する順序は、ジエタノールアミンを先に、水を後にすることが好ましい。
また、水とジエタノールアミンとは、あらかじめ混合しておき、混合物の状態で加えてもよい。<< Addition of water and diethanolamine mixture (second step) >>
In the high refractive resin composition of the present invention, diethanolamine and water are further added after the alcohol produced by heating and hydrolysis is distilled off, that is, in the second step in the production method of the present invention.
The high-refractive resin composition of the present invention is finally cured by heat treatment after being processed into a film shape. At that time, a part of diethanolamine coordinated to Ti atoms is volatilized or liberated outside the system. To do. If water is present at this time, a TiO structure further grows and contributes to a higher refractive index. That is, the final cured product has a high refractive index by adding water. This is because the conformation that is volatilized or liberated by heating of diethanolamine coordinated to Ti atoms further causes a condensation reaction to grow a TiO structure. In addition, diethanolamine added at the same time contributes to the stabilization of the system and can control the rapid generation of titanium oxide particles.
If water is added first, the reaction proceeds rapidly if the addition amount is large, and problems such as gelation and precipitation of particles may occur. Therefore, the order of adding water and diethanolamine should be diethanolamine first. It is preferable to drain the water later.
Further, water and diethanolamine may be mixed in advance and added in the form of a mixture.
水とジエタノールアミンとをあらかじめ混合する場合、水とジエタノールアミンとの混合物のうち水の添加量は、チタンアルコキシド３〜７モルに対し、２〜１８モルであることが好ましく、６〜１８モルであることがより好ましい。
水（ｘ）とジエタノールアミン（ｙ）との混合比率（ｘ：ｙ）としては、２：２〜１８：２とすることが好ましく、６：２〜１８：２とすることがより好ましい。
ただし、これらの混合比率（ｘ：ｙ）の範囲はチタンアルコキシドの量に依存しており、例えば、チタンアルコキシドが３モルの場合２：２〜１４：２、４モルの場合２：２〜１４：２、５モルの場合２：２〜１４：２、６モルの場合２：２〜１８：２、７モルの場合２：２〜２０：２が好ましい混合比率となる。チタンアルコキシドの量がさらに多い場合、好ましい混合比率における水の上限が増加方向にシフトしていくものと考えられる。When water and diethanolamine are mixed in advance, the amount of water in the mixture of water and diethanolamine is preferably 2 to 18 mol, preferably 6 to 18 mol, relative to 3 to 7 mol of titanium alkoxide. Is more preferable.
The mixing ratio (x: y) of water (x) and diethanolamine (y) is preferably 2: 2 to 18: 2, and more preferably 6: 2 to 18: 2.
However, the range of these mixing ratios (x: y) depends on the amount of titanium alkoxide. For example, when the titanium alkoxide is 3 mol, 2: 2 to 14: 2, and when it is 4 mol, 2: 2 to 14 : 2 and 5 moles: 2: 2 to 14: 2, 6 moles 2: 2 to 18: 2, 7 moles 2: 2 to 20: 2 are preferred mixing ratios. When the amount of titanium alkoxide is larger, it is considered that the upper limit of water at a preferable mixing ratio shifts in an increasing direction.
＜膜状光学部材＞
本発明の膜状光学部材は、既述の本発明の高屈折樹脂組成物を用いて形成されるものであり、例えば、基材上に塗布、乾燥し、必要に応じて硬化させることにより得ることができる。高屈折樹脂組成物を基材上に塗布する方法としては、特に制限はないが、例えば、刷毛塗り、スピン塗布法、スプレー法、スリットコーター、グラビア印刷、スクリーン印刷等を挙げることができる。
また、前記基材としては、ガラス板、プラスチック板、プラスチックフィルム、太陽電池セル等を挙げることができる。<Film optical member>
The film-like optical member of the present invention is formed using the above-described highly refractive resin composition of the present invention. For example, the film-shaped optical member is obtained by coating on a substrate, drying, and curing as necessary. be able to. The method for applying the high refractive resin composition onto the substrate is not particularly limited, and examples thereof include brush coating, spin coating, spraying, slit coater, gravure printing, and screen printing.
Examples of the substrate include a glass plate, a plastic plate, a plastic film, and a solar battery cell.
また、高屈折樹脂組成物の塗布後に行う乾燥は、膜中の溶剤が十分に揮発すればよく、その方法や条件は特に制限はないが、例えば、ホットプレート、電気炉等を用い、好ましくは５０〜１５０℃、より好ましくは６０〜１２０℃の範囲で行うことができる。乾燥温度５０℃未満では、溶媒成分などの乾燥が不十分になる恐れがあり、１５０℃を超えるとモノマ成分などが揮発してしまう恐れがあり、良好な硬化膜を得ることが困難になる傾向がある。 In addition, the drying performed after the application of the high refractive resin composition is not limited as long as the solvent in the film is sufficiently volatilized, and the method and conditions thereof are not particularly limited, for example, using a hot plate, an electric furnace, etc. It can be carried out in the range of 50 to 150 ° C, more preferably 60 to 120 ° C. If the drying temperature is less than 50 ° C., drying of the solvent component or the like may be insufficient, and if it exceeds 150 ° C., the monomer component or the like may volatilize, which tends to make it difficult to obtain a good cured film. There is.
また、乾燥後の硬化は、熱硬化性配合の場合には、その成分や配合量により硬化温度と時間を適宜決定すればよいが、好ましくは１００〜２００℃の温度で２〜６０分間、より好ましくは１３０〜２００℃の温度で２〜３０分間加熱して行うことができる。この加熱が１００℃未満であると、十分な硬化が行えない恐れがある。 In addition, in the case of thermosetting blending, curing after drying may be performed by appropriately determining the curing temperature and time depending on the component and blending amount, but preferably at a temperature of 100 to 200 ° C. for 2 to 60 minutes, Preferably it can carry out by heating for 2 to 30 minutes at the temperature of 130-200 degreeC. If this heating is less than 100 ° C., sufficient curing may not be achieved.
また、高屈折樹脂組成物が光硬化性配合の場合についても特に制限はないが、高圧水銀灯などを用い、１００〜２０００ｍＪ／ｃｍ２で露光し、最終硬化させることが好ましい。Moreover, although there is no restriction | limiting in particular also about the case where a high refractive resin composition is a photocurable compound, It is preferable to expose at 100-2000 mJ / cm < 2 > using a high pressure mercury lamp etc. and to make it harden | cure.
本発明に係る膜状光学部材の膜厚は、高屈折樹脂組成物の粘度を調整したり、膜形成手段やその条件を適宜選択することにより、容易に所望厚さに形成することが可能である。 The film-shaped optical member according to the present invention can be easily formed to have a desired thickness by adjusting the viscosity of the high refractive resin composition or by appropriately selecting the film forming means and its conditions. is there.
例えば、前記溶媒成分である溶剤の配合量を少なくすると、高屈折樹脂組成物の粘度が上昇し、比較的厚膜の光学部材を形成しやすくなり、前記溶媒成分の配合量を多くすると、高屈折樹脂組成物の粘度が低下し、比較的薄膜の光学部材を形成しやすくなる。 For example, if the blending amount of the solvent component is reduced, the viscosity of the highly refractive resin composition is increased, and it becomes easier to form a relatively thick optical member. The viscosity of the refractive resin composition decreases, and it becomes easier to form a relatively thin optical member.
また、高屈折樹脂組成物の塗布手段として、スピン塗布法を適用する場合には、その回転数を下げたり、塗布回数を増やしたりすることで、比較的厚膜の光学部材を形成することができ、その回転数を上げたり、塗布回数を減らしたりすることで、比較的薄膜の光学部材を形成することが可能である。具体的に好ましい厚さは、用途にもよるが１〜１０００μｍの範囲である。 In addition, when applying a spin coating method as a coating means for the high refractive resin composition, it is possible to form a relatively thick optical member by decreasing the number of rotations or increasing the number of coatings. A relatively thin optical member can be formed by increasing the number of rotations or decreasing the number of coatings. A specific preferable thickness is in the range of 1 to 1000 μm although it depends on the application.
以下に実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.
［実施例１］
４つ口のセパラブルフラスコ（１００ｍｌ）の４つの口にそれぞれ、攪拌羽、窒素供給、揮発成分を留去できるように連結管、及びリービッヒ冷却器を接続しておいた。このセパラブルフラスコに、ジエタノールアミン１４．７２ｇ、水１．４４ｇ及び１−ペンタノール１７．９４ｇを入れ、窒素流下、攪拌した。数分後、攪拌が十分に行われたのを確認し、チタニウムテトライソプロポキシド２８．４２ｇをなるべく空気に触れないように注意しながら加えた。[Example 1]
A four-neck separable flask (100 ml) was connected with a stirring tube, nitrogen supply, a connecting tube and a Liebig condenser so that volatile components could be distilled off. In this separable flask, 14.72 g of diethanolamine, 1.44 g of water, and 17.94 g of 1-pentanol were added and stirred under a nitrogen flow. After a few minutes, it was confirmed that stirring was sufficiently performed, and 28.42 g of titanium tetraisopropoxide was added with care so as not to touch the air as much as possible.
チタニウムテトライソプロポキシドを加えると、フラスコの温度は上昇したが、室温（２５℃）程度にまで冷えた後、８０℃オイルバスを用いて、揮発成分の留去を行った。この際の留去物は、チタニウムテトライソプロポキシドの加水分解反応による副生成物のイソプロピルアルコールである。 When titanium tetraisopropoxide was added, the temperature of the flask rose, but after cooling to about room temperature (25 ° C.), the volatile components were distilled off using an 80 ° C. oil bath. The distillate at this time is isopropyl alcohol, which is a by-product of the hydrolysis reaction of titanium tetraisopropoxide.
別に用意したサンプル管を用い、水４．９０ｇ及びジエタノールアミン４．２ｇをよく混ぜて混合物を得た。そして、前記留去を６時間行った後に、セパラブルフラスコを室温（２５℃）まで冷却し、この混合物を添加した。この液体をＡ液（高屈折樹脂組成物）という。 Using a separately prepared sample tube, 4.90 g of water and 4.2 g of diethanolamine were mixed well to obtain a mixture. And after performing the said distillation for 6 hours, the separable flask was cooled to room temperature (25 degreeC), and this mixture was added. This liquid is referred to as A liquid (high refractive resin composition).
セパラブルフラスコに、Ｎ−メチルピロリドン１４９４ｇに、ポリエステルジオール（クラレ（株）製、商品名クラレポリオールＰ１０１０）４９６５ｇを加えたものを入れ、十分に攪拌した。これに４，４’−ジシクロヘキシルメタンジイソシアネート（住化バイエルウレタン（株）製、商品名ディスモジュール−Ｗ １００９ｇを２時間かけて滴下し、Ｂ１液（ポリマ又はオリゴマ）を得た。 In a separable flask, 1495 g of N-methylpyrrolidone and 4965 g of polyester diol (trade name, Kuraray Polyol P1010, manufactured by Kuraray Co., Ltd.) were added and stirred sufficiently. 4,4'-Dicyclohexylmethane diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name DISMODULE-W 1009 g) was added dropwise over 2 hours to obtain a B1 liquid (polymer or oligomer).
Ａ液１００重量部に対し、Ｂ１液１０重量部を加え十分に攪拌した樹脂組成液を、半導体用シリコンウエハとスライドガラスにスピンコートし、１００℃のホットプレートで５分間加熱、溶剤を除去し、薄膜を得た。この薄膜の波長４５０ｎｍの光に対する単位膜厚あたりの吸光度（Ｏ．Ｄ．／μｍ）は０．０００７８０で、波長６３２．８ｎｍの光に対する屈折率は１．６８であった。なお、形成した薄膜の膜厚は、屈折率測定用が０．５μｍ、吸光度測定用が１１μｍであった。
また、屈折率の測定及び吸光度の測定は以下のようにして行った。
〈屈折率の測定〉
得られた高屈折樹脂組成物をＮＭＰ（Ｎ−メチルピロリドン）を用い約１．５倍に希釈した。次いで、スピンコーターを用い、半導体用シリコンウエハ上に１０００ｒｐｍ、１０秒、２０００ｒｐｍ、３０秒にて塗布した。その後、１５０℃に調整したホットプレートにて１５分間加熱し、薄膜を得た。この薄膜をファイブラボ社製エリプソメータＭＡＲＹ−１０２で、Ｈｅ−Ｎｅレーザー波長（６３２．８ｎｍ）での屈折率を測定した。
〈吸光度の測定〉
得られた高屈折樹脂組成物を、そのままスライドガラス上にスピンコーターを用い塗布した。これを１５０℃のホットプレートで１５分間加熱し、薄膜を得た。このとき、膜厚が１０μｍ程度となるようにスピンコーターの回転数を調整した。得られたガラス基板上の膜を、ＵＶ−ＶＩＳ分光光度計、日本分光社製ＪＡＳＣＯ Ｖ−５４０を用い、吸光度スペクトルを測定し、薄膜の測定値で除したものでＯ．Ｄ．／μｍ単位のスペクトルを得た。ここでは特に、波長４５０ｎｍの値で評価した。To 100 parts by weight of A liquid, 10 parts by weight of B1 liquid and sufficiently stirred, the resin composition liquid is spin-coated on a semiconductor silicon wafer and a slide glass, and heated on a hot plate at 100 ° C. for 5 minutes to remove the solvent. A thin film was obtained. The thin film had an absorbance (OD / μm) per unit film thickness with respect to light with a wavelength of 450 nm of 0.000780 and a refractive index with respect to light with a wavelength of 632.8 nm of 1.68. In addition, the film thickness of the formed thin film was 0.5 μm for refractive index measurement and 11 μm for absorbance measurement.
The refractive index and the absorbance were measured as follows.
<Measurement of refractive index>
The obtained high refractive resin composition was diluted about 1.5 times using NMP (N-methylpyrrolidone). Subsequently, it apply | coated on the silicon wafer for semiconductors at 1000 rpm, 10 seconds, 2000 rpm, and 30 seconds using the spin coater. Then, it heated for 15 minutes with the hotplate adjusted to 150 degreeC, and the thin film was obtained. This thin film was measured for refractive index at a He—Ne laser wavelength (632.8 nm) with an ellipsometer MARY-102 manufactured by Fibravo.
<Measurement of absorbance>
The obtained high refractive resin composition was directly applied on a slide glass using a spin coater. This was heated on a hot plate at 150 ° C. for 15 minutes to obtain a thin film. At this time, the rotation speed of the spin coater was adjusted so that the film thickness was about 10 μm. The obtained film on the glass substrate was measured by using a UV-VIS spectrophotometer, JASCO V-540 manufactured by JASCO Corporation, and the absorbance spectrum was measured and divided by the measured value of the thin film. D. A spectrum in units of / μm was obtained. Here, in particular, the evaluation was made with a value of a wavelength of 450 nm.
［実施例２］
実施例１で得たＡ液１００重量部に対し、Ｂ２液として、アクリル系ＵＶ樹脂（日立化成工業（株）製、商品名ヒタロイド７９８１）１０重量部を加え十分に攪拌した樹脂組成液を、半導体用シリコンウエハとスライドガラスにスピンコートし、１００℃のホットプレートで５分間加熱、溶剤を除去し、薄膜を得、紫外線を照射して硬化させた。この薄膜の波長４５０ｎｍの光に対する単位膜厚あたりの吸光度（Ｏ．Ｄ．／μｍ）は０．０００８４２で、波長６３２．８ｎｍの光に対する屈折率は１．７０であった。形成した薄膜の膜厚は、屈折率測定用が約０．５μｍ、吸光度測定用が約１０μｍであった。なお、これらの測定方法は実施例１と同様である。[Example 2]
With respect to 100 parts by weight of the liquid A obtained in Example 1, a resin composition liquid obtained by sufficiently adding 10 parts by weight of an acrylic UV resin (manufactured by Hitachi Chemical Co., Ltd., trade name Hitaroid 7981) as the B2 liquid, A silicon wafer for semiconductor and a slide glass were spin-coated, heated on a hot plate at 100 ° C. for 5 minutes, the solvent was removed, a thin film was obtained, and cured by irradiation with ultraviolet rays. The thin film had an absorbance (OD / μm) per unit film thickness with respect to light with a wavelength of 450 nm of 0.000842, and a refractive index with respect to light with a wavelength of 632.8 nm was 1.70. The thickness of the formed thin film was about 0.5 μm for refractive index measurement and about 10 μm for absorbance measurement. These measurement methods are the same as those in Example 1.
［実施例３］
実施例１で得たＡ液１００重量部に対し、Ｂ３液としてエポキシ樹脂（大日本インキ（株）製、商品名ＥＸＡ−４８５０−１０００）１０重量部を加え十分に攪拌した樹脂組成液を、半導体用シリコンウエハとスライドガラスにスピンコートし、８０℃のホットプレートで５分間加熱、溶剤を除去し、さらに１５０℃のホットプレートで１５分間加熱硬化し、薄膜を得た。この薄膜の波長４５０ｎｍの光に対する単位膜厚あたりの吸光度（Ｏ．Ｄ．／μｍ）は０．０００５６４で、波長６３２．８ｎｍの光に対する屈折率は１．７３であった。形成した薄膜の膜厚は、屈折率測定用が約０．５μｍ、吸光度測定用が約１０μｍであった。なお、これらの測定方法は実施例１と同様である。[Example 3]
To 100 parts by weight of A liquid obtained in Example 1, 10 parts by weight of an epoxy resin (Dainippon Ink Co., Ltd., trade name EXA-4850-1000) was added as B3 liquid, and the resin composition liquid sufficiently stirred was A silicon wafer for semiconductor and a slide glass were spin-coated, heated on a hot plate at 80 ° C. for 5 minutes, the solvent was removed, and further heated and cured on a hot plate at 150 ° C. for 15 minutes to obtain a thin film. The light absorbency per unit film thickness (OD / μm) for light having a wavelength of 450 nm of this thin film was 0.000564, and the refractive index for light having a wavelength of 632.8 nm was 1.73. The thickness of the formed thin film was about 0.5 μm for refractive index measurement and about 10 μm for absorbance measurement. These measurement methods are the same as those in Example 1.
［比較例１］
４つ口のセパラブルフラスコ（１００ｍｌ）の４つの口にそれぞれ、攪拌羽、窒素供給、揮発成分を留去できるように連結管、及びリービッヒ冷却器を接続しておいた。このセパラブルフラスコに、ジエタノールアミン１４．７２ｇ、水１．４４ｇ及び１−ペンタノール１７．９４ｇを入れ、窒素流下、攪拌した。数分後、攪拌が十分に行われたのを確認し、チタニウムテトライソプロポキシド２８．４２ｇをなるべく空気に触れないように注意しながら、加えた。[Comparative Example 1]
A four-neck separable flask (100 ml) was connected with a stirring tube, nitrogen supply, a connecting tube and a Liebig condenser so that volatile components could be distilled off. In this separable flask, 14.72 g of diethanolamine, 1.44 g of water, and 17.94 g of 1-pentanol were added and stirred under a nitrogen flow. After a few minutes, it was confirmed that the stirring was sufficiently performed, and 28.42 g of titanium tetraisopropoxide was added with care so as not to touch the air as much as possible.
チタニウムテトライソプロポキシドを加えると、セパラブルフラスコの温度は上昇したが、室温（２５℃）程度にまで冷えた後、８０℃オイルバスを用いて、揮発成分の留去を行った。この際の留去物は、チタニウムテトライソプロポキシドの加水分解反応による副生成物のイソプロピルアルコールである。この液体をＣ液という。 When titanium tetraisopropoxide was added, the temperature of the separable flask rose, but after cooling to about room temperature (25 ° C.), the volatile components were distilled off using an 80 ° C. oil bath. The distillate at this time is isopropyl alcohol, which is a by-product of the hydrolysis reaction of titanium tetraisopropoxide. This liquid is called C liquid.
セパラブルフラスコに、Ｎ−メチルピロリドン１４９４ｇにクラレ（株）製、商品名クラレポリオールＰ１０１０、４９６５ｇを加えたものを入れ、十分に攪拌した。これに住化バイエルウレタン（株）製、商品名ディスモジュール−Ｗ １００９ｇを２時間かけて滴下し、Ｂ１液（ポリマ又はオリゴマ）を得た。 A separable flask containing 1494 g of N-methylpyrrolidone and Kuraray Co., Ltd., trade name Kuraray Polyol P1010, 4965 g was added and sufficiently stirred. Sumitomo Bayer Urethane Co., Ltd. product name Dismodule-W 1009g was dripped at this over 2 hours, and B1 liquid (polymer or oligomer) was obtained.
Ｃ液１００重量部に対し、Ｂ１液１０重量部を加え十分に攪拌した樹脂組成液を、半導体用シリコンウエハとスライドガラスに滴下しようとしたところ、組成液は空気に触れると瞬時に表面に薄皮を生じ、光学特性を測定できる塗膜が得られなかった。 When 100 parts by weight of liquid C was added to 10 parts by weight of liquid B1 and sufficiently stirred, an attempt was made to drop the resin composition liquid onto a silicon wafer for semiconductors and a glass slide. The coating film which can measure an optical characteristic was not obtained.
以上の実施例・比較例の結果を表１に示す。 The results of the above examples and comparative examples are shown in Table 1.
表１より、実施例１〜３は、透明、高屈折率で、かつ所望の膜厚の光学部材を形成することができたのに対し、アルコールを留去した後、さらにあらかじめ混合しておいた水とジエタノールアミンとの混合物を加えてない比較例１は、光学特性を測定できる塗膜すら得ることができなかったことが分かる。 From Table 1, Examples 1 to 3 were able to form an optical member having a desired film thickness with transparency and a high refractive index. It can be seen that Comparative Example 1 in which no mixture of water and diethanolamine was added could not obtain even a coating film capable of measuring optical properties.
以下の実施例４〜２５、及び参考例１〜３は、ポリマなどを用いず、含金属屈折率中間体のみを含む高屈折樹脂組成物を硬化させた実施例である。 Examples 4 to 25 and Reference Examples 1 to 3 below are examples in which a high refractive resin composition containing only a metal-containing refractive index intermediate is cured without using a polymer or the like.
［実施例４］
４つ口のセパラブルフラスコ（２０００ｍｌ）の４つの口にそれぞれ、攪拌羽、窒素供給、揮発成分を留去できるように連結管、及びリービッヒ冷却器を接続しておいた。ジエタノールアミン２６２．９ｇ、水１８．０ｇ及び１−ペンタノール３２５．２ｇをセパラブルフラスコに入れ、窒素流下、攪拌した。数分後、攪拌が十分に行われたのを確認し、チタニウムテトライソプロポキシド４２６．３ｇをなるべく空気に触れないように注意しながら加えた。[Example 4]
A connecting tube and a Liebig condenser were connected to the four necks of a four-necked separable flask (2000 ml) so that the stirring blades, nitrogen supply, and volatile components could be distilled off, respectively. 262.9 g of diethanolamine, 18.0 g of water, and 325.2 g of 1-pentanol were placed in a separable flask and stirred under a nitrogen stream. After a few minutes, it was confirmed that stirring was sufficiently performed, and 426.3 g of titanium tetraisopropoxide was added with care so as not to touch the air as much as possible.
チタニウムテトライソプロポキシドを加えると、フラスコの温度は上昇したが、室温（２５℃）程度にまで冷えた後、８０℃オイルバスを用いて、揮発成分の留去を行った。この際の留去物は、チタニウムテトライソプロポキシドの加水分解反応による副生成物のイソプロピルアルコールである。 When titanium tetraisopropoxide was added, the temperature of the flask rose, but after cooling to about room temperature (25 ° C.), the volatile components were distilled off using an 80 ° C. oil bath. The distillate at this time is isopropyl alcohol, which is a by-product of the hydrolysis reaction of titanium tetraisopropoxide.
別に用意したサンプル管を用い、水１８．０ｇ及びジエタノールアミン１０５．１ｇをよく混ぜて混合物を得た。そして、前記留去を６時間行った後に、セパラブルフラスコを室温（２５℃）まで冷却し、この混合物を添加し（表２において「後添加」と表記する。）、高屈折樹脂組成物を得た。この高屈折樹脂組成物の溶液状態、色、粘度、ＮＶ、吸光度を評価・測定したところ表２に示す結果を得た。なお、各評価項目の評価方法は以下の通りである。
〈溶液状態〉
調製した高屈折樹脂組成物を目視により観察し、濁りが全く観察されなかった場合を「良」、若干の濁りが観察された場合を「微濁」、一見して濁りが観察された場合を「濁」として評価した。
〈色〉
調製した高屈折樹脂組成物を目視により観察し、溶液の色を観察し、透明の場合を「透」、淡い黄色味を帯びていた場合を「淡」、黄色を帯びていた場合を「黄」、橙色を帯びていた場合を「橙」として評価した。
〈粘度〉
調製した高屈折樹脂組成物の粘度をＥ型粘度計により測定した。
〈ＮＶ（不揮発分含有率）〉
調製した高屈折樹脂組成物をアルミ箔に１ｇ滴下して１８０℃・２時間の熱処理をし、熱処理前後の重量変化を測定し算出した。
ＮＶ＝（熱処理後重量）／（熱処理前重量）
〈吸光度（溶液）の測定〉
ディスポセル（光路長：１ｃｍ）に溶液を注入し、分光光度計（日本分光社製、ＪＡＳＣＯ Ｖ−５４０）により吸光度スペクトルを測定し、代表値として、波長４５０ｎｍの吸光度をセル光路長（１ｃｍ）で除して、単位Ｏ．Ｄ．／ｃｍとして評価した。Using a separately prepared sample tube, 18.0 g of water and 105.1 g of diethanolamine were mixed well to obtain a mixture. And after performing the said distillation for 6 hours, a separable flask was cooled to room temperature (25 degreeC), this mixture was added (it describes as "post-addition" in Table 2), and the high refractive resin composition was obtained. Obtained. When the solution state, color, viscosity, NV, and absorbance of this highly refractive resin composition were evaluated and measured, the results shown in Table 2 were obtained. The evaluation method for each evaluation item is as follows.
<Solution state>
When the prepared high refractive resin composition is visually observed, no turbidity is observed at all, "good", when some turbidity is observed as "slightly turbid", at first glance when turbidity is observed Evaluated as “turbidity”.
<color>
The prepared high refractive resin composition is visually observed, and the color of the solution is observed. When transparent, it is `` transparent '', when it is light yellow, `` pale '', when it is yellow, `` yellow ”, The case of being orange was evaluated as“ orange ”.
<viscosity>
The viscosity of the prepared highly refractive resin composition was measured with an E-type viscometer.
<NV (nonvolatile content)>
1 g of the prepared highly refractive resin composition was dropped onto an aluminum foil and heat-treated at 180 ° C. for 2 hours, and the weight change before and after the heat treatment was measured and calculated.
NV = (weight after heat treatment) / (weight before heat treatment)
<Measurement of absorbance (solution)>
The solution was injected into a disposable cell (optical path length: 1 cm), and the absorbance spectrum was measured with a spectrophotometer (JASCO, JASCO V-540). As a representative value, the absorbance at a wavelength of 450 nm was measured as the cell optical path length (1 cm). Divided by the unit O.D. D. / Cm.
次いで、上記のように調製したＡ液から得られる薄膜の屈折率と吸光度とを以下のようにして測定した。測定結果を表２に示す。
〈屈折率の測定〉
得られた高屈折樹脂組成物と１−ペンタノールとを２：１（重量比）で混合し、シリコンウエハ上に滴下し、５０００ｒｐｍ、３０秒のスピンコート、及び１５０℃、１０分の熱処理後、ファイブラボ社製、エリプソメータＭＡＲＹ−１０２により測定した。
〈吸光度（薄膜）の測定〉
得られた高屈折樹脂組成物を、スライドガラス上に滴下し、５００ｒｐｍ、３０秒のスピンコーター、及び１５０℃のホットプレートで１０分間の熱処理後、分光光度計（日本分光社製、ＪＡＳＣＯ Ｖ−５４０）により光を基板のガラス側から入射し、吸光度スペクトルを測定した。この吸光度の波長４５０ｎｍでの値を塗布膜厚で除し、単位厚み当たりの吸光度Ｏ．Ｄ．／μｍとして評価した。Next, the refractive index and absorbance of the thin film obtained from the liquid A prepared as described above were measured as follows. The measurement results are shown in Table 2.
<Measurement of refractive index>
The obtained high refractive resin composition and 1-pentanol were mixed at a ratio of 2: 1 (weight ratio), dropped onto a silicon wafer, spin-coated at 5000 rpm for 30 seconds, and heat treatment at 150 ° C. for 10 minutes. , Measured by Ellipsometer MARY-102, manufactured by Fibrabo.
<Measurement of absorbance (thin film)>
The obtained highly refractive resin composition was dropped on a slide glass, heat-treated for 10 minutes with a spin coater at 500 rpm for 30 seconds, and a hot plate at 150 ° C., and then a spectrophotometer (JASCO VJ, JASCO V- 540), light was incident from the glass side of the substrate, and the absorbance spectrum was measured. The absorbance at a wavelength of 450 nm is divided by the coating film thickness to obtain the absorbance per unit thickness O.D. D. / Μm.
［実施例５〜７、及び参考例１］
実施例４で得られた高屈折樹脂組成物に対し、後添加における水の量を表２に示すように添加した高屈折樹脂組成物を調製し、同様の評価を行った。評価結果を表２に示す。[Examples 5 to 7 and Reference Example 1]
For the high refractive resin composition obtained in Example 4, a high refractive resin composition was prepared by adding the amount of water in post-addition as shown in Table 2, and the same evaluation was performed. The evaluation results are shown in Table 2.
［実施例８〜１１、及び参考例２］
チタニウムテトライソプロポキシドを４５４．８ｇ、ジエタノールアミンを２５２．３ｇ、水を２１．６ｇ、及び１−ペンタノール３０９．５ｇをに変更したこと以外は実施例４〜７と同様にして実施例８〜１１及び参考例２の高屈折樹脂組成物を調製し、実施例４と同様に評価を行った。評価結果を表３に示す。[Examples 8 to 11 and Reference Example 2]
Examples 8 to 7 were the same as Examples 4 to 7 except that 454.8 g of titanium tetraisopropoxide, 252.3 g of diethanolamine, 21.6 g of water, and 309.5 g of 1-pentanol were changed. 11 and Reference Example 2 were prepared and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 3.
［実施例１２〜１５、及び参考例３］
チタニウムテトライソプロポキシドを４９７．４ｇ、ジエタノールアミンを２５７．６ｇ、水を２５．２ｇ、及び１−ペンタノール３１４．０ｇをに変更したこと以外は実施例４〜７と同様にして実施例１２〜１５及び参考例３の高屈折樹脂組成物を調製し、実施例４と同様に評価を行った。評価結果を表４に示す。[Examples 12 to 15 and Reference Example 3]
Examples 12 to 7 were the same as Examples 4 to 7 except that 497.4 g of titanium tetraisopropoxide, 257.6 g of diethanolamine, 25.2 g of water, and 314.0 g of 1-pentanol were changed. 15 and Reference Example 3 were prepared and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 4.
［実施例１６〜２０］
チタニウムテトライソプロポキシドを５１１．６ｇ、ジエタノールアミンを２５２．３ｇ、水を２７．０ｇ、及び１−ペンタノール３０６．１ｇをに変更したこと以外は実施例４〜７と同様にして実施例１６〜２０の高屈折樹脂組成物を調製し、実施例４と同様に評価を行った。評価結果を表５に示す。[Examples 16 to 20]
Examples 16 to 16 were carried out in the same manner as in Examples 4 to 7 except that 511.6 g of titanium tetraisopropoxide, 252.3 g of diethanolamine, 27.0 g of water, and 306.1 g of 1-pentanol were changed. 20 highly refractive resin compositions were prepared and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 5.
［実施例２１〜２５］
チタニウムテトライソプロポキシドを５３７．２ｇ、ジエタノールアミンを２５５．５ｇ、水を２９．２ｇ、及び１−ペンタノール３０８．８ｇをに変更したこと以外は実施例４〜７と同様にして実施例２１〜２５の高屈折樹脂組成物を調製し、実施例４と同様に評価を行った。評価結果を表６に示す。[Examples 21 to 25]
Examples 21 to 21 were carried out in the same manner as in Examples 4 to 7 except that 537.2 g of titanium tetraisopropoxide, 255.5 g of diethanolamine, 29.2 g of water, and 308.8 g of 1-pentanol were changed. 25 high refractive resin compositions were prepared and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 6.
表２〜表６より、後添加の水を増量すると、濁りの発生が見られるが、この場合、チタニウムテトライソプロポキシドを増量すると、濁りが消失することが分かる。
また、粘度及びＮＶはともに、水の後添加量を増量すると小さくなった。液体の吸光度は、後添加の水を増量すると吸光度が低下するが、一定量を超えると濁りが生じ、吸光度が上昇した。From Tables 2 to 6, it can be seen that when the amount of post-added water is increased, turbidity is generated, but in this case, when the amount of titanium tetraisopropoxide is increased, the turbidity disappears.
Moreover, both the viscosity and NV decreased as the amount of water added later was increased. As for the absorbance of the liquid, when the amount of post-added water was increased, the absorbance decreased, but when it exceeded a certain amount, turbidity occurred and the absorbance increased.
Claims (12)
前記アルコールを留去した後、さらにジエタノールアミンと水とを加えてなることを特徴とする高屈折樹脂組成物。A high refractive resin composition comprising a metal-containing high refractive intermediate obtained by mixing and heating titanium alkoxide, diethanolamine and water, and distilling off the by-product alcohol produced by hydrolysis,
A high refractive resin composition comprising diethanolamine and water added after the alcohol is distilled off.
前記含金属高屈折中間体を得た後、ジエタノールアミンと水とをさらに加える第２の工程と、
を有することを特徴とする高屈折樹脂組成物の製造方法。A first step in which titanium alkoxide, diethanolamine and water are mixed and heated to distill off by-product alcohol produced by hydrolysis to obtain a metal-containing highly refractive intermediate;
A second step of further adding diethanolamine and water after obtaining the metal-containing highly refractive intermediate;
A process for producing a highly refractive resin composition, comprising:
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| JP2006083029A (en) * | 2004-09-17 | 2006-03-30 | Kyoto Univ | Nanocrystal of metal oxide, and its manufacturing method |
| JP2006193700A (en) * | 2004-12-16 | 2006-07-27 | Dainippon Ink & Chem Inc | Organic and inorganic hybrid particle |
| JP2006311820A (en) * | 2005-05-09 | 2006-11-16 | Kubota Corp | Receiving net attaching and detaching structure of threshing apparatus |
-
2008
- 2008-12-10 JP JP2009545429A patent/JPWO2009075287A1/en active Pending
- 2008-12-10 WO PCT/JP2008/072399 patent/WO2009075287A1/en active Application Filing
- 2008-12-11 TW TW97148289A patent/TW200936660A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62250025A (en) * | 1986-04-23 | 1987-10-30 | Toyo Electric Mfg Co Ltd | Resin curing accelerator |
| JPH0714834B2 (en) * | 1987-10-19 | 1995-02-22 | 東レ株式会社 | Method for forming titania thin film |
| JP2003252626A (en) * | 2002-03-04 | 2003-09-10 | Japan Science & Technology Corp | Titanium dioxide precursor, manufacturing method of the same and titanium dioxide and its manufacturing method using the same |
| JP2006083029A (en) * | 2004-09-17 | 2006-03-30 | Kyoto Univ | Nanocrystal of metal oxide, and its manufacturing method |
| JP2006193700A (en) * | 2004-12-16 | 2006-07-27 | Dainippon Ink & Chem Inc | Organic and inorganic hybrid particle |
| JP2006311820A (en) * | 2005-05-09 | 2006-11-16 | Kubota Corp | Receiving net attaching and detaching structure of threshing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009075287A1 (en) | 2009-06-18 |
| TW200936660A (en) | 2009-09-01 |
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