JP2022167558A - Divinylbenzyl fluorene compound and method for producing the same, curable resin composition obtained from the same, curable resin cured product, optical article, and imaging device - Google Patents
Divinylbenzyl fluorene compound and method for producing the same, curable resin composition obtained from the same, curable resin cured product, optical article, and imaging device Download PDFInfo
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- JP2022167558A JP2022167558A JP2021073421A JP2021073421A JP2022167558A JP 2022167558 A JP2022167558 A JP 2022167558A JP 2021073421 A JP2021073421 A JP 2021073421A JP 2021073421 A JP2021073421 A JP 2021073421A JP 2022167558 A JP2022167558 A JP 2022167558A
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- compound
- divinylbenzylfluorene
- curable resin
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- isomer
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- -1 Divinylbenzyl fluorene compound Chemical class 0.000 title claims abstract description 114
- 230000003287 optical effect Effects 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000003384 imaging method Methods 0.000 title abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000005309 thioalkoxy group Chemical group 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000005259 measurement Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- 238000001723 curing Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000523 sample Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 238000000434 field desorption mass spectrometry Methods 0.000 description 7
- 150000002220 fluorenes Chemical class 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 238000012719 thermal polymerization Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 239000003085 diluting agent Substances 0.000 description 4
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 239000012153 distilled water Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- 150000001879 copper Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
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- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- FHQRDEDZJIFJAL-UHFFFAOYSA-N 4-phenylmorpholine Chemical compound C1COCCN1C1=CC=CC=C1 FHQRDEDZJIFJAL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
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- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、加工性に優れ、かつ、透明性と高屈折率性を有するジビニルベンジルフルオレン化合物及びその製造方法、並びに、これから得られる硬化性樹脂組成物、それを硬化して得られた硬化性樹脂硬化物、これを含んでなる光学物品及び撮像装置に関する。 The present invention provides a divinylbenzylfluorene compound having excellent processability, transparency and high refractive index, a method for producing the same, a curable resin composition obtained therefrom, and a curable property obtained by curing the same. The present invention relates to a resin cured product, an optical article containing the same, and an imaging device.
光学用オーバーコート剤、ハードコート剤、反射防止膜、眼鏡レンズ、光ファイバー、光導波路、ホログラム、各種カメラの光学素子等の光学部品には、近年、加工・生産性に優れる点から樹脂材料が広く用いられており、また、光学部品の小型化、薄型化といった傾向、或いは、反射防止性の調整といった観点から屈折率の高い樹脂材料が求められている。
特に、近年、液晶テレビ、ノートパソコン、携帯ゲーム機、携帯電話等の表示に使用される液晶表示素子において、小型化、高抵抗性、高輝度化の要求が高くなっており、この実現にはプリズムシートの高屈折率化が不可欠である。プリズムシートのような賦形材料を製造するには、高屈折率かつ粘度の低い光学材料が求められている。しかし、従来の樹脂材料は高屈折率化すると粘度が向上し、更には結晶化するという課題があった。
また、カメラ、フィルム一体型カメラ、ビデオカメラ等の各種カメラの光学系に使用される光学素子の材料として、光学ガラスあるいは光学用透明樹脂が使用されている。光学ガラスは、耐熱性や透明性、寸法安定性、耐薬品性等に優れ、様々な屈折率やアッベ数を有する多種類の材料が存在しているが、材料コストが高い上、成形加工性が悪く、また生産性が低いという問題点を有している。とりわけ、収差補正に使用される非球面レンズに加工するには、極めて高度な技術と高いコストがかかるため実用上大きな障害となっている。
上記の光学ガラスに対し、光学用透明樹脂からなる光学レンズは、成形性に優れ、大量生産が可能であり、しかも非球面レンズの製造も容易であるという利点を有しており、現在カメラ用レンズ用途として使用されている。高屈折率の光学用透明樹脂の例としては、ポリカーボネート、ポリエステルあるいはエピスルフィド化合物などが挙げられる。
In recent years, resin materials have been widely used for optical parts such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, holograms, and optical elements of various cameras, due to their excellent processing and productivity. In addition, there is a demand for a resin material with a high refractive index from the viewpoint of miniaturization and thinning of optical components, or from the viewpoint of adjustment of antireflection properties.
In particular, in recent years, liquid crystal display elements used for display in liquid crystal televisions, laptop computers, portable game machines, mobile phones, etc. have been required to be smaller, have higher resistance, and have higher brightness. It is essential to increase the refractive index of the prism sheet. An optical material with a high refractive index and a low viscosity is required for producing a shaping material such as a prism sheet. However, conventional resin materials have a problem that, when the refractive index is increased, the viscosity is improved and crystallized.
In addition, optical glass or optical transparent resin is used as a material for optical elements used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indices and Abbe numbers. However, it has the problem of low productivity. In particular, the processing of an aspherical lens used for aberration correction requires extremely advanced technology and high cost, which poses a major obstacle for practical use.
Compared to the above optical glasses, optical lenses made from optical transparent resins have advantages such as excellent moldability, mass production, and the ease of manufacturing aspherical lenses. Used for lenses. Examples of high refractive index optical transparent resins include polycarbonates, polyesters, episulfide compounds, and the like.
近年屈折率の高い光学材料として、屈折率の高い材料を提供するため、フルオレン骨格を持つ化合物が提案されている。例えば、アクリロイル基がアルキレンオキシ基を介してフルオレン骨格に結合した２官能型化合物や（特許文献１、特許文献２、特許文献３）、フルオレン骨格を含有するジグリシジルエーテルとアクリル酸又はメタクリル酸とを反応させて得られる化合物（特許文献４）が知られており、これらは耐熱性が高く高屈折率であるとして注目されている。然しながら、前記した嵩高く剛直なフルオレンの誘導体は一般に固形または常温で数十Ｐａ・ｓ以上の高粘度液体であるため、プリズムシートなどの賦形材料に用いる場合には、適当な粘度になるよう反応性希釈剤等を多量に用いて希釈する必要があり、そのため得られる硬化物の屈折率が低くなってしまうという課題があった。 In recent years, a compound having a fluorene skeleton has been proposed as an optical material with a high refractive index in order to provide a material with a high refractive index. For example, a bifunctional compound in which an acryloyl group is bonded to a fluorene skeleton via an alkyleneoxy group (Patent Document 1, Patent Document 2, Patent Document 3), a diglycidyl ether containing a fluorene skeleton and acrylic acid or methacrylic acid is known (Patent Document 4), and these are attracting attention as having high heat resistance and a high refractive index. However, the aforementioned bulky and rigid fluorene derivatives are generally solid or highly viscous liquids of several tens of Pa·s or more at room temperature. It is necessary to dilute with a large amount of a reactive diluent or the like, so there is a problem that the refractive index of the resulting cured product is lowered.
一方、特許文献５には、フルオレン化合物及びビニルベンジルハライドをアルカリ存在下で反応させることによって得られる硬化性ポリビニルベンジル化合物が開示されている。しかしながら、当該特許公報で開示されているジビニルベンジルフルオレンで使用されているビニルベンジル単位のｍ－／ｐ－異性体比率が ５０／５０重量％混合物であることに由来して、結晶性が高く、反応性希釈剤への溶解性も低いために、透明性が必要とされる光学部品に使用しようとすると、Ｈａｚｅを生じ、透明性の低い成形品しか得られないという問題点があった。 On the other hand, Patent Document 5 discloses a curable polyvinylbenzyl compound obtained by reacting a fluorene compound and vinylbenzyl halide in the presence of an alkali. However, since the m-/p-isomer ratio of the vinylbenzyl unit used in the divinylbenzylfluorene disclosed in the patent publication is a 50/50% by weight mixture, the crystallinity is high, Because of its low solubility in reactive diluents, when it is used in optical parts that require transparency, it causes haze, resulting in the problem that only molded articles with low transparency can be obtained.
従って、本発明の目的は、透明性、溶解性などの特性が改善された新規なジビニルベンジルフルオレン化合物、この化合物の製造方法、および、それから得られる硬化性樹脂組成物、硬化性樹脂硬化物、光学物品及び撮像装置を提供することにある。 Accordingly, an object of the present invention is to provide a novel divinylbenzylfluorene compound having improved properties such as transparency and solubility, a method for producing this compound, a curable resin composition obtained therefrom, a curable resin cured product, An object of the present invention is to provide an optical article and an imaging device.
ビニル基を分子内に複数有する化合物は、重合により分子間の架橋反応が進行しやすい。この特性を利用して、このような化合物を重合系に添加し共重合させることで架橋体を形成して、重合物を不溶化させたり機能性を付与させたりすることが可能である。
例えば、ビニル基を分子内に複数有する化合物としてはジビニルベンゼンが挙げられるが、これをスチレン重合系に少量加えて共重合させ、さらにスルホン酸基等の官能基を導入することでイオン交換樹脂として使用できる。その他、合成ゴム、ＡＢＳ樹脂、ＭＢＳ樹脂、不飽和ポリエステル樹脂などのスチレン系樹脂の架橋剤や、ポリエチレンの変性剤として使用できる。別の例としては、（メタ）アクリレート等の透明樹脂系と共重合させることで、光導波路や光学レンズといった光学材料に強度や耐熱性等の機能性を付与できる可能性がある。
A compound having a plurality of vinyl groups in a molecule is likely to undergo an intermolecular cross-linking reaction due to polymerization. Taking advantage of this property, it is possible to add such a compound to a polymerization system and copolymerize it to form a crosslinked product, thereby making the polymer insoluble or imparting functionality to it.
For example, a compound having multiple vinyl groups in the molecule includes divinylbenzene. Divinylbenzene can be used as an ion-exchange resin by adding a small amount of this to a styrene polymerization system, copolymerizing it, and introducing a functional group such as a sulfonic acid group. Available. In addition, it can be used as a cross-linking agent for styrenic resins such as synthetic rubbers, ABS resins, MBS resins and unsaturated polyester resins, and as a modifying agent for polyethylene. As another example, by copolymerizing with a transparent resin system such as (meth)acrylate, it may be possible to impart functionality such as strength and heat resistance to optical materials such as optical waveguides and optical lenses.
具体的には、特許文献５に開示されたジビニルベンジルフルオレン化合物が知られているが、使用されているビニルベンジル単位のｍ－／ｐ－異性体比率が ５０／５０重量％混合物であることに由来して、融点が１４５℃と高く、融点が１３０℃以下のジビニルベンジルフルオレン化合物は報告されていない。 Specifically, the divinylbenzylfluorene compound disclosed in Patent Document 5 is known, but the m-/p-isomer ratio of the vinylbenzyl units used is a mixture of 50/50% by weight. Therefore, a divinylbenzylfluorene compound with a melting point as high as 145°C and a melting point of 130°C or lower has not been reported.
このような状況の中、本発明者らは、前記課題を達成するため鋭意検討した結果、ビニルベンジル単位のｍ－／ｐ－異性体比率が０．６～１．０であるジビニルベンジルフルオレン化合物を合成したところ、融点が１３０℃以下で、かつ、反応性希釈剤への溶解性も改善され、しかも、このビニルベンジル単位のｍ－／ｐ－異性体の比率が特定の範囲内にあるジビニルベンジルフルオレン化合物の成形硬化物は、意外にも、全光線透過率、Ｈａｚｅなどの光学特性が十分に改善されており、かつ、高い屈折率を有していることを見出し、本発明を完成した。 Under such circumstances, the present inventors have made intensive studies to achieve the above object, and found that a divinylbenzyl fluorene compound having a vinylbenzyl unit m-/p-isomer ratio of 0.6 to 1.0 was synthesized, the divinyl had a melting point of 130°C or lower, improved solubility in reactive diluents, and a ratio of m-/p-isomers of this vinylbenzyl unit within a specific range. Surprisingly, the molded and cured product of the benzylfluorene compound has sufficiently improved optical properties such as total light transmittance and haze, and has a high refractive index. .
すなわち、本発明は、下記一般式（１）で示されるジビニルベンジルフルオレン化合物であって、
（式中、Ｒ１は独立にハロゲン原子、炭素数１～５のアルキル基、アルコキシ基、チオアルコキシ基、炭素数６～３０のアリール基及び炭素数３～３０のヘテロアリール基から選ばれる一つの置換基を示し、ｘは独立に０～４の整数を示す）
示査走査熱量計を使用して昇温速度：１０℃／分で測定を行った場合、融点が１３０℃以下又は融点を持たないことを特徴とするジビニルベンジルフルオレン化合物である。
本発明のジビニルベンジルフルオレン化合物は、ビニルベンジル基のｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率が０．６～１．０であることが好適である。
That is, the present invention provides a divinylbenzylfluorene compound represented by the following general formula (1),
(wherein R 1 is independently selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a thioalkoxy group, an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 3 to 30 carbon atoms; and x independently represents an integer of 0 to 4)
A divinylbenzylfluorene compound characterized by having a melting point of 130° C. or less or no melting point when measured using a differential scanning calorimeter at a heating rate of 10° C./min.
The divinylbenzylfluorene compound of the present invention preferably has a vinylbenzyl group p-isomer/(m-isomer+p-isomer) ratio of 0.6 to 1.0.
本発明は、下記一般式（２）で示されるフルオレン化合物の１種又は２種以上と、ｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率が０．６～１．０であるビニルベンジルハライドとを、アルカリ存在下で反応させることを特徴とするジビニルベンジルフルオレン化合物の製造方法である。
（式中、Ｒ１、ｘは、一般式（１）におけるものと同義である）
本発明のジビニルベンジルフルオレン化合物の製造方法は、上記ビニルベンジルハライドが、ｍ－ビニルベンジルクロライド及びｐ－ビニルベンジルクロライドからなる群から選ばれる少なくとも１種であり、ｐ－ビニルベンジルクロライド／（ｐ－ビニルベンジルクロライド＋ｍ－ビニルベンジルクロライド）の比率が０．６～１．０であることが好適である。
The present invention provides one or more fluorene compounds represented by the following general formula (2), and a p-isomer/(m-isomer+p-isomer) ratio of 0.6 to 1.0. A method for producing a divinylbenzylfluorene compound, characterized by reacting a certain vinylbenzyl halide in the presence of an alkali.
(Wherein, R 1 and x have the same definitions as in general formula (1))
In the method for producing a divinylbenzyl fluorene compound of the present invention, the vinylbenzyl halide is at least one selected from the group consisting of m-vinylbenzyl chloride and p-vinylbenzyl chloride, and p-vinylbenzyl chloride/(p- The ratio of vinylbenzyl chloride+m-vinylbenzyl chloride) is preferably 0.6 to 1.0.
本発明は、上記ジビニルベンジルフルオレン化合物に、該ジビニルベンジルフルオレン化合物と共重合可能なモノマー、オリゴマーおよび／ またはポリマーを配合してなることを特徴とする硬化性樹脂組成物である。
さらに、本発明は、上記硬化性樹脂組成物を硬化してなる樹脂硬化物、硬化性樹脂硬化物を含んでなる光学物品、及び光学物品が組み込まれてなる撮像装置である。
The present invention is a curable resin composition comprising the divinylbenzylfluorene compound and a monomer, oligomer and/or polymer copolymerizable with the divinylbenzylfluorene compound.
Further, the present invention provides a cured resin obtained by curing the curable resin composition, an optical article containing the cured curable resin, and an imaging device incorporating the optical article.
本発明のジビニルベンジルフルオレン化合物は、溶解性が改善され、その成形硬化物は、透過率、Ｈａｚｅ、屈折率などの光学特性が改善され、光学材料や各種の改質剤として有用である。 INDUSTRIAL APPLICABILITY The divinylbenzylfluorene compound of the present invention has improved solubility, and its molded and cured product has improved optical properties such as transmittance, haze and refractive index, and is useful as an optical material and various modifiers.
以下、本発明のジビニルベンジルフルオレン化合物、硬化性樹脂組成物及びこれに配合される各成分について詳しく説明する。 The divinylbenzylfluorene compound, the curable resin composition, and each component blended therein according to the present invention are described in detail below.
本発明のジビニルベンジルフルオレン化合物は、重合性不飽和結合を２個有する上記一般式（１）で表されるジビニルベンジルフルオレン化合物であって、示査走査熱量計を使用して、昇温速度：１０℃／分で測定を行った場合に、１３０℃以下の融点であるか、又は融点を持たないことを特徴とするジビニルベンジルフルオレン化合物である。 The divinylbenzylfluorene compound of the present invention is a divinylbenzylfluorene compound having two polymerizable unsaturated bonds and represented by the above general formula (1), and is measured using a differential scanning calorimeter at a temperature elevation rate of: A divinylbenzylfluorene compound characterized by having a melting point of 130° C. or lower or having no melting point when measured at 10° C./min.
本発明のジビニルベンジルフルオレン化合物は、融点が１３０℃以下であるか、又は融点を持たないことが必須であるが、融点１２５℃以下であることがより好ましく、１２０℃以下であることが最も好ましい。ジビニルベンジルフルオレン化合物の融点が１３０℃を越えると、結晶性が高くなると共に、ビニル基の熱重合開始温度とも重なり、加工性が悪化すると共に、成形硬化物の透明性が低下する。 The divinylbenzylfluorene compound of the present invention must have a melting point of 130° C. or lower or no melting point, more preferably 125° C. or lower, most preferably 120° C. or lower. . When the melting point of the divinylbenzylfluorene compound exceeds 130° C., the crystallinity is increased and the thermal polymerization initiation temperature of the vinyl group is also overlapped, resulting in deterioration of workability and deterioration of transparency of the molded and cured product.
上記一般式（１）において、Ｒ１は独立にハロゲン原子、炭素数１～６のアルキル基、アルコキシ基、チオアルコキシ基、炭素数６～３０のアリール基及び炭素数３～３０のヘテロアリール基から選ばれる一つの置換基を示すが、好ましくは炭素数１～６のアルキル基、炭素数６～３０のアリール基又は炭素数３～３０のヘテロアリール基である。より好ましくは炭素数１～６のアルキル基、炭素数６～１２のアリール基、炭素数６～１２のヘテロアリール基、さらに好ましくは炭素数１～３のアルキル基である。
ｘは、置換数であり、独立に０～４の整数を示すが、好ましくは０～２の整数、より好ましくは０である。
In the above general formula (1), R 1 is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a thioalkoxy group, an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 3 to 30 carbon atoms. is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms. An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 3 carbon atoms are more preferable.
x is the number of substitutions and independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0.
ジビニルベンジルフルオレン化合物において、ビニルベンジル基のｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率が、好ましくは０．６～１．０であり、より好ましくは０．８以上、さらに好ましくは０．９以上である。１．０が理想的であるが、現実的には上限が０．９９５、より好ましくは０．９９、さらに好ましくは０．９８である。
ｏ－異性体については、熱安定性の観点から、これを含まないことが望ましく、含有した場合であっても、全ビニルベンジル基に対して、５モル％未満である。換言すれば、全ビニルベンジル基において、ｐ－異性体及びｍ－異性体の合計量が９５モル％以上、より好ましくは９９モル％以上である。
In the divinylbenzylfluorene compound, the p-isomer/(m-isomer + p-isomer) ratio of the vinylbenzyl group is preferably 0.6 to 1.0, more preferably 0.8 or more, and further Preferably it is 0.9 or more. Although 1.0 is ideal, the practical upper limit is 0.995, more preferably 0.99, and still more preferably 0.98.
From the viewpoint of thermal stability, the o-isomer is desirably not contained, and even if it is contained, it is less than 5 mol % with respect to all vinylbenzyl groups. In other words, the total amount of p-isomer and m-isomer is 95 mol % or more, more preferably 99 mol % or more, in all vinylbenzyl groups.
ここで、ジビニルベンジルフルオレン化合物のｐ－異性体の構造は、下記一般式（３）で例示される。
ジビニルベンジルフルオレン化合物のｍ－異性体の構造は、下記一般式（３）で例示される。
本発明のジビニルベンジルフルオレン化合物の合成に用いられるフルオレン化合物としては、前記一般式（２）に示されるように、未置換のフルオレン、又はその芳香環部分がアルキル基、アルコキシ基、チオアルコキシ基、アリール基若しくはヘテロアリール基で置換されたフルオレン化合物が挙げられ、これらは単独でも２ 種以上の化合物を混合して用いてもよい。これらの内で、入手が容易で、工業的に実施する上で、最も好適なフルオレン化合物は、未置換のフルオレンである。 As the fluorene compound used for synthesizing the divinylbenzylfluorene compound of the present invention, as shown in the general formula (2), unsubstituted fluorene, or an aromatic ring portion thereof containing an alkyl group, an alkoxy group, a thioalkoxy group, Examples include fluorene compounds substituted with aryl groups or heteroaryl groups, and these may be used alone or in combination of two or more. Among these, unsubstituted fluorene is the most suitable fluorene compound because it is readily available and industrially practical.
次に、本発明のジビニルベンジルフルオレン化合物の合成に用いられるビニルベンジルハライドとしては、ｍ－ビニルベンジルクロライド、ｐ－ビニルベンジルクロライド、ｍ－ビニルベンジルブロマイド、ｐ－ビニルベンジルブロマイド等が挙げられ、これらはそれぞれ単独でも２種以上の化合物を混合して用いてもよい。上記のうち、ｍ－ビニルベンジルクロライドおよびｐ－ビニルベンジルクロライドが、入手が容易で、工業的に実施する上で、最も好ましい。 Examples of the vinylbenzyl halide used in synthesizing the divinylbenzylfluorene compound of the present invention include m-vinylbenzyl chloride, p-vinylbenzyl chloride, m-vinylbenzyl bromide and p-vinylbenzyl bromide. may be used alone or in combination of two or more compounds. Among the above, m-vinylbenzyl chloride and p-vinylbenzyl chloride are readily available and most preferred for industrial practice.
さらに、本発明のジビニルベンジルフルオレン化合物の合成に、ビニルベンジルハライドを使用する場合に、ｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率を０．６～１．０とすることで、透明性、溶解性、加工性などの特性が改善された新規なジビニルベンジルフルオレン化合物を得ることができる。 Furthermore, when vinylbenzyl halide is used in the synthesis of the divinylbenzylfluorene compound of the present invention, the ratio of p-isomer/(m-isomer+p-isomer) should be 0.6 to 1.0. can obtain a novel divinylbenzylfluorene compound with improved properties such as transparency, solubility and processability.
原料としてのビニルベンジルハライドについて、ｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率は、その下限は０．７が好ましく、０．８がより好ましく、０．９がさらに好ましい。一方、その上限は、ビニルベンジルハライドの価格又は製造のしやすさの観点から、０．９９５が好ましい。０．９９がより好ましく。０．９８がさらに好ましい。ｐ－異性体／（ｍ－異性体＋ｐ－異性体）の比率が、０．６未満であると、得られるジビニルベンジルフルオレン化合物の結晶性と融点が上昇し、反応性希釈剤への溶解性も悪化し、ビニル基の熱重合開始温度とも重なるため、成形硬化物の透明性が低下する。 Regarding vinylbenzyl halide as a raw material, the lower limit of the ratio of p-isomer/(m-isomer+p-isomer) is preferably 0.7, more preferably 0.8, and still more preferably 0.9. On the other hand, the upper limit is preferably 0.995 from the viewpoint of the price of vinylbenzyl halide or ease of production. 0.99 is more preferred. 0.98 is more preferred. When the ratio of p-isomer/(m-isomer + p-isomer) is less than 0.6, the obtained divinylbenzylfluorene compound has increased crystallinity and melting point, and solubility in a reactive diluent. Also, the thermal polymerization initiation temperature of the vinyl group also deteriorates, so that the transparency of the molded and cured product is lowered.
本発明のジビニルベンジルフルオレン化合物の合成は、前記一般式（２）で示されるフルオレン又はフルオレン化合物の１種または２種以上と、ビニルベンジルハライドとを、アルカリ存在下で反応させて得ることができる。必要に応じて炭素数２～２０のジハロメチル化合物を添加してもよい。
この反応は、公知のビニルベンジル化反応の条件に準じて行うことができる。ビニルベンジル化反応は、例えば、Ｌ．Ｊ．ＭａｔｈｉａｓらのＪ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｐａｒｔ Ｂ；，２８６９（１９９８）、Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｐａｒｔ Ａ；，５８７（１９９７）あるいはＣ．Ｊ．ＫｅｌｌｙらのＪ．Ｃｈｅｍ．Ｒｅｓ．（Ｓ），４４６（１９９７）に記載されている方法によって行うことができる。
The divinylbenzylfluorene compound of the present invention can be synthesized by reacting one or more of the fluorenes or fluorene compounds represented by the general formula (2) with vinylbenzyl halide in the presence of an alkali. . A dihalomethyl compound having 2 to 20 carbon atoms may be added as necessary.
This reaction can be carried out according to the conditions of a known vinylbenzylation reaction. Vinyl benzylation reactions are described, for example, in L. et al. J. Mathias et al. Polym. Sci. , Part B;, 2869 (1998), J. Am. Polym. Sci. , Part A;, 587 (1997) or C.I. J. Kelly et al. Chem. Res. (S), 446 (1997).
反応溶媒としてはジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、Ｎ－メチルピロリドン、ジオキサン、アセトニトリル、テトラヒドロフラン、エチレングリコールジメチルエーテル、１，３－ジメトキシプロパン、１，２－ジメトキシプロパン、テトラメチレンスルホン、ヘキサメチルホスホアミド、メチルエチルケトン、メチルイソブチルケトン、アセトン、シクロヘキサノン等の非プロトン性極性溶媒、並びに、ベンゼン、トルエン、キシレン等の芳香族溶媒、及び、これらの混合物等が挙げられ、これらの中から原料種や反応条件に応じて反応系が均一になるような溶剤種を選択すればよい。 Examples of reaction solvents include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone, and hexamethylphosphoamide. , methyl ethyl ketone, methyl isobutyl ketone, acetone, aprotic polar solvents such as cyclohexanone, and aromatic solvents such as benzene, toluene, xylene, and mixtures thereof. Depending on the conditions, a solvent species may be selected so that the reaction system becomes uniform.
この反応に用いられるアルカリとしては、アルカリ金属あるいはアルカリ土類金属のアルコキサイド、水素化物、水酸化物、例えばナトリウムメトキサイド、ナトリウムエトキサイド、水素化ナトリウム、ホウ水素化ナトリウム、水素化カリウム、水酸化カリウム等が挙げられ、反応系を非水系とするか、含水系とするかでアルカリ種を選択すればよい。アルカリの使用割合は、原料のフルオレン化合物の９位の水素１当量に対して１．１～３．０当量程度がよい。１当量未満であると、反応速度が著しく遅くなり、反応が完全に進行せず原料が残ってしまい、硬化物性に好ましくない影響を与える。また３当量を超えて用いても残存アルカリの除去に多量の洗浄水などの除去溶剤を使用するため経済的ではない。 The alkali used in this reaction includes alkali metal or alkaline earth metal alkoxides, hydrides and hydroxides such as sodium methoxide, sodium ethoxide, sodium hydride, sodium borohydride, potassium hydride and hydroxides. Potassium and the like can be mentioned, and the alkaline species can be selected depending on whether the reaction system is a non-aqueous system or a hydrous system. The proportion of the alkali to be used is preferably about 1.1 to 3.0 equivalents per equivalent of the hydrogen at the 9-position of the starting fluorene compound. If the amount is less than 1 equivalent, the reaction rate becomes extremely slow, the reaction does not proceed completely, and raw materials remain, which adversely affects cured physical properties. Also, even if it is used in excess of 3 equivalents, it is not economical because a large amount of removal solvent such as washing water is used to remove residual alkali.
反応の際に相間移動触媒を用いることができる。この相間移動触媒としては、各種オニウム塩、例えば、テトラ－ｎ－ブチルアンモニウムブロマイド、テトラ－ｎ－ブチルアンモニウムハイドロゲンサルフェート、ベンジルトリメチルアンモニウムクロライド、トリカプリルメチルアンモニウムクロライド等の四級アンモニウム化合物、テトラ－ｎ－ブチルホスホニウムブロマイド、ベンジルトリフェニルホスホニウムクロライド、テトラフェニルホスホニウムクロライド、テトラフェニルホスホニウムブロマイド等の四級ホスホニウム化合物、ベンジルテトラメチレンスルホニウムブロマイド等の三級スルホニウム化合物及びこれらの混合物が挙げられる。
これらの相間移動触媒の使用量は触媒種、あるいは反応温度により触媒効果が異なるため、一概に規定できないが、一般的には原料のフルオレン化合物の９位の水素１ 当量に対して、０．０１～０．２当量程度使用すればよい。
A phase transfer catalyst can be used during the reaction. As the phase transfer catalyst, various onium salts such as tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride, tricaprylmethylammonium chloride and other quaternary ammonium compounds, tetra-n -butylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and other quaternary phosphonium compounds, benzyltetramethylenesulfonium bromide and other tertiary sulfonium compounds, and mixtures thereof.
The amount of these phase transfer catalysts used cannot be categorically defined because the catalytic effect varies depending on the catalyst type or the reaction temperature, but generally 0.01 About 0.2 equivalent may be used.
反応温度及び反応時間は、使用する原料化合物の種類、反応条件によって異なるため、一概に規定できないが、それぞれ３０～１００℃で０．５～２０時間であればよい。１００℃を超える反応温度では、しばしば熱重合などの好ましくない反応を併発する一方、３０℃ 未満では反応は進むものの、長時間を要することから経済的ではない。 The reaction temperature and reaction time vary depending on the type of raw material compounds used and the reaction conditions, and cannot be generally specified. When the reaction temperature exceeds 100°C, unfavorable reactions such as thermal polymerization often occur at the same time.
本発明ではビニルベンジルハライドのような高い熱重合性を持つ不飽和ハライドを使用することから、必要に応じて熱重合防止剤を反応系に添加してもよい。例えばｔ－ブチルカテコール、２，４－ジ－ｔ－ブチルフェノール、２－ｔ－ブチルフェノール、２－ｔ－ブチル－４－ニトロフェノール、２，４－ジニトロフェノール、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ－ブチルハイドロキノン、レゾルシン、ピロガロール、フェノチアジン、銅塩などが挙げられる。さらに、空気の適量の使用も重合禁止に効果がある。
これらの熱重合防止剤の使用量は、熱重合防止剤の種類によって効果が異なるため、一概に規定出来ないが、およそ硬化性ビニルベンジル化合物に対して数ｐｐｍ～２０００ｐｐｍである。
Since the present invention uses a highly thermally polymerizable unsaturated halide such as vinylbenzyl halide, a thermal polymerization inhibitor may be added to the reaction system as necessary. For example t-butylcatechol, 2,4-di-t-butylphenol, 2-t-butylphenol, 2-t-butyl-4-nitrophenol, 2,4-dinitrophenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, t -Butyl hydroquinone, resorcinol, pyrogallol, phenothiazine, copper salts and the like. Furthermore, the use of a moderate amount of air is also effective in inhibiting polymerization.
The amount of these thermal polymerization inhibitors to be used cannot be categorically defined because the effect differs depending on the type of thermal polymerization inhibitor, but it is about several ppm to 2000 ppm relative to the curable vinylbenzyl compound.
本発明のジビニルベンジルフルオレン化合物は、本発明の効果を阻害しない範囲で、これと共重合可能なモノマー、オリゴマーおよび／ またはポリマーを配合して硬化性樹脂組成物として成形性の改善などを図ることができる。具体例としては、ビニルエステル樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、マレイミド樹脂、ポリフェノールのポリシアナート樹脂などの重合性不飽和基を有するオリゴマーまたはポリマー、トリアリルイソシアヌレート、トリアリルシアヌレートなどのモノマーおよびプレポリマー、スチレン、ビニルトルエン、ジビニルベンゼン、ビニルベンジルエーテル化合物、単官能あるいは多官能（メタ）アクリル酸誘導体化合物等が挙げられる。 The divinylbenzylfluorene compound of the present invention may be mixed with a monomer, oligomer and/or polymer copolymerizable therewith to improve moldability as a curable resin composition within the range that does not impede the effects of the present invention. can be done. Specific examples include oligomers or polymers having polymerizable unsaturated groups such as vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, maleimide resins, polyphenol polycyanate resins, and monomers such as triallyl isocyanurate and triallyl cyanurate. and prepolymers, styrene, vinyltoluene, divinylbenzene, vinylbenzyl ether compounds, monofunctional or polyfunctional (meth)acrylic acid derivative compounds, and the like.
共重合可能なモノマー、オリゴマーおよび／またはポリマーを使用する場合、その使用量は、その種類、本発明のジビニルベンジルフルオレン化合物との相容性、硬化物の用途などによっても異なるため、一概に規定できないが、本発明のジビニルベンジルフルオレン化合物１００重量部に対して、例えば、１０～３００重量部、好ましくは２０～２００重量部、より好ましくは５０～１５０重量部である。３００重量部を超える添加量では、本発明のジビニルベンジル化合物からの分離・滲出などが起こり易くなる。 When a copolymerizable monomer, oligomer and/or polymer is used, the amount used varies depending on the type, compatibility with the divinylbenzylfluorene compound of the present invention, application of the cured product, etc., and is generally defined. Although not possible, it is, for example, 10 to 300 parts by weight, preferably 20 to 200 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the divinylbenzylfluorene compound of the present invention. If the added amount exceeds 300 parts by weight, separation and exudation from the divinylbenzyl compound of the present invention tend to occur.
本発明のジビニルベンジル化合物および硬化性樹脂組成物は、熱、光、電子線などの公知の方法を採用して硬化させることができる。また硬化剤を使用して硬化温度を低くしたり、硬化反応を促進したりすることも有用である。硬化物は、光学レンズ等の光学・電子機器分野の光学部材等に好適に用いることができる。 The divinylbenzyl compound and curable resin composition of the present invention can be cured by employing known methods such as heat, light and electron beams. It is also useful to use a curing agent to lower the curing temperature or accelerate the curing reaction. The cured product can be suitably used for optical members in the fields of optical and electronic equipment such as optical lenses.
硬化剤を使用する場合、例えばベンゾイルパーオキサイド、クメンハイドロパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン－３、ｔ－ブチルクミルパーオキサイド、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルパーベンゾエートなどが挙げられ、これらを用途に応じて使用できる。
その使用量は、本発明のジビニルベンジル化合物または硬化性樹脂組成物中の不飽和基の種類、濃度、使用する硬化剤の種類、半減期温度、必要とする安定性などによって異なるが、概ね本発明のジビニルベンジルフルオレン化合物または硬化性樹脂組成物１００重量部に対して０．１～１０重量部である。
When using a curing agent, for example benzoyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, t-butylcumyl peroxide, methyl ethyl ketone peroxide, Dicumyl peroxide, t-butyl perbenzoate and the like can be mentioned, and these can be used depending on the application.
The amount used varies depending on the type and concentration of unsaturated groups in the divinylbenzyl compound or curable resin composition of the present invention, the type of curing agent used, the half-life temperature, the required stability, etc., but generally It is 0.1 to 10 parts by weight per 100 parts by weight of the divinylbenzylfluorene compound or curable resin composition of the invention.
光硬化させる場合、光重合開始剤を使用するとよい。本発明のジビニルベンジルフルオレン化合物は、重合性化合物としてラジカル重合性であるビニル基（エチレン性不飽和基）を有するので、光ラジカル重合開始剤を使用することができる。
光重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；アセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、２－ヒドロキシ－２－メチル－フェニルプロパン－１－オン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オンなどのアセトフェノン類；２－エチルアントラキノン、２－ターシャリーブチルアントラキノン、２－クロロアントラキノン、２－アミルアントラキノンなどのアントラキノン類；２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントンなどのチオキサントン類；アセトフエノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフエノン、４－ベンゾイル－４'－メチルジフェニルサルファイド、４，４'－ビスメチルアミノベンゾフェノンなどのベンゾフェノン類；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のホスフィンオキサイド類等が挙げられる。
For photocuring, a photopolymerization initiator may be used. Since the divinylbenzylfluorene compound of the present invention has a radically polymerizable vinyl group (ethylenically unsaturated group) as a polymerizable compound, a radical photopolymerization initiator can be used.
Examples of photopolymerization initiators include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl ]-Acetophenones such as 2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone benzophenones; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
これらは、単独又は２種以上の混合物として使用でき、更にはトリエタノールアミン、メチルジエタノールアミンなどの第３級アミン、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル等の安息香酸誘導体等の促進剤などと組み合わせて使用することができる。 These can be used alone or as a mixture of two or more, and furthermore, tertiary amines such as triethanolamine and methyldiethanolamine, N,N-dimethylaminobenzoic acid ethyl ester, and N,N-dimethylaminobenzoic acid isoamyl ester. It can be used in combination with accelerators such as benzoic acid derivatives such as
光重合開始剤の市販品としては、例えばＩｒｇａｃｕｒｅ１８４、３６９、６５１、５００、８１９、９０７、７８４、２９５９、ＣＧＩ－１７００、－１７５０、－１８５０、ＣＧ２４－６１、Ｄａｒｏｃｕｒ ｌ１１６、１１７３（以上、チバ・スペシャルティ・ケミカルズ（株）製）、Ｌｕｃｉｒｉｎ ＴＰＯ、ＬＲ８８９３、ＬＲ８９７０（以上、ＢＡＳＦ社製）、ユベクリルＰ３６（ＵＣＢ社製）等が挙げられる。
その使用量は、例えば、本発明のジビニルベンジルフルオレン化合物または硬化性樹脂組成物１００重量部に対して、０．１～１０重量部である。
Commercially available photopolymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 116, 1173 (above, Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, LR8893, LR8970 (manufactured by BASF), Ubecryl P36 (manufactured by UCB), and the like.
The amount used is, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the divinylbenzylfluorene compound or curable resin composition of the present invention.
この他、ナフテン酸マンガン、ナフテン酸鉛、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸亜鉛、ジメチルアニリン、フェニルモルフォリンなどの公知の硬化促進剤を使用することもできる。 In addition, known curing accelerators such as manganese naphthenate, lead naphthenate, zinc naphthenate, cobalt naphthenate, zinc octylate, dimethylaniline, and phenylmorpholine can also be used.
硬化温度は、重合性不飽和基の種類、硬化剤の種類と使用量などによって異なるため、一概に規定できないが、２０～２５０℃、好ましくは５０～２５０℃である。硬化温度が２０℃未満では硬化が不十分となる場合がある。
また硬化条件の調整のために、ハイドロキノン、ベンゾキノン、銅塩などの公知の硬化遅延剤を配合してもよい。
The curing temperature varies depending on the type of polymerizable unsaturated group, the type and amount of curing agent used, and cannot be generally defined, but is 20 to 250°C, preferably 50 to 250°C. If the curing temperature is less than 20°C, curing may be insufficient.
In order to adjust curing conditions, known curing retarders such as hydroquinone, benzoquinone and copper salts may be blended.
さらに、本発明の硬化性樹脂組成物には、必要により酸化防止剤、離型剤、光増感剤、有機溶剤、シランカップリング剤、レベリング剤、消泡剤、帯電防止剤、更には紫外線吸収剤、光安定剤、無機、有機各種フィラー、防かび剤、抗菌剤などを本発明の硬化性樹脂組成物に添加し、それぞれ目的とする機能性を付与することも可能である。 Furthermore, if necessary, the curable resin composition of the present invention contains an antioxidant, a release agent, a photosensitizer, an organic solvent, a silane coupling agent, a leveling agent, an antifoaming agent, an antistatic agent, and even an ultraviolet ray. Absorbents, light stabilizers, various inorganic and organic fillers, antifungal agents, antibacterial agents, etc. can be added to the curable resin composition of the present invention to provide desired functionality.
本発明の硬化性樹脂組成物は、各成分を任意の順序で混合することにより得ることができる。本発明の硬化性樹脂組成物は経時的に安定である。 The curable resin composition of the present invention can be obtained by mixing each component in any order. The curable resin composition of the present invention is stable over time.
本発明の硬化性樹脂組成物は、紫外線等の活性エネルギー線を照射することにより硬化物を得ることができる。ここで、活性エネルギー線を照射して硬化する場合に用いられる光源の具体例としては、例えば、キセノンランプ、カーボンアーク、殺菌灯、紫外線用蛍光灯、複写用高圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、あるいは走査型、カーテン型電子線加速路による電子線等を挙げることができる。また、本発明の硬化性樹脂組成物を紫外線照射により硬化する場合、硬化に必要な紫外線照射量は３００～２００００ｍＪ／ｃｍ２程度でよい。なお、樹脂組成物を十分に硬化するために、窒素ガス等の不活性ガス雰囲気中で紫外線等の活性エネルギー線を照射することが望ましい。 The curable resin composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays. Here, specific examples of the light source used for curing by irradiating active energy rays include, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high-pressure mercury lamp for copying, a medium-pressure mercury lamp, and a high-pressure mercury lamp. , an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam from a scanning or curtain electron beam acceleration path. When the curable resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet irradiation required for curing may be approximately 300 to 20000 mJ/cm 2 . In order to sufficiently cure the resin composition, it is desirable to irradiate active energy rays such as ultraviolet rays in an inert gas atmosphere such as nitrogen gas.
本発明の硬化性樹脂組成物は、プラスチックレンズ等のような注型物に使用することができる。本発明の樹脂組成物を用いたプラスチックレンズの作製法としては、ポリ塩化ビニル、エチレン酢酸ビニル共重合体等からなるガスケットと所望の形状の２枚のガラス鋳型によって造られた型を作り、これに本発明の樹脂組成物を注入した後、紫外線等の活性エネルギー線を照射して樹脂組成物を硬化し、硬化物を型より剥離する方法等がある。 The curable resin composition of the present invention can be used for castings such as plastic lenses. As a method for producing a plastic lens using the resin composition of the present invention, a mold is prepared by using a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer or the like and two glass molds having a desired shape. After injecting the resin composition of the present invention into the mold, the resin composition is cured by irradiation with active energy rays such as ultraviolet rays, and the cured product is released from the mold.
本発明の硬化性樹脂組成物をプリズムレンズシート用樹脂組成物としてフィルム状基材に塗布する方法としては、業界公知の種々の方法を用いることができる。具体的な方法としては、例えば、樹脂組成物を表面にプリズムレンズの形状を有する金型上に塗布し、樹脂組成物の層を設け、その樹脂組成物層の上に無色透明なフィルム状基材（例えば、ポリ塩化ビニル、ポリスチレン、ポリカーボネート、ポリ（メタ）アクリレート、ポリエステル、ポリエチレンテレフタレート等）を気泡が入らないように圧着し、次いでその状態でフィルム状基材側から高圧水銀灯を用いて紫外線を照射して樹脂組成物の層を硬化した後、プリズムレンズ状の樹脂層を形成したフィルム状基材を金型より剥離する方法を挙げることができる。 As a method for applying the curable resin composition of the present invention as a resin composition for a prism lens sheet to a film substrate, various methods known in the industry can be used. As a specific method, for example, a resin composition is applied onto the surface of a mold having a shape of a prism lens, a layer of the resin composition is provided, and a colorless and transparent film-like substrate is formed on the resin composition layer. Materials (for example, polyvinyl chloride, polystyrene, polycarbonate, poly (meth) acrylate, polyester, polyethylene terephthalate, etc.) are crimped so as not to contain air bubbles, and then in that state, ultraviolet light is applied from the film-like substrate side using a high-pressure mercury lamp. After curing the layer of the resin composition by irradiating with, the film-like substrate on which the resin layer in the form of prism lenses is formed can be peeled off from the mold.
紫外線等の活性エネルギー線を照射して得られる本発明の光学材料用樹脂組成物の硬化物の屈折率は、２５℃で１．５９以上であることが好ましく、より好ましくは２５℃で１．６０以上である。特に好ましくは、２５℃で１．６２以上である。特に本発明の光学材料用硬化性樹脂組成物でプリズムレンズシートを作製する場合、硬化物の屈折率が２５℃で１．５９未満であると充分な正面輝度を確保できないという問題が生じることがある。 The refractive index of the cured product of the resin composition for optical materials of the present invention obtained by irradiation with active energy rays such as ultraviolet rays is preferably 1.59 or more at 25°C, more preferably 1.59 at 25°C. 60 or more. Particularly preferably, it is 1.62 or more at 25°C. In particular, when a prism lens sheet is produced from the curable resin composition for optical materials of the present invention, if the refractive index of the cured product is less than 1.59 at 25° C., there may arise a problem that sufficient front luminance cannot be ensured. be.
本発明の硬化物のアッベ数は４０．０以下であることが好ましく、より好ましくは３０．０以下である。硬化物のアッベ数が４０．０を超えると、撮像素子の薄型化を行う際に、色収差が大きく色のにじみが生じるため好ましくない。 The Abbe number of the cured product of the present invention is preferably 40.0 or less, more preferably 30.0 or less. If the Abbe number of the cured product exceeds 40.0, it is not preferable because chromatic aberration is large and color bleeding occurs when the thickness of the imaging device is reduced.
本発明の硬化物の吸水率は、１．０ｗｔ％以下であることが好ましく、より好ましくは０．５ｗｔ％以下である。特に好ましくは、０．３５ｗｔ％以下であり、最も好ましくは、０．２ｗｔ％以下である。硬化物の吸水率が１．０ｗｔ％を超えると、吸水に伴って、材料の屈折率が変化するため、色収差が大きくなり、色のにじみが生じる傾向がある。 The water absorption of the cured product of the present invention is preferably 1.0 wt% or less, more preferably 0.5 wt% or less. Particularly preferably, it is 0.35 wt% or less, and most preferably 0.2 wt% or less. If the water absorption of the cured product exceeds 1.0 wt %, the refractive index of the material changes with water absorption, which tends to increase chromatic aberration and cause color bleeding.
本発明の硬化性樹脂組成物を成形、硬化して得られる樹脂硬化物は、光学物品として好適に使用できる。光学物品の中でも、とりわけプリズムレンズシート、フレネルレンズ、レンチキュラーレンズ、眼鏡レンズ、非球面レンズ等の光学レンズとして有用である。そして、このような光学レンズは、撮像装置に好適に組み込まれる。また、本発明の硬化性樹脂組成物又は樹脂硬化物は、その他にも、光ディスク、光ファイバー、光導波路等のオプトエレクトロニクス向けの光学物品、多層基板、プリプレグ、樹脂付き金属箔、印刷インキ、塗料、クリアーコート剤、ツヤニス等にも使用できる。 A resin cured product obtained by molding and curing the curable resin composition of the present invention can be suitably used as an optical article. Among optical articles, it is particularly useful as an optical lens such as a prism lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens, and an aspherical lens. Such an optical lens is preferably incorporated into an imaging device. In addition, the curable resin composition or resin cured product of the present invention can also be used for optical articles for optoelectronics such as optical discs, optical fibers, and optical waveguides, multilayer substrates, prepregs, metal foils with resin, printing inks, paints, It can also be used as a clear coat agent, gloss varnish, etc.
以下に、本発明の実施の形態の一つである、光学物品を組み込んだ撮像装置を例示する。
撮像装置用レンズモジュールを備えた種々の機器、例えば、カメラ、コンピューター、ワードプロセッサー、プリンター、コピー機、ファックス、電話、モバイル機器（携帯電話、スマートフォン、ゲーム機器、タブレット等の携帯情報端末（ＰＤＡ））、自動車機器、建築用機器、天文用機器等に、本発明の光学物品を好適に使用できる。特に、小型の撮像装置用レンズ（さらには高精度のレンズ）、例えば、小型カメラ（例えば、携帯電話用カメラ（いわゆるカメラ付き携帯電話のカメラ）、車載用カメラモジュール等）等の撮像装置用レンズモジュールとして有用である。
携帯電話、スマートフォン、ゲーム機器、タブレット等の携帯電子端末には、小型で薄型な撮像装置が搭載されている。このような撮像装置には、受光素子と、受光素子上に被写体像を形成するためのレンズと、を有するレンズモジュールが備えられている。
撮像装置に用いられるレンズモジュールとしては、例えば、特開２０１０-２６６６６４号公報、特開２００３-０４６８２５号公報、特開２００６-３１３１８５号公報、特開２００３-０３２５２５号公報、ＷＯ２０１１/０７４５３１号などに開示された撮像装置に利用できる。
本発明の光学レンズは、上記の通り例示された撮像装置のレンズ又はレンズ部として好適に使用できる。
An imaging device incorporating an optical article, which is one embodiment of the present invention, will be exemplified below.
Various devices equipped with lens modules for imaging devices, such as cameras, computers, word processors, printers, copiers, fax machines, telephones, mobile devices (mobile phones, smart phones, game devices, personal digital assistants (PDAs) such as tablets) , automotive equipment, architectural equipment, astronomical equipment, etc., the optical article of the present invention can be suitably used. In particular, lenses for compact imaging devices (and high-precision lenses), for example, lenses for imaging devices such as compact cameras (e.g., mobile phone cameras (so-called mobile phone cameras with cameras), vehicle camera modules, etc.) Useful as a module.
2. Description of the Related Art Portable electronic terminals such as mobile phones, smart phones, game machines, and tablets are equipped with small and thin imaging devices. Such an imaging device is provided with a lens module having a light receiving element and a lens for forming a subject image on the light receiving element.
As a lens module used in an imaging device, for example, JP-A-2010-266664, JP-A-2003-046825, JP-A-2006-313185, JP-A-2003-032525, WO2011/074531, etc. It can be used for the disclosed imaging device.
The optical lens of the present invention can be suitably used as the lens or lens section of the imaging device exemplified above.
以下、本発明について実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、各例中の部は特に記載がない場合いずれも重量部であり、各物性の評価は以下に示す方法によって行った。 EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. The parts in each example are parts by weight unless otherwise specified, and the physical properties were evaluated by the following methods.
１）分子量及び分子量分布
分子量及び分子量分布測定は、ＧＰＣ（東ソー製、ＨＬＣ－８２２０ＧＰＣ）を使用し、分析カラムとして、東ソー製、ＴＳＫｇｅｌ ＭｕｌｔｉｐｏｒｅＨＸＬ－Ｍ：２本、ＴＳＫｇｅｌ Ｇ１０００ＨＸＬ：１本、ガードカラムにＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＭＰ（ＸＬ）：１本を使用し、溶媒にテトラヒドロフラン（ＴＨＦ）、流量１．０ｍｌ／ｍｉｎ、カラム温度３８℃、単分散ポリスチレンによる検量線を用いて行った。
1) Molecular weight and molecular weight distribution GPC (manufactured by Tosoh, HLC-8220GPC) is used for molecular weight and molecular weight distribution measurement, and the analytical columns are TSKgel MultiporeH XL -M manufactured by Tosoh: 2, TSKgel G1000H XL : 1, guard. Using one TSKguard column MP (XL) as a column, tetrahydrofuran (THF) as a solvent, a flow rate of 1.0 ml/min, a column temperature of 38° C., and a calibration curve using monodisperse polystyrene.
２）ジビニルベンジルフルオレン化合物の構造
日本電子製ＪＮＭ－ＬＡ６００型核磁気共鳴分光装置を用い、１３Ｃ－ＮＭＲ及び１Ｈ－ＮＭＲ分析により決定した。溶媒としてクロロホルム－ｄ１を使用し、テトラメチルシランの共鳴線を内部標準として使用した。また、ジビニルベンジルフルオレン化合物の質量は、日立製作所製、Ｍ-８０Ｂ型質量分析装置を使用し、ＦＤ-ＭＳ分析を行うことにより測定した。
2) Structure of divinylbenzylfluorene compound Determined by 13 C-NMR and 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d 1 was used as solvent and the resonance line of tetramethylsilane was used as internal standard. Further, the mass of the divinylbenzylfluorene compound was measured by FD-MS analysis using Hitachi, Ltd. M-80B type mass spectrometer.
３）ガラス転移温度（Ｔｇ）、融点（Ｔｍ）、及び軟化温度の測定
ジビニルベンジルフルオレン化合物をガラス基板に乾燥後の厚さが、２０μｍになるように均一に塗布した後、ホットプレートを用いて、９０℃で３０分間加熱し、乾燥させた。得られたガラス基板上の樹脂膜はガラス基板と共に、ＴＭＡ（熱機械分析装置）測定装置にセットし、窒素気流下、昇温速度１０℃／分で２２０℃まで昇温し、更に、２２０℃で２０分間加熱処理することにより、残存する溶媒を除去した。ガラス基板を室温まで放冷した後、ＴＭＡ測定装置中の試料に分析用プローブを接触させ、窒素気流下、昇温速度１０℃／分で３０℃から３６０℃までスキャンさせることにより測定を行い、接線法により軟化温度を求めた。サンプルの耐熱性により、プローブが樹脂膜を貫通せず、膜厚よりも小さなプローブ侵入量を示さない場合には、軟化温度の指標としてプローブが侵入しなかった最高温度以上と表示した。
ジビニルベンジルフルオレン化合物の融点は、ＤＳＣ（示差走査型熱量計）を使用し、窒素気流下、昇温速度１０℃／分で－２０℃から３２０℃までスキャンさせることにより測定を行った。
3) Measurement of glass transition temperature (Tg), melting point (Tm), and softening temperature A divinylbenzylfluorene compound was evenly applied to a glass substrate so that the thickness after drying was 20 μm, and then heated using a hot plate. , 90° C. for 30 minutes and dried. The resulting resin film on the glass substrate was set in a TMA (thermo-mechanical analyzer) measurement device together with the glass substrate, and heated to 220°C at a temperature elevation rate of 10°C/min under a nitrogen stream. Residual solvent was removed by heat treatment at rt for 20 minutes. After allowing the glass substrate to cool to room temperature, an analysis probe is brought into contact with the sample in the TMA measurement device, and measurement is performed by scanning from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min under a nitrogen stream, The softening temperature was determined by the tangent method. When the probe did not penetrate the resin film due to the heat resistance of the sample and the amount of probe penetration was not smaller than the film thickness, the maximum temperature at which the probe did not penetrate was indicated as an index of the softening temperature.
The melting point of the divinylbenzylfluorene compound was measured using a DSC (differential scanning calorimeter) by scanning from −20° C. to 320° C. at a heating rate of 10° C./min under a nitrogen stream.
４）３００℃における重量減少量、耐熱変色性、及びハンダ耐熱性試験の測定
ジビニルベンジルフルオレン化合物の３００℃に於ける重量減少量及び耐熱変色性の測定は、試料をＴＧＡ（熱天秤）測定装置にセットし、窒素気流下、昇温速度１０℃／分で３０℃から３２０℃までスキャンさせることにより測定を行い、３００℃に於ける重量減少量を求めると共に、測定後の試料の変色量を目視にて確認し、Ａ：熱変色無し、Ｂ：淡黄色、Ｃ：茶色、Ｄ：黒色に分類することにより耐熱変色性の評価を行った。
さらに、ジビニルベンジルフルオレン化合物のハンダ耐熱性試験は、２．０ｍｍ厚で１０ｍｍ角の硬化させた試験片シートを２８０℃の鉛フリーはんだ槽に３０秒間浸漬させた後、試験片を引き上げ、浸漬後の試験片の形状の変化を目視にて確認し、Ａ：変化無し、Ｂ：反りあり、Ｃ：変形・膨れ有りに分類することによりハンダ耐熱性の評価を行った。
4) Measurement of weight loss at 300°C, heat discoloration resistance, and soldering heat resistance test Weight loss and heat discoloration of the divinylbenzylfluorene compound at 300°C were measured using a TGA (thermal balance) measuring device. and measured by scanning from 30° C. to 320° C. at a heating rate of 10° C./min under a nitrogen stream to determine the amount of weight loss at 300° C., and the amount of discoloration of the sample after measurement. It was confirmed visually, and heat discoloration resistance was evaluated by classifying into A: no heat discoloration, B: pale yellow, C: brown, and D: black.
Furthermore, in the solder heat resistance test of the divinylbenzylfluorene compound, a cured test piece sheet of 2.0 mm thickness and 10 mm square was immersed in a lead-free solder bath at 280 ° C. for 30 seconds. The change in the shape of the test piece was visually confirmed, and the solder heat resistance was evaluated by classifying it into A: no change, B: warping, and C: deformation and swelling.
５）耐溶剤性の測定
ジビニルベンジルフルオレン化合物の耐溶剤性の測定は、真空プレス成形により、硬化させた試料板をトルエンに室温で１０分間浸漬し、浸漬後の試料の変化を目視にて確認し、Ａ：変化無し、Ｂ：膨潤、Ｃ：変形・膨れ有りに分類することにより耐溶剤性の評価を行った。
5) Measurement of solvent resistance The solvent resistance of the divinylbenzylfluorene compound is measured by immersing a cured sample plate in toluene at room temperature for 10 minutes by vacuum press molding, and visually confirming changes in the sample after immersion. Then, solvent resistance was evaluated by classifying into A: No change, B: Swelling, and C: Deformation/swelling.
６）Ｈａｚｅ及び全光線透過率の測定
２ｍｍ厚もしくは２００μｍ厚の平板試験片を作製し、Ｈａｚｅ（濁度）及び全光線透過率を、分光式色差計（日本電色社製、ＳＺ－Σ９０）を用い測定した。
6) Measurement of Haze and total light transmittance A flat plate test piece with a thickness of 2 mm or 200 μm is prepared, and Haze (turbidity) and total light transmittance are measured using a spectroscopic color difference meter (manufactured by Nippon Denshoku Co., Ltd., SZ-Σ90). was measured using
７）屈折率・アッベ数
４ｃｍ×０．８ｃｍのテストピースを作製し、屈折率及びアッベ数を多波長アッベ屈折計（アタゴ社製、「多波長アッベ屈折率計 DR-M2」）を用い測定した。中間液にはサンプルより屈折率の高いイオウヨウ化メチレン溶液を用い、Ｄ線５８９ｎｍの干渉フィルターを用い屈折率とアッベ数を測定した。
7) Refractive index/Abbé number A test piece of 4 cm × 0.8 cm is prepared, and the refractive index and Abbe number are measured using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., "Multi-wavelength Abbe refractometer DR-M2"). did. A methylene sulfur iodide solution having a refractive index higher than that of the sample was used as the intermediate liquid, and the refractive index and Abbe number were measured using an interference filter for the D-line of 589 nm.
８）分光透過率
厚さ１．０ｍｍの平行平板をテストピースとして、分光光度計（コニカミノルタ社製、「CM－３６００ｄ」）用いて波長：４００ｎｍの分光透過率を測定した。測定タイミングは、１９０℃６０分でのポストキュアを行った耐熱試験前と、エアーオーブン中、２６０℃、８分間の耐熱試験後とした。
8) Spectral Transmittance A parallel plate having a thickness of 1.0 mm was used as a test piece, and the spectral transmittance at a wavelength of 400 nm was measured using a spectrophotometer (manufactured by Konica Minolta, "CM-3600d"). The measurement timing was before the heat resistance test in which post-curing was performed at 190° C. for 60 minutes, and after the heat resistance test in an air oven at 260° C. for 8 minutes.
９）吸水率
厚さ１ｍｍ、幅３０ｍｍ、長さ３０ｍｍの平板状のサンプルを作製し、真空下、１００℃、２時間の条件で乾燥させ、室温まで冷却した後、デシケーター中で恒量となるまで静置し、恒量となったサンプル質量を初期値（ｍ０）とした。次に、このサンプルを８５℃、相対湿度８５％の恒温恒湿器中に５００時間、放置した後の質量（ｍｄ）を測定し、初期値と浸漬後の質量の変化から下記式を用いて吸水率を測定した。
（ｍｄ―ｍ０）×１００／ｍ０＝吸水率（％）
9) Water absorption A plate-shaped sample with a thickness of 1 mm, a width of 30 mm, and a length of 30 mm is prepared, dried under vacuum at 100°C for 2 hours, cooled to room temperature, and then placed in a desiccator until it reaches a constant weight. The initial value (m0) was defined as the mass of the sample which became constant after standing still. Next, the mass (md) after leaving this sample in a constant temperature and humidity chamber at 85° C. and a relative humidity of 85% for 500 hours is measured, and the following formula is used from the initial value and the change in mass after immersion. Water absorption was measured.
(md-m0) x 100/m0 = water absorption (%)
実施例１ ジビニルベンジルフルオレン化合物（Ａ－１）の合成
フルオレン ２０３．５４ｇ（純度：９８％、１．２０ｍｏｌ）、トルエン８００ｇ、テトラ－ｎ－ ブチルアンモニウムブロミド１８．０９ｇ（純度：９８％、０．０５５モル）、ハイドロキノン２．７８ｇ（純度：９９％、０．０２５モル）、さらに、ＮａＯＨ １７４．４２ｇ（純度：９７％、４．２３モル）を水 ３２０ｍｌに溶解させたＮａＯＨ水溶液を仕込み、撹拌しながら６０℃まで昇温して均一の溶液にした。この溶液にＡＧＣセイミケミカル社製ビニルベンジルクロリドＣＭＳ－１４（ｍ－／ｐ－異性体：５／９５重量％混合物） ４４９．８３ｇ（純度９５％、２．８モル）を２０分かけて滴下し、その後６０～６１℃で８時間反応させた。得られた緑色の反応生成物に２００ｍｌのトルエンを追加してから、溶液を２Ｎ塩酸で中和した後、蒸留水で３回洗浄し、トルエンを減圧除去後、得られた淡黄色粘稠固体を新鮮なメタノールから再結晶することにより、ＤＳＣ測定から融点が１１９℃の白色の固体３４９．４４ｇ（収率７２．８％）を得た。これを化合物Ａ－１とする。
化合物Ａ－１の構造の確認は１Ｈ－ＮＭＲスペクトル、１３Ｃ－ＮＭＲスペクトル、ＩＲスペクトル、ＦＤ－ＭＳ測定により行った。ＦＤ－ＭＳの測定結果からＭｗは４００であり、これらの測定結果から生成物はジビニルベンジルフルオレン（一般式１において、Ｒ１が水素原子）であり、ＮＭＲスペクトルから、ビニルベンジル単位は、ｍ－／ｐ－異性体：５／９５％混合物であることを確認した。化合物Ａ－１を室温で、トルエンに１０ｗｔ％の濃度で、溶解させたところ、透明な溶液が得られ、良好な溶解性を有していることを確認した。
Example 1 Synthesis of divinylbenzylfluorene compound (A-1) 203.54 g of fluorene (purity: 98%, 1.20 mol), 800 g of toluene, 18.09 g of tetra-n-butylammonium bromide (purity: 98%, 0.20 mol). 055 mol), 2.78 g of hydroquinone (purity: 99%, 0.025 mol), and a NaOH aqueous solution prepared by dissolving 174.42 g of NaOH (purity: 97%, 4.23 mol) in 320 ml of water, and stirred. The temperature was raised to 60° C. while stirring to form a uniform solution. To this solution, 449.83 g (95% purity, 2.8 mol) of vinylbenzyl chloride CMS-14 (m-/p-isomer: 5/95% by weight mixture) manufactured by AGC Seimi Chemical Co., Ltd. was added dropwise over 20 minutes. , and then reacted at 60 to 61° C. for 8 hours. After adding 200 ml of toluene to the obtained green reaction product, the solution was neutralized with 2N hydrochloric acid and then washed with distilled water three times. was recrystallized from fresh methanol to give 349.44 g (72.8% yield) of a white solid with a melting point of 119° C. by DSC measurement. This is referred to as Compound A-1.
The structure of compound A-1 was confirmed by 1 H-NMR spectrum, 13 C-NMR spectrum, IR spectrum and FD-MS measurement. From the results of FD-MS measurement, Mw is 400. From these measurement results, the product is divinylbenzylfluorene (R 1 is a hydrogen atom in general formula 1), and from the NMR spectrum, the vinylbenzyl unit is m- /p-isomer: confirmed to be a 5/95% mixture. When compound A-1 was dissolved in toluene at a concentration of 10 wt % at room temperature, a transparent solution was obtained, confirming that it has good solubility.
化合物Ａ－１を２．０ｍｍのスペーサーを介して、金型に入れ、真空プレス成形機を使用して、真空下、２００℃、１時間硬化を行った。
得られた硬化シートを切り出し、光学特性、引張特性の測定及び熱分析を実施した。その結果、全光線透過率：９１．３％、Ｈａｚｅ：０．３０、屈折率：１．６５２、アッベ数：２３．６、線膨張係数：８３ｐｐｍ／℃、吸水率：０．１５％、耐溶剤性：Ａ、ハンダ耐熱性：Ａであった。
また、ＴＭＡ測定の結果、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３００℃に於ける重量減少量は０．３ｗｔ％、耐熱変色性はＡであった。
Compound A-1 was placed in a mold via a 2.0 mm spacer, and cured at 200° C. for 1 hour under vacuum using a vacuum press molding machine.
The resulting cured sheet was cut out and subjected to measurement of optical properties, tensile properties and thermal analysis. As a result, total light transmittance: 91.3%, haze: 0.30, refractive index: 1.652, Abbe number: 23.6, linear expansion coefficient: 83 ppm/°C, water absorption: 0.15%, resistance Solvent resistance: A, solder heat resistance: A.
Moreover, as a result of TMA measurement, the softening temperature was 300° C. or higher. As a result of TGA measurement, the weight loss at 300° C. was 0.3 wt %, and the heat discoloration resistance was A.
比較例１ ジビニルベンジルフルオレン化合物（Ｂ－１）の合成
フルオレン ２０３．５４ｇ（純度：９８％、１．２０ｍｏｌ）、トルエン８００ｇ、テトラ－ｎ－ ブチルアンモニウムブロミド１８．０９ｇ（純度：９８％、０．０５５モル）、ハイドロキノン２．７８ｇ（純度：９９％、０．０２５モル）、さらに、ＮａＯＨ １７４．４２ｇ（純度：９７％、４．２３モル）を水 ３２０ｍｌに溶解させたＮａＯＨ水溶液を仕込み、撹拌しながら６０℃まで昇温して均一の溶液にした。この溶液にダウケミカル社製ビニルベンジルクロリドＶＢＣ（ｍ－／ｐ－異性体：５７／４３重量％混合物） ４４５．１４ｇ（純度９６％、２．８モル）を２０分かけて滴下し、その後６０～６１℃で８時間反応させた。得られた緑色の反応生成物に２００ｍｌのトルエンを追加してから、溶液を２Ｎ塩酸で中和した後、蒸留水で３回洗浄し、トルエンを減圧除去後、得られた淡黄色粘稠固体を新鮮なトルエンから再結晶することにより、ＤＳＣ測定から融点が１４４℃の白色の固体３２４．４８ｇ（収率６７．６％）を得た。これを化合物Ｂ－１とする。
化合物Ｂ－１の構造の確認は１Ｈ－ＮＭＲスペクトル、１３Ｃ－ＮＭＲスペクトル、ＩＲスペクトル、ＦＤ－ＭＳ測定により行った。ＦＤ－ＭＳの測定結果からＭｗは４００であり、これらの測定結果から生成物ジビニルベンジルフルオレン（一般式１において、Ｒ１が水素原子）であり、ビニルベンジル単位は、ｍ－／ｐ－異性体：５７／４３％混合物であった。化合物Ｂ－１を室温で、トルエンに１０ｗｔ％の濃度で、溶解させたところ、白濁した溶液が得られ、溶解性は不十分であることを確認した。
Comparative Example 1 Synthesis of divinylbenzylfluorene compound (B-1) 203.54 g of fluorene (purity: 98%, 1.20 mol), 800 g of toluene, 18.09 g of tetra-n-butylammonium bromide (purity: 98%, 0.25 mol). 055 mol), 2.78 g of hydroquinone (purity: 99%, 0.025 mol), and a NaOH aqueous solution prepared by dissolving 174.42 g of NaOH (purity: 97%, 4.23 mol) in 320 ml of water, and stirred. The temperature was raised to 60° C. while stirring to form a uniform solution. 445.14 g (purity 96%, 2.8 mol) of vinylbenzyl chloride VBC (m-/p-isomer: 57/43% by weight mixture) manufactured by Dow Chemical Co. was added dropwise to this solution over 20 minutes. The reaction was allowed to proceed at ~61°C for 8 hours. After adding 200 ml of toluene to the obtained green reaction product, the solution was neutralized with 2N hydrochloric acid and then washed with distilled water three times. was recrystallized from fresh toluene to give 324.48 g (67.6% yield) of a white solid with a melting point of 144° C. by DSC measurement. This is referred to as compound B-1.
The structure of compound B-1 was confirmed by 1 H-NMR spectrum, 13 C-NMR spectrum, IR spectrum and FD-MS measurement. From the results of FD-MS measurement, Mw is 400. From these measurement results, the product is divinylbenzylfluorene (in general formula 1, R 1 is a hydrogen atom), and the vinylbenzyl units are m-/p-isomers. : 57/43% mixture. When compound B-1 was dissolved in toluene at a concentration of 10 wt % at room temperature, a cloudy solution was obtained, confirming that the solubility was insufficient.
化合物Ｂ－１を２．０ｍｍのスペーサーを介して、金型に入れ、真空プレス成形機を使用して、真空下、２００℃、１時間硬化を行った。
得られた硬化シートを切り出し、光学特性、引張特性の測定及び熱分析を実施した。
その結果、全光線透過率：８９．６％、Ｈａｚｅ：３．６４、屈折率：１．６４８、アッベ数：２３．９、線膨張係数：８７ｐｐｍ／℃、吸水率：０．１６％、耐溶剤性：Ａ、ハンダ耐熱性：Ａであった。
また、ＴＭＡ測定の結果、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３００℃に於ける重量減少量は０．４ｗｔ％、耐熱変色性はＡであった。
Compound B-1 was placed in a mold via a 2.0 mm spacer, and cured at 200° C. for 1 hour under vacuum using a vacuum press molding machine.
The resulting cured sheet was cut out and subjected to measurement of optical properties, tensile properties and thermal analysis.
As a result, total light transmittance: 89.6%, haze: 3.64, refractive index: 1.648, Abbe number: 23.9, linear expansion coefficient: 87 ppm/°C, water absorption: 0.16%, resistance Solvent resistance: A, solder heat resistance: A.
Moreover, as a result of TMA measurement, the softening temperature was 300° C. or higher. As a result of TGA measurement, the weight loss at 300° C. was 0.4 wt %, and the heat discoloration resistance was A.
比較例２ ジビニルベンジルフルオレン化合物（Ｃ－１）の合成
フルオレン ２０３．５４ｇ（純度：９８％、１．２０ｍｏｌ）、トルエン８００ｇ、テトラ－ｎ－ ブチルアンモニウムブロミド１８．０９ｇ（純度：９８％、０．０５５モル）、ハイドロキノン２．７８ｇ（純度：９９％、０．０２５モル）、さらに、ＮａＯＨ １７４．４２ｇ（純度：９７％、４．２３モル）を水 ３２０ｍｌに溶解させたＮａＯＨ水溶液を仕込み、撹拌しながら６０℃まで昇温して均一の溶液にした。この溶液にセイミケミカル社製ビニルベンジルクロリドＣＭＳ－Ｐ（ｍ－／ｐ－異性体：５０／５０重量％混合物）４４９．８３ｇ（純度９５％、２．８モル）を２０分かけて滴下し、その後６０～６１℃で８時間反応させた。得られた緑色の反応生成物に２００ｍｌのトルエンを追加してから、溶液を２Ｎ塩酸で中和した後、蒸留水で３回洗浄し、トルエンを減圧除去後、得られた淡黄色粘稠固体を新鮮なトルエンから再結晶することにより、ＤＳＣ測定から融点が１４５℃の白色の固体３１３．９２ｇ（収率６５．４％）を得た。これを化合物Ｃ－１とする。
化合物Ｃ－１の構造の確認は１Ｈ－ＮＭＲスペクトル、１３Ｃ－ＮＭＲスペクトル、ＩＲスペクトル、ＦＤ－ＭＳ測定により行った。ＦＤ－ＭＳの測定結果からＭｗは４００であり、これらの測定結果から生成物ジビニルベンジルフルオレン（一般式１において、Ｒ１が水素原子）であり、ビニルベンジル単位は、ｍ－／ｐ－異性体：５０／５０％混合物であった。化合物Ｃ－１を室温で、トルエンに１０ｗｔ％の濃度で、溶解させたところ、白濁した溶液が得られ、溶解性は不十分であることを確認した。
Comparative Example 2 Synthesis of divinylbenzylfluorene compound (C-1) 203.54 g of fluorene (purity: 98%, 1.20 mol), 800 g of toluene, 18.09 g of tetra-n-butylammonium bromide (purity: 98%, 0.25 mol). 055 mol), 2.78 g of hydroquinone (purity: 99%, 0.025 mol), and a NaOH aqueous solution prepared by dissolving 174.42 g of NaOH (purity: 97%, 4.23 mol) in 320 ml of water, and stirred. The temperature was raised to 60° C. while stirring to form a uniform solution. To this solution, 449.83 g (95% purity, 2.8 mol) of vinylbenzyl chloride CMS-P (m-/p-isomer: 50/50% by weight mixture) manufactured by Seimi Chemical Co., Ltd. was added dropwise over 20 minutes, After that, the mixture was reacted at 60-61° C. for 8 hours. After adding 200 ml of toluene to the obtained green reaction product, the solution was neutralized with 2N hydrochloric acid and then washed with distilled water three times. was recrystallized from fresh toluene to give 313.92 g (65.4% yield) of a white solid with a melting point of 145° C. by DSC measurement. This is referred to as compound C-1.
The structure of compound C-1 was confirmed by 1 H-NMR spectrum, 13 C-NMR spectrum, IR spectrum and FD-MS measurement. From the results of FD-MS measurement, Mw is 400. From these measurement results, the product is divinylbenzylfluorene (in general formula 1, R 1 is a hydrogen atom), and the vinylbenzyl units are m-/p-isomers. : 50/50% mixture. When compound C-1 was dissolved in toluene at a concentration of 10 wt % at room temperature, a cloudy solution was obtained, confirming that the solubility was insufficient.
化合物Ｃ－１を２．０ｍｍのスペーサーを介して、金型に入れ、真空プレス成形機を使用して、真空下、２００℃、１時間硬化を行った。
得られた硬化シートを切り出し、光学特性、引張特性の測定及び熱分析を実施した。その結果、全光線透過率：８９．４％、Ｈａｚｅ：４．１４、屈折率：１．６４９、アッベ数：２３．９、線膨張係数：８８ｐｐｍ／℃、吸水率：０．１８％、耐溶剤性：Ａ、ハンダ耐熱性：Ａであった。
また、ＴＭＡ測定の結果、軟化温度は３００℃以上であった。ＴＧＡ測定の結果、３００℃に於ける重量減少量は０．４２ｗｔ％、耐熱変色性はＡであった。
Compound C-1 was placed in a mold via a 2.0 mm spacer, and cured at 200° C. for 1 hour under vacuum using a vacuum press molding machine.
The resulting cured sheet was cut out and subjected to measurement of optical properties, tensile properties and thermal analysis. As a result, total light transmittance: 89.4%, haze: 4.14, refractive index: 1.649, Abbe number: 23.9, linear expansion coefficient: 88 ppm/°C, water absorption: 0.18%, resistance Solvent resistance: A, solder heat resistance: A.
Moreover, as a result of TMA measurement, the softening temperature was 300° C. or higher. As a result of TGA measurement, the weight loss at 300° C. was 0.42 wt %, and the heat discoloration resistance was A.
実施例２及び比較例３～４
実施例１及び比較例１，２で得られた化合物Ａ－１、Ｂ－１、Ｃ－１を使用し、表１に示す割合で各成分を配合し、硬化性樹脂組成物を得た。次に、この硬化性樹脂組成物を、各種試験方法により硬化し性能評価を行った。性能評価結果も表１に示す。
Example 2 and Comparative Examples 3-4
Using the compounds A-1, B-1 and C-1 obtained in Example 1 and Comparative Examples 1 and 2, each component was blended in the ratio shown in Table 1 to obtain a curable resin composition. Next, this curable resin composition was cured by various test methods and evaluated for performance. Performance evaluation results are also shown in Table 1.
共重合可能なモノマー：
ＮＫエステル Ａ－ＬＥＮ－１０；２－（ｏ－フェニルフェノキシ）エチルアクリレート（新中村化学工業株式会社製）
硬化剤：
パーブチルＰ；α，α’－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン（日油株式会社製）
光重合開始剤：
イルガキュア１８４；１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（チバ・スペシャリティ・ケミカルズ社製）
安定剤：
アデカスタブＡＯ－６０；ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（株式会社ＡＤＥＫＡ）
Copolymerizable monomers:
NK ester A-LEN-10; 2-(o-phenylphenoxy) ethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Hardener:
Perbutyl P; α,α'-bis(t-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation)
Photoinitiator:
Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals)
Stabilizer:
ADEKA STAB AO-60; pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (ADEKA Co., Ltd.)
本発明のジビニルベンジルフルオレン化合物、及び、硬化性樹脂組成物、並びに、硬化性樹脂組成物を成形、硬化して得られる樹脂硬化物は、光学材料として優れる。とりわけプリズムレンズシート、フレネルレンズ、レンチキュラーレンズ、眼鏡レンズ、非球面レンズ等の光学プラスチックレンズ用材料として有用であるそして、このようなレンズは、撮像装置に有利に使用される。また、本発明の硬化性樹脂組成物又は樹脂硬化物はその他にも、光ディスク、光ファイバー、光導波路等のオプトエレクトロニクス向け用途、多層基板、プリプレグ、樹脂付き金属箔、印刷インキ、塗料、クリアーコート剤、ツヤニス等にも使用できる。
本発明の変性ビニル芳香族系共重合体は、電気・電子産業、宇宙・航空機産業、建築・建設産業等の分野において、誘電材料、絶縁材料、耐熱材料、構造材料、接着剤、封止剤、塗料、コーティング剤、シーリング材、印刷インキ、塗料、クリアーコート剤、ツヤニス、分散剤等としても有用である。熱可塑性樹脂又は硬化性樹脂組成物の耐熱性、誘電特性、接着性・密着性及び光学特性等の特性を改質する改質剤として使用することもできる。
The divinylbenzylfluorene compound of the present invention, the curable resin composition, and the resin cured product obtained by molding and curing the curable resin composition are excellent as optical materials. In particular, it is useful as a material for optical plastic lenses such as prism lens sheets, Fresnel lenses, lenticular lenses, spectacle lenses, and aspherical lenses, and such lenses are advantageously used in imaging devices. In addition, the curable resin composition or resin cured product of the present invention can also be used for optoelectronic applications such as optical discs, optical fibers, and optical waveguides, multilayer substrates, prepregs, metal foils with resin, printing inks, paints, and clear coating agents. , can also be used for gloss varnish, etc.
The modified vinyl aromatic copolymer of the present invention is used as dielectric materials, insulating materials, heat-resistant materials, structural materials, adhesives, sealants, etc. , paints, coating agents, sealants, printing inks, paints, clear coating agents, gloss varnishes, dispersants, and the like. It can also be used as a modifier for modifying properties such as heat resistance, dielectric properties, adhesiveness/bonding properties, and optical properties of thermoplastic resins or curable resin compositions.
Claims (9)
（式中、Ｒ１は独立にハロゲン原子、炭素数１～５のアルキル基、アルコキシ基、チオアルコキシ基、炭素数６～３０のアリール基及び炭素数３～３０のヘテロアリール基から選ばれる一つの置換基を示し、ｘは独立に０～４の整数を示す）
示査走査熱量計を使用して昇温速度：１０℃／分で測定を行った場合、融点が１３０℃以下又は融点を持たないことを特徴とするジビニルベンジルフルオレン化合物。 A divinylbenzylfluorene compound represented by the following general formula (1),
(wherein R 1 is independently selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a thioalkoxy group, an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 3 to 30 carbon atoms; and x independently represents an integer of 0 to 4)
A divinylbenzylfluorene compound having a melting point of 130°C or less or no melting point when measured using a differential scanning calorimeter at a heating rate of 10°C/min.
（式中、Ｒ１は独立にハロゲン原子、炭素数１～５のアルキル基、アルコキシ基、チオアルコキシ基および炭素数６～３０のアリール基から選ばれる一つの置換基を示し、ｘは独立に０～４の整数を示す） One or more fluorene compounds represented by the following general formula (2) and a vinylbenzyl halide having a p-isomer/(m-isomer+p-isomer) ratio of 0.6 to 1.0 and in the presence of an alkali.
(wherein R 1 is independently a substituent selected from a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a thioalkoxy group and an aryl group having 6 to 30 carbon atoms, and x is independently indicates an integer from 0 to 4)
9. An image pickup apparatus comprising the optical article according to claim 7 or 8.
Priority Applications (1)
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| JP2021073421A JP2022167558A (en) | 2021-04-23 | 2021-04-23 | Divinylbenzyl fluorene compound and method for producing the same, curable resin composition obtained from the same, curable resin cured product, optical article, and imaging device |
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|---|---|---|---|
| JP2021073421A JP2022167558A (en) | 2021-04-23 | 2021-04-23 | Divinylbenzyl fluorene compound and method for producing the same, curable resin composition obtained from the same, curable resin cured product, optical article, and imaging device |
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| JP2022167558A true JP2022167558A (en) | 2022-11-04 |
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