JP2008119890A - Method for producing thin optical lens molding - Google Patents
Method for producing thin optical lens molding Download PDFInfo
- Publication number
- JP2008119890A JP2008119890A JP2006304053A JP2006304053A JP2008119890A JP 2008119890 A JP2008119890 A JP 2008119890A JP 2006304053 A JP2006304053 A JP 2006304053A JP 2006304053 A JP2006304053 A JP 2006304053A JP 2008119890 A JP2008119890 A JP 2008119890A
- Authority
- JP
- Japan
- Prior art keywords
- cyclic olefin
- optical lens
- gate
- cavity
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000465 moulding Methods 0.000 title abstract description 21
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 32
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 32
- -1 Cyclic olefin Chemical class 0.000 claims description 61
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000003892 spreading Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 37
- 229920001577 copolymer Polymers 0.000 description 37
- 239000000178 monomer Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 24
- 238000007142 ring opening reaction Methods 0.000 description 23
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- 238000001746 injection moulding Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000012644 addition polymerization Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
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- 238000005649 metathesis reaction Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000007906 compression Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- QVRBGKYLLCLCHL-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene Chemical compound CC1C=CC=C1 QVRBGKYLLCLCHL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JWQKMEKSFPNAIB-UHFFFAOYSA-N Silvestrene Natural products CC(=C)C1CCC=C(C)C1 JWQKMEKSFPNAIB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
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- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PTOQCUYVGKZAFS-UHFFFAOYSA-N ethenylcycloheptane Chemical compound C=CC1CCCCCC1 PTOQCUYVGKZAFS-UHFFFAOYSA-N 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
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- 125000000962 organic group Chemical group 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
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- IGCQXPZQGHULRC-UHFFFAOYSA-N 1-ethenylcycloheptene Chemical compound C=CC1=CCCCCC1 IGCQXPZQGHULRC-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/2701—Details not specific to hot or cold runner channels
- B29C45/2708—Gates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00019—Production of simple or compound lenses with non-spherical faces, e.g. toric faces
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Ophthalmology & Optometry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、薄型の光学レンズ成形体の製造方法に関する。より詳しくは、本発明は、特定のゲートを有する金型装置を用いて射出成形を行う、薄型の光学レンズ成形体の製造方法に関する。 The present invention relates to a method for manufacturing a thin optical lens molded body. More specifically, the present invention relates to a method for manufacturing a thin optical lens molded body, in which injection molding is performed using a mold apparatus having a specific gate.
近年、携帯電話本体の薄型化などにより、携帯電話に搭載されるカメラレンズモジュールも薄型化が進んでいる。カメラレンズモジュールの薄型化にあたっては、そのモジュールを構成する部品である光学レンズの厚み自体を薄くする設計が行われている。 In recent years, camera lens modules mounted on mobile phones are becoming thinner due to the thinness of mobile phone bodies. In order to reduce the thickness of the camera lens module, a design is made to reduce the thickness of the optical lens, which is a component constituting the module.
ここで、光学レンズには加工性および設計の自由度の観点から、透明な熱可塑性樹脂が用いられており、その中でも、光学歪みおよび耐熱性の観点から、環状オレフィン系樹脂が好適に使用されている(特許文献1、非特許文献1、2)。
しかしながら、このような環状オレフィン系樹脂を用いて、薄型の光学レンズ成形体を射出成形にて加工する場合は、光学レンズ内部に発生する光学歪みが大きくなったり、また、面精度が低くなったりする問題があった。 However, when a thin optical lens molded body is processed by injection molding using such a cyclic olefin-based resin, the optical distortion generated inside the optical lens increases, and the surface accuracy decreases. There was a problem to do.
したがって、本発明の目的は、上記のような問題を解決しようとするものであって、光学歪みが小さく、面精度の安定性に優れた薄型の光学レンズ成形体の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for manufacturing a thin optical lens molded body that is intended to solve the above-described problems and has small optical distortion and excellent surface accuracy stability. is there.
本発明者らは、上記問題点を解決すべく鋭意研究した結果、特定のゲートを有する金型装置を用いて射出成形すれば、光学歪みが小さく、面精度の安定性に優れた薄型の光学レンズ成形体を作製できることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have found that a thin optical device with small optical distortion and excellent surface accuracy stability can be obtained by injection molding using a mold apparatus having a specific gate. The present inventors have found that a lens molded body can be produced and have completed the present invention.
すなわち、本発明に係る光学レンズ成形体の製造方法は、
光学レンズ成形体に対応するキャビティーとゲートとが、ゲート開口部を介して結合している金型装置により、環状オレフィン系樹脂を射出成形して、
鍔部とレンズ部とが、凹部を介して結合しており、該鍔部の厚みが0.5mm以下、該凹部
の厚みが該鍔部の厚み以下かつ0.4mm以下であり、直径が10mm以下の光学レンズ成形体を
製造する方法であって、
上記ゲート開口部における上記キャビティーの高さ方向のゲートの厚みt1と、上記ゲ
ート開口部における上記キャビティーの高さ方向の鍔部の厚みt2とが、下記式(1)を
満たし、かつ、上記ゲートが、上記ゲート開口部に向かって、上記キャビティーの高さ方向の一方が狭まっており、該高さ方向に狭まる傾斜角度βが、下記式(2)を満たす上記金型装置により、上記環状オレフィン系樹脂を射出成形することを特徴とする。
That is, the method for producing an optical lens molded body according to the present invention includes:
Cyclic olefin-based resin is injection-molded by a mold device in which a cavity and a gate corresponding to an optical lens molded body are bonded through a gate opening,
The collar part and the lens part are connected through a recess, the thickness of the collar part is 0.5 mm or less, the thickness of the recess is less than the thickness of the collar part and 0.4 mm or less, and the diameter is 10 mm or less. A method for producing an optical lens molded body, comprising:
The thickness t 1 of the gate in the height direction of the cavity in the gate opening and the thickness t 2 of the flange in the height direction of the cavity in the gate opening satisfy the following formula (1): In addition, the mold apparatus is such that one of the cavities in the height direction is narrowed toward the gate opening, and the inclination angle β narrowed in the height direction satisfies the following formula (2): Thus, the cyclic olefin-based resin is injection-molded.
t2×0.1≦t1≦t2×0.8 (1)
20°≦β≦60° (2)
上記ゲートは、上記ゲート開口部に向かって、上記キャビティーの幅方向の両方が均等
に狭まっており、該幅方向に狭まる傾斜角度αが、下記式(3)を満たすことが好ましい。
t 2 × 0.1 ≦ t 1 ≦ t 2 × 0.8 (1)
20 ° ≦ β ≦ 60 ° (2)
In the gate, it is preferable that both of the width directions of the cavities are uniformly narrowed toward the gate opening, and an inclination angle α narrowing in the width direction satisfies the following formula (3).
30°≦α≦60° (3)
または、上記ゲートは、上記ゲート開口部に向かって、上記キャビティーの幅方向の両方が均等に広がっており、該幅方向に広がる傾斜角度αが、下記式(4)を満たすことが好ましい。
30 ° ≦ α ≦ 60 ° (3)
Alternatively, in the gate, it is preferable that both of the width directions of the cavities spread uniformly toward the gate opening, and the inclination angle α spreading in the width direction satisfies the following formula (4).
30°≦α≦60° (4)
上記ゲートは、フラット部を有し、該フラット部を介して上記キャビティーと結合しており、該フラット部の長さLが0.2〜2.0mmであることが好ましい。
30 ° ≦ α ≦ 60 ° (4)
It is preferable that the gate has a flat portion and is coupled to the cavity through the flat portion, and the length L of the flat portion is 0.2 to 2.0 mm.
上記環状オレフィン系樹脂は、少なくとも1種の極性基を含むことが好ましい。 The cyclic olefin resin preferably contains at least one polar group.
本発明によれば、光学歪が小さく面精度が良好な薄型の光学レンズ成形体が得られる。この光学レンズ成形体は、携帯電話のカメラレンズユニットやパーソナルコンピューターのカメラユニットなど小型のカメラユニットを構成する光学レンズとして有用である。 According to the present invention, a thin optical lens molded body with small optical distortion and good surface accuracy can be obtained. This optical lens molded body is useful as an optical lens constituting a small camera unit such as a camera lens unit of a mobile phone or a camera unit of a personal computer.
以下、本発明について詳細に説明する。
本発明に係る光学レンズ成形体の製造方法は、特定のゲートを有する金型装置により、環状オレフィン系樹脂を射出成形して、特定の形状を有する光学レンズ成形体を製造する方法である。
Hereinafter, the present invention will be described in detail.
The method for manufacturing an optical lens molded body according to the present invention is a method for manufacturing an optical lens molded body having a specific shape by injection molding a cyclic olefin-based resin with a mold apparatus having a specific gate.
1.環状オレフィン系樹脂
本発明に用いられる環状オレフィン系樹脂としては、下記式(I)で表される環状オレフィン化合物から導かれる単位を有する(共)重合体が挙げられる。この(共)重合体は、上記環状オレフィン化合物を含む単量体を重合して得られる。
1. Cyclic Olefin Resin Examples of the cyclic olefin resin used in the present invention include (co) polymers having units derived from a cyclic olefin compound represented by the following formula (I). This (co) polymer is obtained by polymerizing a monomer containing the cyclic olefin compound.
(式中、R1〜R4は、それぞれ独立に、水素原子、ハロゲン原子、1価の炭化水素基または極性基を示し、R1およびR2、またはR3およびR4は、一体化して2価の有機基を形成してもよく、R1またはR2と、R3またはR4とで互いに結合して単環構造または多環構造を形成してもよい。mは0または正の整数を示し、pは0または正の整数を示す。)
上記式(I)において、R1およびR3がそれぞれ独立に、水素原子、または炭素数が好ましくは1〜10、より好ましくは1〜4、特に好ましくは1もしくは2の炭化水素基であり;R2およびR4のうちの一方が水素原子であり、他方が上記1価の極性基であることがより好ましい。この場合、R1またはR3で表される上記炭化水素基としては、アルキル基が好ましく、メチル基が特に好ましい。さらに、R2およびR4のうちの一方が、下記式(II)で表される極性基である環状オレフィンを用いると、さらに、高いガラス転移温度および低い吸湿性を有するとともに、各種材料との密着性に優れた環状オレフィン系樹脂が得られる点で好ましい。
(In the formula, R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a polar group, and R 1 and R 2 , or R 3 and R 4 are integrated with each other. A divalent organic group may be formed, and R 1 or R 2 and R 3 or R 4 may be bonded to each other to form a monocyclic structure or a polycyclic structure, where m is 0 or positive Represents an integer, and p represents 0 or a positive integer.)
In the above formula (I), R 1 and R 3 are each independently a hydrogen atom or a hydrocarbon group preferably having 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2 carbon atoms; More preferably, one of R 2 and R 4 is a hydrogen atom, and the other is the monovalent polar group. In this case, the hydrocarbon group represented by R 1 or R 3 is preferably an alkyl group, and particularly preferably a methyl group. Furthermore, when one of R 2 and R 4 is a cyclic olefin that is a polar group represented by the following formula (II), it has a high glass transition temperature and low hygroscopicity, and It is preferable at the point from which the cyclic olefin resin excellent in adhesiveness is obtained.
−(CH2)nCOOR (II)
上記式(II)中、Rは、炭素数が好ましくは1〜12、さらに好ましくは1〜4、特に好ましくは1または2の炭化水素基である。ここで、上記炭化水素基としては、アルキル基が好ましい。また、nは、通常0〜5であり、nの値が小さい環状オレフィンほど、ガラス転移温度が高い環状オレフィン系樹脂が得られるため好ましく、nが0である環状オレフィン(−COOR)は合成が容易であるため特に好ましい。
- (CH 2) n COOR ( II)
In the above formula (II), R is a hydrocarbon group having preferably 1 to 12, more preferably 1 to 4, particularly preferably 1 or 2, carbon atoms. Here, the hydrocarbon group is preferably an alkyl group. In addition, n is usually 0 to 5, and a cyclic olefin having a smaller value of n is preferable because a cyclic olefin-based resin having a high glass transition temperature is obtained. A cyclic olefin (—COOR) in which n is 0 is synthesized. It is particularly preferable because it is easy.
特に、R1がアルキル基であり、R2が上記式(II)で表される極性基であり、R3お
よびR4が水素原子であると、吸湿性の低い環状オレフィン系樹脂が得られる点で好まし
い。
In particular, when R 1 is an alkyl group, R 2 is a polar group represented by the above formula (II), and R 3 and R 4 are hydrogen atoms, a cyclic olefin resin having low hygroscopicity can be obtained. This is preferable.
R1およびR2、またはR3およびR4は、一体化して2価の有機基を形成してもよく、R1またはR2と、R3またはR4とで互いに結合して単環構造または多環構造を形成してもよい。 R 1 and R 2 , or R 3 and R 4 may be combined to form a divalent organic group, and R 1 or R 2 and R 3 or R 4 are bonded to each other to form a monocyclic structure Or you may form a polycyclic structure.
mは0または正の整数を示し、好ましくは0〜3の整数を示す。pは0または正の整数を示し、好ましくは0〜3の整数を示す。また、より好ましくはm+pが0〜4の整数、特に好ましくはm+pが0〜2の整数である。最も好ましくはm=1、p=0である。m=1、p=0である環状オレフィンを用いると、ガラス転移温度が高く、かつ機械的強度にも優れた環状オレフィン系樹脂が得られる。 m represents 0 or a positive integer, and preferably represents an integer of 0 to 3. p represents 0 or a positive integer, and preferably represents an integer of 0 to 3. More preferably, m + p is an integer of 0-4, and particularly preferably, m + p is an integer of 0-2. Most preferably, m = 1 and p = 0. When a cyclic olefin with m = 1 and p = 0 is used, a cyclic olefin resin having a high glass transition temperature and excellent mechanical strength can be obtained.
上記式(I)で表される環状オレフィンは1種単独で用いても、2種以上を組み合わせて用いてもよい。
上記環状オレフィンとしては、具体的には、以下の化合物が例示できるが、これらの化合物に限定されるものではない。
ビシクロ[2.2.1]ヘプト−2−エン、
トリシクロ[4.3.0.12,5]−8−デセン、
トリシクロ[4.4.0.12,5]−3−ウンデセン、
テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
ペンタシクロ[6.5.1.13,6.02,7.09,13]−4−ペンタデセン、
5−メチルビシクロ[2.2.1]ヘプト−2−エン、
5−エチルビシクロ[2.2.1]ヘプト−2−エン、
5−メトキシカルボニルビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−5−メトキシカルボニルビシクロ[2.2.1]ヘプト−2−エン、
5−シアノビシクロ[2.2.1]ヘプト−2−エン、
8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−エトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−n−プロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデ
セン、
8−イソプロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデ
セン、
8−n−ブトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセ
ン、
8−メチル−8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3
−ドデセン、
8−メチル−8−エトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3
−ドデセン、
8−メチル−8−n−プロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10
]−3−ドデセン、
8−メチル−8−イソプロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10
]−3−ドデセン、
8−メチル−8−n−ブトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]
−3−ドデセン、
5−エチリデンビシクロ[2.2.1]ヘプト−2−エン、
8−エチリデンテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
5−フェニルビシクロ[2.2.1]ヘプト−2−エン、
8−フェニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
5−フルオロビシクロ[2.2.1]ヘプト−2−エン、
5−フルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−ペンタフルオロエチルビシクロ[2.2.1]ヘプト−2−エン、
5,5−ジフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,6−ジフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,5−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−5−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリス(フルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,5,6,6−テトラフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,5,6,6−テトラキス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,5−ジフルオロ−6,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,6−ジフルオロ−5,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリフルオロ−5−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−フルオロ−5−ペンタフルオロエチル−6,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,6−ジフルオロ−5−ヘプタフルオロ−iso−プロピル−6−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−クロロ−5,6,6−トリフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,6−ジクロロ−5,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリフルオロ−6−トリフルオロメトキシビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリフルオロ−6−ヘプタフルオロプロポキシビシクロ[2.2.1]ヘプト−2−エン、
8−フルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−ジフルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−トリフルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−ペンタフルオロエチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン
、
8,8−ジフルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,9−ジフルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,8−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3
−ドデセン、
8,9−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3
−ドデセン、
8−メチル−8−トリフルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3
−ドデセン、
8,8,9−トリフルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン
、
8,8,9−トリス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10
]−3−ドデセン、
8,8,9,9−テトラフルオロテトラシクロ[4.4.0.12,5.17,10]−3−ド
デセン、
8,8,9,9−テトラキス(トリフルオロメチル)テトラシクロ[4.4.0.12,5
.17,10]−3−ドデセン、
8,8−ジフルオロ−9,9−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,9−ジフルオロ−8,9−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,8,9−トリフルオロ−9−トリフルオロメチルテトラシクロ[4.4.0.12,5
.17,10]−3−ドデセン、
8,8,9−トリフルオロ−9−トリフルオロメトキシテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,8,9−トリフルオロ−9−ペンタフルオロプロポキシテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フルオロ−8−ペンタフルオロエチル−9,9−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,9−ジフルオロ−8−ヘプタフルオロiso−プロピル−9−トリフルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−クロロ−8,9,9−トリフルオロテトラシクロ[4.4.0.12,5.17,10]−
3−ドデセン、
8,9−ジクロロ−8,9−ビス(トリフルオロメチル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−(2,2,2−トリフルオロエトキシカルボニル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−メチル−8−(2,2,2−トリフルオロエトキシカルボニル)テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン
などを挙げることができる。
The cyclic olefin represented by the above formula (I) may be used alone or in combination of two or more.
Specific examples of the cyclic olefin include the following compounds, but are not limited to these compounds.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 2,5 ] -8-decene,
Tricyclo [4.4.0.1 2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3
-Dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3
-Dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10
] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10
] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ]
-3-dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3
-Dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3
-Dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3
-Dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10
] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 2,5
. 1 7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 2,5
. 1 7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 2,5 . 1 7,10 ] −
3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene.
上記環状オレフィン化合物を含む単量体を重合して得られる(共)重合体としては、具体的には、
(1)上記式(I)で表される環状オレフィンの開環重合体
(2)上記式(I)で表される環状オレフィンと共重合性単量体との開環共重合体
(3)上記(1)または(2)の開環(共)重合体の水素添加(共)重合体
(4)上記(1)または(2)の開環(共)重合体をフリーデルクラフト反応により環化したのち、水素添加した(共)重合体
(5)上記式(I)で表される環状オレフィンと不飽和二重結合含有化合物との飽和共重合体
(6)上記式(I)で表される環状オレフィンと、ビニル系環状炭化水素系単量体およびシクロペンタジエン系単量体から選ばれる1種以上の単量体との付加型(共)重合体およびその水素添加(共)重合体
(7)上記式(I)で表される環状オレフィンとアクリレートとの交互共重合体
が挙げられる。
As a (co) polymer obtained by polymerizing a monomer containing the cyclic olefin compound, specifically,
(1) Ring-opening polymer of cyclic olefin represented by the above formula (I) (2) Ring-opening copolymer of the cyclic olefin represented by the above formula (I) and a copolymerizable monomer (3) Hydrogenation (co) polymer of the ring-opening (co) polymer of (1) or (2) (4) The ring-opening (co) polymer of (1) or (2) is cyclized by Friedel-Craft reaction. (5) a saturated copolymer of a cyclic olefin represented by the above formula (I) and an unsaturated double bond-containing compound (6) represented by the above formula (I) Addition (co) polymer of the cyclic olefin to be used and one or more monomers selected from vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and hydrogenated (co) polymers thereof (7) An alternating copolymer of a cyclic olefin represented by the above formula (I) and an acrylate may be mentioned.
(1)開環重合体および(2)開環共重合体
開環重合体(1)および開環共重合体(2)は、メタセシス触媒の存在下で、上記環状オレフィンを開環重合させるか、または上記環状オレフィンと共重合性単量体とを開環共重合させて得られる。
(1) Ring-opening polymer and (2) Ring-opening copolymer Are the ring-opening polymer (1) and the ring-opening copolymer (2) ring-opening polymerized in the presence of a metathesis catalyst? Or obtained by ring-opening copolymerization of the cyclic olefin and a copolymerizable monomer.
<共重合性単量体>
上記共重合性単量体としては、シクロオレフィンが挙げられ、炭素数が好ましくは4〜20、より好ましくは5〜12のシクロオレフィンが望ましい。より具体的には、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテン、ジシクロペンタジエンなどを挙げることができる。これらのシクロオレフィンは、1種単独で用いても、2種以上を併用してもよい。
<Copolymerizable monomer>
Examples of the copolymerizable monomer include cycloolefin, and a cycloolefin having 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms is desirable. More specifically, cyclobutene, cyclopentene, cycloheptene, cyclooctene, dicyclopentadiene and the like can be mentioned. These cycloolefins may be used alone or in combination of two or more.
上記環状オレフィンと上記共重合性単量体との使用割合は、重量比(環状オレフィン/共重合性単量体)で100/0〜50/50が好ましく、100/0〜60/40がより好ましい。なお、「環状オレフィン/共重合性単量体=100/0」は、環状オレフィンを単独重合する場合を意味する。 The use ratio of the cyclic olefin and the copolymerizable monomer is preferably 100/0 to 50/50, more preferably 100/0 to 60/40 in terms of weight ratio (cyclic olefin / copolymerizable monomer). preferable. “Cyclic olefin / copolymerizable monomer = 100/0” means that the cyclic olefin is homopolymerized.
<開環重合用触媒>
開環(共)重合反応において用いられるメタセシス触媒は、下記の化合物(a)と化合物(b)との組合せからなる触媒である。
(a)W、MoおよびReの化合物から選ばれる少なくとも1種の化合物。
(b)デミングの周期律表IA族元素(例えば、Li、Na、Kなど)、IIA族元素(例えば、Mg、Caなど)、IIB族元素(例えば、Zn、Cd、Hgなど)、IIIA族元素(例えば、B、Alなど)、IVA族元素(例えば、Si、Sn、Pbなど)およびIVB族元素(例えば、Ti、Zrなど)から選ばれる少なくとも1つの元素を含む化合物であって、上記元素と炭素との結合、または上記元素と水素との結合を少なくとも1つ有する化合物から選ばれる少なくとも1種の化合物。
<Catalyst for ring-opening polymerization>
The metathesis catalyst used in the ring-opening (co) polymerization reaction is a catalyst comprising a combination of the following compound (a) and compound (b).
(A) at least one compound selected from compounds of W, Mo and Re.
(B) Deming periodic table group IA elements (for example, Li, Na, K, etc.), group IIA elements (for example, Mg, Ca, etc.), group IIB elements (for example, Zn, Cd, Hg, etc.), group IIIA A compound containing at least one element selected from an element (eg, B, Al, etc.), a group IVA element (eg, Si, Sn, Pb, etc.) and a group IVB element (eg, Ti, Zr, etc.), At least one compound selected from compounds having at least one bond between an element and carbon, or at least one bond between the element and hydrogen.
また、上記メタセシス触媒は、その活性を高めるために、後述の添加剤(c)を含んでいてもよい。
上記化合物(a)の具体例としては、WCl6、MoCl6、ReOCl3など、特開平
1−132626号公報の第8頁左下欄第6行〜第8頁右上欄第17行に記載の化合物を挙げることができる。
The metathesis catalyst may contain an additive (c) described later in order to increase its activity.
Specific examples of the compound (a) include compounds such as WCl 6 , MoCl 6 , and ReOCl 3 described in JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right column, line 17. Can be mentioned.
上記化合物(b)の具体例としては、n−C4H9Li、(C2H5)3Al、(C2H5)2AlCl、(C2H5)1.5AlCl1.5、(C2H5)AlCl2、メチルアルモキサン、L
iHなど、特開平1−132626号公報の第8頁右上欄第18行〜第8頁右下欄第3行に記載の化合物を挙げることができる。
Specific examples of the compound (b) include n-C 4 H 9 Li, (C 2 H 5 ) 3 Al, (C 2 H 5 ) 2 AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 , (C 2 H 5) AlCl 2, methylalumoxane, L
Examples include iH and the compounds described in JP-A-1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3.
上記添加剤(c)としては、アルコール類、アルデヒド類、ケトン類、アミン類などを好適に用いることができ、さらに特開平1−132626号公報の第8頁右下欄第16行〜第9頁左上欄第17行に記載の化合物を使用することもできる。 As the additive (c), alcohols, aldehydes, ketones, amines and the like can be suitably used. Further, JP-A-1-132626, page 8, lower right column, lines 16 to 9. The compounds described in the upper left column, line 17 of the page can also be used.
上記化合物(a)と化合物(b)との割合は、金属原子比〔(a):(b)〕で、通常1:1〜1:50、好ましくは1:2〜1:30である。
上記添加剤(c)と化合物(a)との割合は、モル比〔(c):(a)〕で、通常0.005:1〜15:1、好ましくは0.05:1〜7:1である。
The ratio of the said compound (a) and a compound (b) is metal atom ratio [(a) :( b)], and is usually 1: 1-1: 50, Preferably it is 1: 2-1: 30.
The ratio of the additive (c) to the compound (a) is a molar ratio [(c) :( a)] and is usually 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1.
メタセシス触媒の使用量は、上記化合物(a)と環状オレフィンとのモル比〔(a):環状オレフィン〕が通常1:500〜1:50,000、好ましくは1:1,000〜1
:10,000となる量である。
The amount of the metathesis catalyst used is such that the molar ratio of the compound (a) to the cyclic olefin [(a): cyclic olefin] is usually 1: 500 to 1: 50,000, preferably 1: 1,000 to 1.
: An amount of 10,000.
<重合反応用溶媒>
開環(共)重合反応において、溶媒は、後述する分子量調節剤溶液を構成する溶媒や、環状オレフィンおよび/またはメタセシス触媒の溶媒として使用される。このような溶媒としては、たとえば、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカンなどのアルカン類;シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナンなどのシクロアルカン類;ベンゼン、トルエン、キシレン、エチルベンゼン、クメンなどの芳香族炭化水素;クロロブタン、ブロモヘキサン、塩化メチレン、ジクロロエタン、ヘキサメチレンジブロミド、クロロホルム、テトラクロロエチレンなどのハロゲン化アルカン;クロロベンゼンなどのハロゲン化アリール;酢酸エチル、酢酸n−ブチル、酢酸iso−ブチル、プロピオン酸メチル、ジメトキシエタンなどの飽和カルボン酸エステル類;ジブチルエーテル、テトラヒドロフラン、ジメトキシエタンなどのエーテル類などを挙げることができる。これらの溶媒は単独であるいは混合して用いることができる。これらのうち、芳香族炭化水素が好ましい。
<Solvent for polymerization reaction>
In the ring-opening (co) polymerization reaction, the solvent is used as a solvent constituting a molecular weight modifier solution described later, a solvent for a cyclic olefin and / or a metathesis catalyst. Examples of such a solvent include alkanes such as pentane, hexane, heptane, octane, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, toluene, xylene, ethylbenzene, Aromatic hydrocarbons such as cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene; aryl halides such as chlorobenzene; ethyl acetate, n-butyl acetate, iso- Saturated carboxylic acid esters such as butyl, methyl propionate, and dimethoxyethane; and ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane. That. These solvents can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.
溶媒の使用量は、溶媒と環状オレフィンとの重量比(溶媒:環状オレフィン)が、通常1:1〜10:1、好ましくは1:1〜5:1となる量が望ましい。
<分子量調節剤>
得られる開環(共)重合体の分子量は、重合温度、触媒の種類、溶媒の種類によって調節することも可能であるが、分子量調節剤を共存させることによっても調節できる。
The amount of the solvent used is desirably such that the weight ratio of the solvent to the cyclic olefin (solvent: cyclic olefin) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.
<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but can also be adjusted by coexisting a molecular weight regulator.
好適な分子量調節剤としては、たとえば、エチレン、プロペン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセンなどのα−オレフィン類およびスチレンを挙げることができ、これらのうち、1−ブテン、1−ヘキセンが特に好ましい。また、これらの分子量調節剤は、単独であるいは2種以上を混合して用いることができる。 Suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene. Of these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more.
分子量調節剤の使用量は、開環重合反応に供される環状オレフィン1モルに対して、通常0.005〜0.6モル、好ましくは0.01〜0.5モルである。
上記開環共重合体は、環状オレフィンと共重合性単量体とを開環共重合させて得ることができるが、さらに、ポリブタジエン、ポリイソプレンなどの共役ジエン化合物、スチレン−ブタジエン共重合体、エチレン−非共役ジエン共重合体、ポリノルボルネンなどの主鎖に炭素−炭素間二重結合を2つ以上含む不飽和炭化水素系ポリマーなどの存在下で環状オレフィンを開環共重合させてもよい。
The usage-amount of a molecular weight regulator is 0.005-0.6 mol normally with respect to 1 mol of cyclic olefins used for ring-opening polymerization reaction, Preferably it is 0.01-0.5 mol.
The ring-opening copolymer can be obtained by ring-opening copolymerization of a cyclic olefin and a copolymerizable monomer, and further includes conjugated diene compounds such as polybutadiene and polyisoprene, styrene-butadiene copolymer, Cyclic olefins may be subjected to ring-opening copolymerization in the presence of an unsaturated hydrocarbon polymer containing two or more carbon-carbon double bonds in the main chain such as an ethylene-nonconjugated diene copolymer or polynorbornene. .
(3)水素添加(共)重合体
上記開環(共)重合体は、そのままでも用いることができるが、さらにこれに水素添加して得られる水素添加(共)重合体(3)は、耐衝撃性に優れた樹脂として有用である。
(3) Hydrogenated (co) polymer The above ring-opening (co) polymer can be used as it is, but the hydrogenated (co) polymer (3) obtained by further hydrogenation to this has a resistance to resistance. It is useful as a resin having excellent impact properties.
水素添加反応は、通常の方法、すなわち開環(共)重合体を含む溶液に水素添加触媒を添加し、これに常圧〜300気圧、好ましくは3〜200気圧の水素ガスを0〜200℃、好ましくは20〜180℃で作用させて行うことができる。 In the hydrogenation reaction, a hydrogenation catalyst is added to an ordinary method, that is, a solution containing a ring-opening (co) polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C. The reaction can be carried out preferably at 20 to 180 ° C.
<水素添加触媒>
上記水素添加触媒としては、通常のオレフィン性化合物の水素添加反応に用いられる触媒を使用することができる。この水素添加触媒としては、不均一系触媒および均一系触媒が挙げられる。
<Hydrogenation catalyst>
As said hydrogenation catalyst, the catalyst used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.
不均一系触媒としては、パラジウム、白金、ニッケル、ロジウム、ルテニウムなどの貴
金属触媒物質を、カーボン、シリカ、アルミナ、チタニアなどの担体に担持させた固体触媒を挙げることができる。均一系触媒としては、ナフテン酸ニッケル/トリエチルアルミニウム、ニッケルアセチルアセトナート/トリエチルアルミニウム、オクテン酸コバルト/n−ブチルリチウム、チタノセンジクロリド/ジエチルアルミニウムモノクロリド、酢酸ロジウム、クロロトリス(トリフェニルホスフィン)ロジウム、ジクロロトリス(トリフェニルホスフィン)ルテニウム、クロロヒドロカルボニルトリス(トリフェニルホスフィン)ルテニウム、ジクロロカルボニルトリス(トリフェニルホスフィン)ルテニウムなどを挙げることができる。これらの触媒の形態は、粉末でも粒状でもよい。
Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichloro Examples thereof include tris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of these catalysts may be powder or granular.
これらの水素添加触媒は、開環(共)重合体と水素添加触媒との重量比(開環(共)重合体:水素添加触媒)が、1:1×10-6〜1:2となる割合で使用することが好ましい。 In these hydrogenation catalysts, the weight ratio of the ring-opening (co) polymer to the hydrogenation catalyst (ring-opening (co) polymer: hydrogenation catalyst) is 1: 1 × 10 −6 to 1: 2. It is preferable to use in proportions.
上記水素添加(共)重合体(3)は、優れた熱安定性を有し、成形加工時や製品として使用する際の加熱によっても、その特性が劣化することはない。
水素添加(共)重合体(3)の水素添加率は、1H−NMRにより500MHzの条件
で測定した値が、通常50%以上、好ましく70%以上、より好ましくは90%以上、特に好ましくは98%以上、最も好ましくは99%以上である。水素添加率が高いほど、熱や光に対する安定性が優れ、長期にわたって安定した特性を有する導光体などの成形品を得ることができる。
The hydrogenated (co) polymer (3) has excellent thermal stability, and its characteristics are not deteriorated even by heating during molding or use as a product.
The hydrogenation rate of the hydrogenated (co) polymer (3) is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably measured by 1 H-NMR under the condition of 500 MHz. 98% or more, most preferably 99% or more. The higher the hydrogenation rate, the better the stability to heat and light, and it is possible to obtain a molded article such as a light guide having stable characteristics over a long period of time.
また、上記水素添加(共)重合体(3)は、ゲル含有量が5重量%以下であることが好ましく、特に1重量%以下であることが好ましい。
(4)水素添加(共)重合体
水素添加(共)重合体(4)は、上記(1)または(2)の開環(共)重合体をフリーデルクラフト反応により環化したのち、水素添加することにより得られる。
The hydrogenated (co) polymer (3) preferably has a gel content of 5% by weight or less, particularly preferably 1% by weight or less.
(4) Hydrogenated (co) polymer The hydrogenated (co) polymer (4) is obtained by cyclizing the ring-opened (co) polymer of the above (1) or (2) by Friedel-Craft reaction. It is obtained by adding.
上記開環(共)重合体をフリーデルクラフト反応により環化する方法は、特に限定されず、たとえば、特開昭50−154399号公報に記載の酸性化合物を用いた公知の方法が採用できる。 The method for cyclizing the ring-opened (co) polymer by Friedel-Craft reaction is not particularly limited, and for example, a known method using an acidic compound described in JP-A No. 50-154399 can be employed.
上記酸性化合物として具体的には、AlCl3、BF3、FeCl3、Al2O3、HCl
、CH3ClCOOH、ゼオライト、活性白土などのルイス酸、ブレンステッド酸が挙げ
られる。
Specific examples of the acidic compound include AlCl 3 , BF 3 , FeCl 3 , Al 2 O 3 , HCl
, CH 3 ClCOOH, zeolite, Lewis acid such as activated clay, and Bronsted acid.
環化された開環(共)重合体は、上記(3)の水素添加反応と同様にして、水素添加することができる。
(5)飽和共重合体
飽和共重合体(5)は、付加重合触媒の存在下で、上記環状オレフィンに不飽和二重結合含有化合物を付加重合させることにより得られる。付加重合法は従来公知の方法を適用できる。
The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the hydrogenation reaction of (3) above.
(5) Saturated copolymer The saturated copolymer (5) can be obtained by addition polymerization of an unsaturated double bond-containing compound to the cyclic olefin in the presence of an addition polymerization catalyst. A conventionally known method can be applied to the addition polymerization method.
<不飽和二重結合含有化合物>
不飽和二重結合含有化合物としては、たとえば、エチレン、プロピレン、ブテンなどのオレフィン系化合物を挙げることができ、これらのうち、炭素数が好ましくは2〜12、さらに好ましくは2〜8のオレフィン系化合物が望ましい。
<Unsaturated double bond-containing compound>
Examples of the unsaturated double bond-containing compound include olefinic compounds such as ethylene, propylene, and butene. Among these, olefinic compounds having preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Compounds are desirable.
不飽和二重結合含有化合物の使用量は、環状オレフィンと不飽和二重結合含有化合物との重量比(環状オレフィン/不飽和二重結合含有化合物)で、90/10〜40/60が好ましく、85/15〜50/50がより好ましい。ただし、環状オレフィンと不飽和二
重結合含有化合物との合計重量を100とする。
The use amount of the unsaturated double bond-containing compound is preferably 90/10 to 40/60 in terms of the weight ratio of the cyclic olefin to the unsaturated double bond-containing compound (cyclic olefin / unsaturated double bond-containing compound). 85/15 to 50/50 is more preferable. However, the total weight of the cyclic olefin and the unsaturated double bond-containing compound is 100.
<付加重合触媒>
付加重合触媒としては、チタン化合物、ジルコニウム化合物およびバナジウム化合物から選ばれる少なくとも一種の化合物と、助触媒として有機アルミニウム化合物との組み合わせが挙げられる。
<Addition polymerization catalyst>
Examples of the addition polymerization catalyst include a combination of at least one compound selected from a titanium compound, a zirconium compound, and a vanadium compound, and an organoaluminum compound as a co-catalyst.
上記チタン化合物としては、四塩化チタン、三塩化チタンなどを挙げることができ、ジルコニウム化合物としては、ビス(シクロペンタジエニル)ジルコニウムクロリド、ビス(シクロペンタジエニル)ジルコニウムジクロリドなどを挙げることができ、バナジウム化合物としては、下記式
VO(OR)aXb、またはV(OR)cXd
〔ただし、Rは炭化水素基、Xはハロゲン原子であって、0≦a≦3、0≦b≦3、2≦(a+b)≦3、0≦c≦4、0≦d≦4、3≦(c+d)≦4である。〕
で表されるバナジウム化合物、あるいはこれらの電子供与付加物が挙げられる。
Examples of the titanium compound include titanium tetrachloride and titanium trichloride. Examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride. As the vanadium compound, the following formula VO (OR) a X b or V (OR) c X d
[Wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3, ≦ (c + d) ≦ 4. ]
Or an electron-donating adduct of these compounds.
上記電子供与体としては、アルコール、フェノール類、ケトン、アルデヒド、カルボン酸、有機酸または無機酸のエステル、エーテル、酸アミド、酸無水物、アルコキシシランなどの含酸素電子供与体、アンモニア、アミン、ニトリル、イソシアナートなどの含窒素電子供与体などが挙げられる。 Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.
上記有機アルミニウム化合物としては、アルミニウム−炭素結合またはアルミニウム−水素結合を少なくとも1つ有する化合物が挙げられる。この有機アルミニウム化合物は、単独で用いても、2種以上を併用してもよい。 Examples of the organoaluminum compound include compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond. These organoaluminum compounds may be used alone or in combination of two or more.
チタン化合物、ジルコニウム化合物およびバナジウム化合物から選ばれる化合物の使用量(2種以上を併用する場合はそれらの合計量)と有機アルミニウム化合物の使用量との割合は、チタン原子等に対するアルミニウム原子の比(Al/Ti等)で、通常2以上、好ましくは2〜50、特に好ましくは3〜20である。 The ratio of the amount used of a compound selected from a titanium compound, a zirconium compound and a vanadium compound (the total amount when two or more are used together) and the amount of the organoaluminum compound used is the ratio of aluminum atoms to titanium atoms ( Al / Ti etc.), usually 2 or more, preferably 2 to 50, particularly preferably 3 to 20.
上記付加重合反応において用いられる溶媒としては、上記開環(共)重合反応において例示した溶媒を挙げることができる。
また、飽和共重合体(5)の分子量の調節は、通常、水素を用いて行うことができる。
Examples of the solvent used in the addition polymerization reaction include the solvents exemplified in the ring-opening (co) polymerization reaction.
Moreover, the molecular weight of the saturated copolymer (5) can be usually adjusted using hydrogen.
(6)付加型(共)重合体およびその水素添加(共)重合体
付加型(共)重合体(6)は、上記環状オレフィンに、ビニル系環状炭化水素系単量体およびシクロペンタジエン系単量体から選ばれる1種以上の単量体を付加重合させることにより得られる。
(6) Addition type (co) polymer and hydrogenated (co) polymer thereof The addition type (co) polymer (6) is obtained by adding a vinyl cyclic hydrocarbon monomer and a cyclopentadiene monomer to the cyclic olefin. It can be obtained by addition polymerization of one or more monomers selected from monomers.
<ビニル系環状炭化水素系単量体>
上記ビニル系環状炭化水素系単量体としては、たとえば、4−ビニルシクロペンテン、2−メチル−4−イソプロペニルシクロペンテンなどのビニルシクロペンテン系単量体;4−ビニルシクロペンタン、4−イソプロペニルシクロペンタン等のビニルシクロペンタン系単量体などのビニル化5員環炭化水素系単量体;4−ビニルシクロヘキセン、4−イソプロペニルシクロヘキセン、1−メチル−4−イソプロペニルシクロヘキセン、2−メチル−4−ビニルシクロヘキセン、2−メチル−4−イソプロペニルシクロヘキセンなどのビニルシクロヘキセン系単量体;4−ビニルシクロヘキサン、2−メチル−4−イソプロペニルシクロヘキサンなどのビニルシクロヘキサン系単量体;スチレン、α―メチルスチレン、2−メチルスチレン、3−メチルスチレン、4−メチルスチレン、1−ビニルナフタレン、2−ビニルナフタレン、4−フェニルスチレン、p−メトキシスチレンなどの
スチレン系単量体;d−テルペン、1−テルペン、ジテルペン、d−リモネン、1−リモネン、ジペンテンなどのテルペン系単量体;4−ビニルシクロヘプテン、4−イソプロペニルシクロヘプテンなどのビニルシクロヘプテン系単量体;4−ビニルシクロヘプタン、4−イソプロペニルシクロヘプタン等のビニルシクロヘプタン系単量体などが挙げられる。これらの単量体のうち、スチレン、α−メチルスチレンが好ましい。また、これらの単量体は、1種単独で用いても、2種以上を併用してもよい。
<Vinyl cyclic hydrocarbon monomer>
Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene; 4-vinylcyclopentane and 4-isopropenylcyclopentane. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers such as 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4- Vinylcyclohexene monomers such as vinylcyclohexene and 2-methyl-4-isopropenylcyclohexene; Vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane; Styrene, α-methylstyrene 2-methylstyrene, -Styrene monomers such as methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene; d-terpene, 1-terpene, diterpene, d-limonene, Terpene monomers such as 1-limonene and dipentene; Vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene; 4-vinylcycloheptane and 4-isopropenylcycloheptane And vinylcycloheptane-based monomers. Of these monomers, styrene and α-methylstyrene are preferred. Moreover, these monomers may be used individually by 1 type, or may use 2 or more types together.
<シクロペンタジエン系単量体>
上記シクロペンタジエン系単量体としては、たとえば、シクロペンタジエン、1−メチルシクロペンタジエン、2−メチルシクロペンタジエン、2−エチルシクロペンタジエン、5−メチルシクロペンタジエン、5,5−メチルシクロペンタジエンなどが挙げられる。これらの単量体のうち、シクロペンタジエンが好ましい。また、これらの単量体は、1種単独で用いても、2種以上を併用してもよい。
<Cyclopentadiene monomer>
Examples of the cyclopentadiene monomer include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-methylcyclopentadiene, and the like. . Of these monomers, cyclopentadiene is preferred. Moreover, these monomers may be used individually by 1 type, or may use 2 or more types together.
上記付加重合反応は、上記(5)における付加重合反応と同様にして実施することができる。
上記付加型(共)重合体(6)の水素添加(共)重合体は、上記付加型(共)重合体(6)を、上記(3)と同様の方法により水素添加することにより得ることができる。
The addition polymerization reaction can be carried out in the same manner as the addition polymerization reaction in (5) above.
The hydrogenated (co) polymer of the addition type (co) polymer (6) is obtained by hydrogenating the addition type (co) polymer (6) in the same manner as in the above (3). Can do.
(7)交互共重合体
交互共重合体(7)は、ルイス酸等の存在下で上記環状オレフィンとアクリレートとをラジカル重合させることにより得られる。
(7) Alternating copolymer The alternating copolymer (7) is obtained by radical polymerization of the cyclic olefin and acrylate in the presence of a Lewis acid or the like.
<アクリレート>
上記アクリレートとしては、たとえば、メチルアクリレート、2−エチルヘキシルアクリレート、シクロヘキシルアクリレートなどの炭素数1〜20の直鎖状、分岐状または環状アルキルアクリレート;グリシジルアクリレート、2−テトラヒドロフルフリルアクリレートなどの炭素原子数2〜20の複素環基含有アクリレート;ベンジルアクリレートなどの炭素原子数6〜20の芳香族環基含有アクリレート;イソボロニルアクリレート、ジシクロペンタニルアクリレートなどの炭素数7〜30の多環構造を有するアクリレートが挙げられる。
<Acrylate>
Examples of the acrylate include linear, branched or cyclic alkyl acrylates having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate; carbon atoms such as glycidyl acrylate and 2-tetrahydrofurfuryl acrylate. An acrylate having 2 to 20 heterocyclic groups; an acrylate having 6 to 20 carbon atoms such as benzyl acrylate; a polycyclic structure having 7 to 30 carbon atoms such as isobornyl acrylate and dicyclopentanyl acrylate The acrylate which has.
上記環状オレフィンとアクリレートとの割合は、これらの合計を100モルとして、通常、環状オレフィンが30〜70モル、アクリレートが70〜30モルであり、好ましくは、環状オレフィンが40〜60モル、アクリレートが60〜40モルであり、特に好ましくは、環状オレフィンが45〜55モル、アクリレートが55〜45モルである。 The ratio of the cyclic olefin to the acrylate is generally 30 to 70 mol of cyclic olefin and 70 to 30 mol of acrylate, preferably 40 to 60 mol of cyclic olefin, and acrylate It is 60-40 mol, Most preferably, a cyclic olefin is 45-55 mol, and an acrylate is 55-45 mol.
上記ルイス酸の使用量は、アクリレート100モルに対して0.001〜1モルが好ましい。
また、フリーラジカルを発生する公知の有機過酸化物またはアゾビス系のラジカル重合開始剤を用いることもできる。
As for the usage-amount of the said Lewis' acid, 0.001-1 mol is preferable with respect to 100 mol of acrylates.
In addition, known organic peroxides or azobis-based radical polymerization initiators that generate free radicals can also be used.
重合反応温度は、通常−20℃〜80℃、好ましくは5℃〜60℃である。また、重合反応用溶媒としては、上記開環(共)重合反応において例示した溶媒を挙げることができる。 The polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. Moreover, as a solvent for polymerization reaction, the solvent illustrated in the said ring-opening (co) polymerization reaction can be mentioned.
なお、本発明における「交互共重合体」とは、環状オレフィンに由来する構造単位同士が隣接しない共重合体、すなわち、環状オレフィンに由来する構造単位の隣には必ずアクリレートに由来する構造単位が結合している共重合体を意味する。ただし、アクリレート由来の構造単位同士は隣接して存在していてもよい。 The “alternate copolymer” in the present invention is a copolymer in which structural units derived from cyclic olefins are not adjacent to each other, that is, a structural unit derived from acrylate is always adjacent to a structural unit derived from cyclic olefin. It means a copolymer that is bonded. However, the acrylate-derived structural units may be present adjacent to each other.
本発明に用いられる環状オレフィン系樹脂の固有粘度〔ηinh〕は、0.2〜5dl/
gが好ましく、0.3〜3dl/gがさらに好ましく、0.4〜1.5dl/gが特に好ましい。また、テトラヒドロフランを溶媒として、ゲルパーミエーションクロマトグラフィー(GPC、カラム:東ソー(株)製TSKgel G7000HXL×1、TSKgel GMHXL×2およびTSKgel G2000HXL×1の4本を直列に接続した。)で測定されるポリスチレン換算の分子量は、数平均分子量(Mn)が好ましくは8,000〜100,000、さらに好ましくは10,000〜80,000、特に好ましくは12,000〜50,000であり、重量平均分子量(Mw)が好ましくは20,000〜300,000、さらに好ましくは30,000〜250,000、特に好ましくは40,000〜200,000である。
The intrinsic viscosity [η inh ] of the cyclic olefin resin used in the present invention is 0.2 to 5 dl /
g is preferable, 0.3 to 3 dl / g is more preferable, and 0.4 to 1.5 dl / g is particularly preferable. In addition, it was measured by gel permeation chromatography (GPC, column: TSKgel G7000HXL × 1, TSKgel GMHXL × 2 and TSKgel G2000HXL × 1 connected in series) using tetrahydrofuran as a solvent. The molecular weight in terms of polystyrene is preferably a number average molecular weight (Mn) of 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and a weight average molecular weight. (Mw) is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably 40,000 to 200,000.
固有粘度〔ηinh〕、数平均分子量(Mn)および重量平均分子量(Mw)が上記範囲
にある環状オレフィン系樹脂は、成形加工性に優れ、この樹脂によれば、耐熱性、耐水性、耐薬品性および機械的特性に優れた成形品が得られる。
Cyclic olefin resins having intrinsic viscosity [η inh ], number average molecular weight (Mn) and weight average molecular weight (Mw) in the above ranges are excellent in moldability, and according to this resin, heat resistance, water resistance, A molded product having excellent chemical properties and mechanical properties can be obtained.
また、上記環状オレフィン系樹脂のガラス転移温度(Tg)は、通常120℃以上、好ましくは120〜350℃、さらに好ましくは120〜250℃、特に好ましくは130〜200℃である。Tgが上記範囲にある環状オレフィン系樹脂は、高温条件下での使用や、コーティングおよび印刷などの加熱を伴う二次加工においても変形しにくく、また、成形加工性に優れ、成形加工時の熱による劣化も起こりにくい。 Moreover, the glass transition temperature (Tg) of the said cyclic olefin resin is 120 degreeC or more normally, Preferably it is 120-350 degreeC, More preferably, it is 120-250 degreeC, Most preferably, it is 130-200 degreeC. Cyclic olefin resins having a Tg in the above range are less likely to be deformed even when used under high temperature conditions or during secondary processing involving heating such as coating and printing, and have excellent moldability and heat during molding. Deterioration due to is difficult to occur.
また、本発明では、下記式(5)で示される修正Crossモデルにより溶融粘度を表した
ときの指数定数nが0.3以上0.5以下である環状オレフィン系樹脂が用いられる。
なお、一般に、熱可塑性樹脂は、剪断速度によって見かけの粘度が変化する非ニュートン性の流体である。このような非ニュートン性流体の粘度特性を記述するため、いくつかのレオロジーモデルが提唱されているが、ここでは下記式(5)で定義される修正Cross
モデルを用いる。
In the present invention, a cyclic olefin resin having an exponential constant n of 0.3 or more and 0.5 or less when melt viscosity is expressed by a modified Cross model represented by the following formula (5) is used.
In general, a thermoplastic resin is a non-Newtonian fluid whose apparent viscosity changes depending on the shear rate. Several rheological models have been proposed to describe the viscosity characteristics of such non-Newtonian fluids. Here, the modified cross defined by the following equation (5) is used.
Use the model.
本発明に用いる環状オレフィン系樹脂は、剪断速度に対して溶融粘度の変化がある程度大きいことが特徴である。この特性は上記式(5)中の指数定数nの値で表され、nの値
が大きいほど、剪断速度に対して溶融粘度の変化が大きいことを意味する。
The cyclic olefin resin used in the present invention is characterized in that the change in melt viscosity with respect to the shear rate is large to some extent. This characteristic is represented by the value of the index constant n in the above formula (5), and the larger the value of n, the greater the change in melt viscosity with respect to the shear rate.
本発明に用いる環状オレフィン系樹脂は、nが0.3以上、0.5以下である。nが0.3未満
であると、射出成形時に薄肉部での流動性が不足し、レンズの面精度を光学設計内に収めた場合、レンズ部となる厚肉部に局所歪が発生するとともに、流動末端でのバリの発生が生ずることがある。また、nが0.5を越えると、レンズ金型キャビティー内の充填圧力が不足し、レンズの面精度を維持することが著しく困難となる場合がある。したがって、上記のような形状を有する薄型の光学レンズの製造には、nが上記範囲にある環状オレフィン系樹脂が好適に用いられる。
In the cyclic olefin resin used in the present invention, n is 0.3 or more and 0.5 or less. When n is less than 0.3, the fluidity in the thin part is insufficient during injection molding, and when the lens surface accuracy is kept within the optical design, local distortion occurs in the thick part that becomes the lens part, and Generation of burrs at the ends may occur. On the other hand, if n exceeds 0.5, the filling pressure in the lens mold cavity is insufficient, and it may be extremely difficult to maintain the surface accuracy of the lens. Therefore, for the production of a thin optical lens having the above-described shape, a cyclic olefin resin having n in the above range is preferably used.
本発明に用いる環状オレフィン系樹脂は、射出成形の前に、予め、公知の方法で溶存する水分や酸素成分を除去することが好ましい。この際、熱風乾燥機、除湿乾燥機、窒素循環式乾燥機、除湿窒素循環式乾燥機、真空乾燥機など、公知の乾燥装置が用いられる。これらの乾燥装置のうち、色相均一性を有する成型品が得られやすい点で、減圧乾燥機、または窒素などの不活性ガスを循環させる乾燥機を使用することが好ましい。 It is preferable that the cyclic olefin resin used in the present invention removes water and oxygen components dissolved by a known method in advance before injection molding. At this time, a known drying device such as a hot air dryer, a dehumidifying dryer, a nitrogen circulating dryer, a dehumidifying nitrogen circulating dryer, or a vacuum dryer is used. Among these dryers, it is preferable to use a vacuum dryer or a dryer that circulates an inert gas such as nitrogen because a molded product having hue uniformity is easily obtained.
乾燥温度および乾燥時間は特に限定されるものではないが、通常Tg−100℃〜Tg−20℃で、通常2〜6時間乾燥される。
2.光学レンズ成形体
本発明の光学レンズは、鍔部とレンズ部とが、凹部を介して結合しており、直径が10mm以下である。
Although a drying temperature and drying time are not specifically limited, Usually, it is dried at Tg-100 degreeC-Tg-20 degreeC for 2 to 6 hours normally.
2. Optical Lens Molded Body In the optical lens of the present invention, the collar portion and the lens portion are coupled via a recess, and the diameter is 10 mm or less.
図5は、本発明の光学レンズにおいて、レンズ部を垂直方向から見た外観図である。図5に示すように、本発明の光学レンズは、鍔部、凹部および光の光路となるレンズ部を有する。なお、上記鍔部は、レンズ部外部に設けられた、レンズを保持する部位をいい、レンズ部の保持および組み立て時のレンズの固定、レンズ間隔の保持に利用できる。上記凹部は鍔部とレンズ部の間の薄肉部をいう。また、上記直径とは、図5のように光学レンズを点線で補って円としたとき、この円の直径をいう。 FIG. 5 is an external view of the lens portion viewed from the vertical direction in the optical lens of the present invention. As shown in FIG. 5, the optical lens of the present invention has a collar portion, a concave portion, and a lens portion that serves as an optical path of light. Note that the collar portion is a portion that is provided outside the lens portion and holds the lens, and can be used for holding the lens portion, fixing the lens during assembly, and holding the lens interval. The said recessed part says the thin part between a collar part and a lens part. Further, the diameter means the diameter of this circle when the optical lens is complemented with a dotted line as shown in FIG.
上記光学レンズの断面形状は特に限定されず、図6−1〜6−6に例示したように、球面、非球面の凹状、凸状などであってもよい。なお、図6−1〜6−6は、図5における線Aに沿った断面図である。 The cross-sectional shape of the optical lens is not particularly limited, and may be spherical, aspherical concave, convex, or the like as illustrated in FIGS. FIGS. 6-1 to 6-6 are cross-sectional views taken along line A in FIG.
また、本発明の光学レンズは、上記鍔部の厚みが0.5mm以下、上記凹部の厚みが該鍔部
の厚み以下、かつ0.4mm以下である。ここで、上記鍔部の厚みはレンズ端部の位置で測定
した値を意味する。上記凹部は、レンズ部と鍔部の間に位置し、鍔部からレンズ部の方向に見た場合、鍔部よりも薄肉の部分である。上記凹部は、その薄肉部の厚みが最も薄くなる位置で測定した値を意味する。
In the optical lens of the present invention, the thickness of the collar portion is 0.5 mm or less, and the thickness of the concave portion is equal to or less than the thickness of the collar portion and 0.4 mm or less. Here, the thickness of the collar portion means a value measured at the position of the lens end portion. The concave portion is located between the lens portion and the heel portion, and is a thinner portion than the ridge portion when viewed from the heel portion toward the lens portion. The said recessed part means the value measured in the position where the thickness of the thin part becomes the thinnest.
レンズ部の厚みの最大値が0.8mm以下であることが好ましい。このような薄型の光学レンズは、鍔部および凹部も薄い。したがって、本発明の光学レンズによれば、レンズユニットの厚みを薄くできるため、携帯電話などに搭載するカメラ機器の薄型化に有効である。 It is preferable that the maximum thickness of the lens portion is 0.8 mm or less. Such a thin optical lens has thin ridges and recesses. Therefore, according to the optical lens of the present invention, the thickness of the lens unit can be reduced, which is effective in reducing the thickness of a camera device mounted on a mobile phone or the like.
3.金型装置
本発明において、上記環状オレフィン系樹脂を射出成形する際に用いる金型装置では、図1(a)に示すように、キャビティーとゲートとが、ゲート開口部を介して結合している。上記キャビティーは、光学レンズ成形体に対応する形状を有しており、光学レンズ成形体の鍔部、凹部およびレンズ部それぞれに対応する空間部を有する。また、上記金型装置において、上記ゲートは、キャビティーとランナー(図示せず)とを接合している。
3. Mold apparatus In the present invention, in the mold apparatus used when the above cyclic olefin-based resin is injection-molded, as shown in FIG. 1 (a), the cavity and the gate are coupled via the gate opening. Yes. The cavity has a shape corresponding to the optical lens molded body, and has a space portion corresponding to each of the flange portion, the concave portion, and the lens portion of the optical lens molded body. In the mold apparatus, the gate joins a cavity and a runner (not shown).
図1(b)に示すように、本発明に用いる金型装置において、上記ゲート開口部における上記キャビティーの高さ方向のゲートの厚みt1と、上記ゲート開口部における上記キ
ャビティーの高さ方向の鍔部の厚みt2とが、下記式(1)を満たし、かつ、上記ゲート
が、上記ゲート開口部に向かって、上記キャビティーの高さ方向の一方が狭まっており、該高さ方向に狭まる傾斜角度βが、下記式(2)を満たすことを特徴とする。
As shown in FIG. 1B, in the mold apparatus used in the present invention, the gate thickness t 1 in the height direction of the cavity in the gate opening and the height of the cavity in the gate opening. The thickness t 2 of the ridge portion in the direction satisfies the following formula (1), and the gate is narrowed at one side in the height direction of the cavity toward the gate opening. The inclination angle β narrowed in the direction satisfies the following formula (2).
t2×0.1≦t1≦t2×0.8 (1)
20°≦β≦60° (2)
t1がt2×0.1よりも小さいと、光学レンズ成形体の面精度が劣ることがあり、t1
がt2×0.8よりも大きいと、光学レンズ成形体内に局所的な光学歪が発生しやすい。
また、βが20°より小さいと、光学レンズ成形体内に局所的な光学歪みが発生しやすく、βが60°より大きいと、光学レンズ成形体の面精度が劣るとともに、フローマークが発生することがある。
t 2 × 0.1 ≦ t 1 ≦ t 2 × 0.8 (1)
20 ° ≦ β ≦ 60 ° (2)
If t 1 is smaller than t 2 × 0.1, the surface accuracy of the optical lens molded body may be inferior, and t 1
Is larger than t 2 × 0.8, local optical distortion tends to occur in the optical lens molded body.
Further, if β is smaller than 20 °, local optical distortion is likely to occur in the optical lens molded body, and if β is larger than 60 °, the surface accuracy of the optical lens molded body is inferior and a flow mark is generated. There is.
上記ゲートは、図2に示すように、上記ゲート開口部に向かって、上記キャビティーの幅方向の両方が均等に狭まっており、該幅方向に狭まる傾斜角度αが、下記式(3)を満たすことが好ましい。 As shown in FIG. 2, the gate is narrowed equally in both the width directions of the cavity toward the gate opening, and the inclination angle α narrowing in the width direction is expressed by the following formula (3). It is preferable to satisfy.
30°≦α≦60° (3)
または、上記ゲートは、図3に示すように、上記ゲート開口部に向かって、上記キャビティーの幅方向の両方が均等に広がっており、該幅方向に広がる傾斜角度αが、下記式(4)を満たすことが好ましい。
30 ° ≦ α ≦ 60 ° (3)
Alternatively, as shown in FIG. 3, both the width directions of the cavities spread uniformly toward the gate opening, and the inclination angle α spreading in the width direction is expressed by the following formula (4). ) Is preferably satisfied.
30°≦α≦60° (4)
上記式(3)および(4)のいずれの場合においても、αが30°より小さいと、光学レンズ成形体内に局所的な光学歪が発生することがあり、αが60°より大きいと、光学レンズ成形体の面精度が劣るとともに、フローマークが発生することがある。
30 ° ≦ α ≦ 60 ° (4)
In both cases of the above formulas (3) and (4), if α is smaller than 30 °, local optical distortion may occur in the optical lens molded body, and if α is larger than 60 °, the optical The surface accuracy of the lens molding may be inferior and a flow mark may be generated.
さらに、上記ゲートは、図4に示すように、フラット部を有し、該フラット部を介して上記キャビティーと結合しており、該フラット部の長さLが0.2〜2.0mmであることが好ましい。 Further, as shown in FIG. 4, the gate has a flat portion and is coupled to the cavity through the flat portion, and the length L of the flat portion is 0.2 to 2.0 mm. preferable.
Lが0.2mm未満の場合は、局所的な光学歪みを低減する効果が得られにくくなり、Lが2.0mmを越える場合は、面精度に劣るとともに、フローマークが発生しやすくなる。
なお、本発明により得られる成形品(光学レンズ成形体)は、上述したような形状を有するとともに、公知の材質を有する金型装置を用いて製造される。金型装置の好ましい材質としては、通常の炭素鋼、ステンレス鋼、またはこれらをベースにした公知の合金類が挙げられ、金型装置の表面に、焼き入れ処理、クロム、チタン、ダイヤモンドなどによる公知のコーティング処理、またはニッケル系金属、銅合金などによるパターン加工のための金属メッキを施してもよい。
When L is less than 0.2 mm, it is difficult to obtain the effect of reducing local optical distortion, and when L exceeds 2.0 mm, the surface accuracy is inferior and a flow mark is likely to occur.
In addition, the molded product (optical lens molded body) obtained by the present invention is manufactured using a mold apparatus having a shape as described above and having a known material. Preferred materials for the mold apparatus include ordinary carbon steel, stainless steel, or known alloys based on these, and the surface of the mold apparatus is known by quenching, chromium, titanium, diamond, etc. Alternatively, metal plating for patterning with a nickel-based metal or copper alloy may be applied.
また、集光や反射防止などを目的として成形品表面にパターンを形成する場合には、金型装置の金属コーティング面もしくは金属メッキ面、またはスタンパ表面に、放電加工機、切削加工機などの公知の加工機で直接パターンを形成してもよく、電鋳などの方法でパターンを形成してもよい。 In addition, when forming a pattern on the surface of a molded product for the purpose of collecting light or preventing reflection, a publicly known electric discharge machine, cutting machine or the like is formed on the metal coating surface or metal plating surface of the mold apparatus or the stamper surface. The pattern may be directly formed by a processing machine, or the pattern may be formed by a method such as electroforming.
さらに、射出成形における、金型装置内でのガス成分の圧縮による高温化に起因する樹脂の炭化や、金型装置内に滞留する揮発成分の凝縮防止を目的として、レンズのキャビティー周囲にガスベント機構を設けてもよい。通常ガスベントの厚みは、50〜150nmの深さ
で形成される。ガスベントはキャビティーの一部に設けてもよいが、ゲート部を除く全面に形成することも好ましい。また、このようなガスベントは、金型装置のゲート部、またはランナー部に形成してもよい。
Furthermore, in injection molding, a gas vent around the lens cavity is used to prevent carbonization of the resin due to high temperatures due to compression of gas components in the mold apparatus and to prevent condensation of volatile components that remain in the mold apparatus. A mechanism may be provided. Normally, the thickness of the gas vent is formed to a depth of 50 to 150 nm. The gas vent may be provided in a part of the cavity, but is preferably formed on the entire surface except the gate portion. Moreover, you may form such a gas vent in the gate part of a metal mold apparatus, or a runner part.
4.射出成形
本発明では、上記ゲートを有する金型装置により、上記環状オレフィン系樹脂を射出成形して、上記形状を有する光学レンズ成形体を製造する。
4). Injection Molding In the present invention, the cyclic olefin-based resin is injection-molded by the mold apparatus having the gate to produce an optical lens molded body having the shape.
射出成形に用いられる射出成形機は、上記金型装置を使用できれば特に限定されないが、たとえば、シリンダーの方式としてはインライン方式、プリプラ方式;駆動方式としては油圧式、電動式、ハイブリッド式;型締め方式としては直圧式、トグル式;射出方向としては横型、縦型などが挙げられる。また、型締め方式は射出圧縮できるものでもよい。シリンダー径および型締め力は目的の成形品の形状により決まるが、一般に成形品の投影面積が大きい場合は型締め力を大きくすることが好ましく、成形品の容量が大きい場合はシリンダー径の大きくすることが好ましい。 The injection molding machine used for the injection molding is not particularly limited as long as the above mold apparatus can be used. For example, the cylinder system is an inline system, a pre-plastic system; the drive system is a hydraulic system, an electric system, a hybrid system; Examples of the method include a direct pressure type and a toggle type; examples of the injection direction include a horizontal type and a vertical type. The mold clamping method may be one that can be injection-compressed. Cylinder diameter and clamping force are determined by the shape of the target molded product. Generally, it is preferable to increase the clamping force when the projected area of the molded product is large, and increase the cylinder diameter when the molded product has a large capacity. It is preferable.
シリンダーがインライン式の場合、圧縮比、長さ/直径の比、サブフライトの有無など
のスクリュー形状は適宜選択でき、スクリュー表面には、クロム系、チタン系、窒化物系、炭素系など、公知のコーティングを施してもよい。また、計量や射出動作の安定性を向上するためにスクリューの回転や圧力を制御する機構などを設けてもよい。また、シリンダー内や樹脂組成物を貯蔵するホッパー内を減圧にしたり、シリンダーおよびホッパーを窒素などの不活性ガスでシールしたりすることは、成形品が安定に得られるという観点から好ましい。
When the cylinder is an in-line type, the screw shape such as compression ratio, length / diameter ratio, subflight presence, etc. can be selected as appropriate, and the screw surface is known such as chromium, titanium, nitride, carbon, etc. The coating may be applied. Further, a mechanism for controlling the rotation and pressure of the screw may be provided in order to improve the stability of measurement and injection operation. Moreover, it is preferable from a viewpoint that a molded article can be obtained stably to reduce the pressure in the cylinder or the hopper for storing the resin composition, or to seal the cylinder and the hopper with an inert gas such as nitrogen.
射出成形の際、成形品のソリの低減や安定した連続成形のために、金型装置のキャビティー内を減圧する方法または射出圧縮方法が好適に用いられる。
金型装置のキャビティー内を減圧して射出成形する場合、減圧度は、ゲージ圧で、好ましくは−0.08MPa以下、さらに好ましくは−0.09MPa以下、特に好ましくは−0.1MPa以下である。上記範囲を超えると、減圧度が不足し、光透過性および光拡散性に優れた成形品を得られないことがある。
At the time of injection molding, a method of reducing the pressure in the cavity of the mold apparatus or an injection compression method is preferably used in order to reduce warpage of the molded product and stable continuous molding.
When injection molding is performed by reducing the pressure in the cavity of the mold apparatus, the degree of vacuum is a gauge pressure, preferably −0.08 MPa or less, more preferably −0.09 MPa or less, and particularly preferably −0.1 MPa or less. is there. When the above range is exceeded, the degree of reduced pressure is insufficient, and a molded article having excellent light transmittance and light diffusibility may not be obtained.
上記範囲の減圧度は、公知の方法、たとえば真空ポンプを使用して達成される。キャビティー周囲やエジェクター機構部などに、Oリングなどの公知のシール材を使用することが好ましく、成形品に不純物が混入しないなどの範囲で真空用のグリスなどを使用してもよい。また、真空ポンプ等の減圧装置と接続するための吸引口は、金型装置内の任意の場所に設ければよいが、通常、エジェクター機構部、スプルーおよびランナーの端部、入れ子構造部などに設けられる。また、真空吸引シーケンスは、金型装置の開閉に併せて電磁バルブなどで制御してもよく、常時運転してもよく、溶融樹脂の充填時に金型装置のキャビティー内を所望の減圧度にできる方法であれば特に制限されない。 The degree of vacuum in the above range is achieved using a known method such as a vacuum pump. It is preferable to use a known sealing material such as an O-ring around the cavity or the ejector mechanism, and vacuum grease or the like may be used as long as impurities are not mixed into the molded product. In addition, a suction port for connecting to a decompression device such as a vacuum pump may be provided at an arbitrary location in the mold device, but usually in the ejector mechanism, the end of the sprue and runner, the nested structure, etc. Provided. In addition, the vacuum suction sequence may be controlled by an electromagnetic valve or the like in conjunction with opening and closing of the mold apparatus, and may be operated at all times. There is no particular limitation as long as it can be performed.
金型装置のキャビティー内を減圧して射出成形する場合、キャビティーを閉じ減圧になった状態で溶融樹脂を射出するため、通常、射出遅延時間を設定する。射出遅延時間は、使用する真空ポンプの能力およびキャビティーサイズに依存するが、通常0.5〜3秒程度である。 When injection molding is performed by reducing the pressure in the cavity of the mold apparatus, the injection delay time is usually set in order to inject the molten resin with the cavity closed and the pressure reduced. The injection delay time depends on the capacity of the vacuum pump used and the cavity size, but is usually about 0.5 to 3 seconds.
一方、射出圧縮成形方法では、キャビティー間隔を成形品の厚みの1.5〜20倍に設定し、その隙間に溶融樹脂を射出し、シリンダー側で測定される樹脂の圧力を200〜2,000kgf/cm2の範囲に保持しながら、金型装置内の成形品面を圧縮し、キャビ
ティーの間隔を狭くすればよい。
On the other hand, in the injection compression molding method, the cavity interval is set to 1.5 to 20 times the thickness of the molded product, molten resin is injected into the gap, and the resin pressure measured on the cylinder side is 200 to 2, What is necessary is just to compress the molded product surface in a metal mold | die apparatus, narrowing the space | interval of a cavity, hold | maintaining in the range of 000 kgf / cm < 2 >.
また、金型装置のコアを成形品の厚みの1.1倍〜10倍に設定して可動状態とし、そこに溶融樹脂を射出して、射出開始あるいは射出終了後から、可動側コアを平均速度0.01mm/sec〜1mm/secで圧縮してもよい。 Further, the mold apparatus core is set to a movable state by setting the core to 1.1 to 10 times the thickness of the molded product, and the molten resin is injected therein, and after the injection starts or ends, the movable core is averaged. The compression may be performed at a speed of 0.01 mm / sec to 1 mm / sec.
これらの射出圧縮成形方法には、公知の成形機が用いられる。
射出成形のその他の条件は、特に限定されるものではないが、通常、シリンダー温度が260〜350℃、金型装置温度は、環状オレフィン系樹脂のガラス転移温度Tgに基づいて、通常Tg−1〜Tg−40℃、好ましくはTg−5〜Tg−25℃の範囲である。また、射出速度は、本発明の成形品の大きさや成形機のシリンダーサイズにより異なるが、たとえば、シリンダー径が28mmの場合、通常80mm/sec以上、好ましくは90〜250mm/secである。保圧では、成形品の形状が保持できる程度の最小圧・時間に適宜調整することが好ましい。
A known molding machine is used for these injection compression molding methods.
Other conditions for injection molding are not particularly limited, but the cylinder temperature is usually 260 to 350 ° C., and the mold apparatus temperature is usually Tg-1 based on the glass transition temperature Tg of the cyclic olefin resin. It is -Tg-40 degreeC, Preferably it is the range of Tg-5-Tg-25 degreeC. The injection speed varies depending on the size of the molded product of the present invention and the cylinder size of the molding machine. For example, when the cylinder diameter is 28 mm, it is usually 80 mm / sec or more, preferably 90 to 250 mm / sec. In the holding pressure, it is preferable to appropriately adjust the minimum pressure and time so that the shape of the molded product can be maintained.
[実施例]
以下、本発明を実施例により説明するが、本発明は、この実施例により何ら限定されるものではない。なお、以下において「部」および「%」は、特に断らない限り、「重量部」および「重量%」である。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified.
<環状オレフィン系樹脂の物性の測定方法>
また、環状オレフィン系樹脂の各種物性は以下の方法により測定した。
(屈折率)
環状オレフィン系樹脂を射出成形して40mm×60mm×3.2mmの平板を作製し、(Tg+5)℃で30分間アニールを行った。その後、さらに25℃、50RH%の環境下に1週間放置した後、25℃、50RH%の環境下で屈折率計(カールツァイスイエナ社製 PR−2)を用いて屈折率を測定した。
<Method for measuring physical properties of cyclic olefin resin>
Further, various physical properties of the cyclic olefin resin were measured by the following methods.
(Refractive index)
Cyclic olefin-based resin was injection-molded to prepare a 40 mm × 60 mm × 3.2 mm flat plate, and annealed at (Tg + 5) ° C. for 30 minutes. Thereafter, the sample was further left for 1 week in an environment of 25 ° C. and 50 RH%, and then the refractive index was measured using a refractometer (PR-2 manufactured by Carl Zeiss Jena) in an environment of 25 ° C. and 50 RH%.
(固有粘度:ηinh)
クロロホルムを溶媒として、重合体濃度0.5g/dlの試料を調製し、30℃の条件下でウベローデ粘度計にて測定した。
(Intrinsic viscosity: η inh )
A sample having a polymer concentration of 0.5 g / dl was prepared using chloroform as a solvent, and measured with an Ubbelohde viscometer at 30 ° C.
(分子量)
東ソー株式会社製HLC−8020ゲルパーミエーションクロマトグラフィー(GPC、カラム:東ソー(株)製TSKgel G7000HXL×1、TSKgel GMHXL×2およびTSKgel G2000HXL×1の4本を直列に接続した。)を用い、テトラヒドロフラン(THF)溶媒で測定し、ポリスチレン換算の重量平均分子量(Mw)および分子量分布(Mw/Mn)を求めた。なお、Mnはポリスチレン換算の数平均分子量を表す。
(Molecular weight)
Using Tosoh Corporation HLC-8020 gel permeation chromatography (GPC, column: TSKgel G7000HXL × 1, TSKgel GMHXL × 2 and TSKgel G2000HXL × 1 manufactured by Tosoh Corporation) were connected in series. It measured with the (THF) solvent and calculated | required the polystyrene conversion weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn). In addition, Mn represents the number average molecular weight of polystyrene conversion.
(ガラス転移温度:Tg)
セイコーインスツルメンツ社製DSC6200を用いて、昇温速度20℃/分、窒素気流下で測定した。
(Glass transition temperature: Tg)
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature was increased at a rate of temperature increase of 20 ° C./min under a nitrogen stream.
(溶融粘度)
ツインキャピラリーレオメータを用いて溶融粘度を測定した。測定温度を240度、260℃、280℃、300℃および320℃の中から任意に3点選び、それぞれの温度において、せん断
速度10〜10,000s-1の範囲で溶融粘度を測定した。測定したデータに基づき最小二乗法に
てフィッティングを行い(上記式(1))、係数および定数を決定した。
(Melt viscosity)
The melt viscosity was measured using a twin capillary rheometer. Three measurement temperatures were arbitrarily selected from 240 ° C., 260 ° C., 280 ° C., 300 ° C. and 320 ° C., and the melt viscosity was measured at a shear rate of 10 to 10,000 s −1 at each temperature. Fitting was performed by the least square method based on the measured data (the above formula (1)), and the coefficients and constants were determined.
<環状オレフィン系樹脂の合成>
[合成例1]
環状オレフィンとして8−メチル−8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン250部と、分子量調節剤として1−ヘキセン41部
と、開環重合反応用溶媒としてトルエン750部とを窒素置換した反応容器内に仕込み、
この溶液を60℃に加熱した。次いで、反応容器内の溶液に、トリエチルアルミニウムのトルエン溶液(濃度1.5モル/L)0.62部と、t−ブタノール/メタノールで変性した六塩化タングステン(t−ブタノール:メタノール:タングステン=0.35モル:0.3モル:1モル)のトルエン溶液(濃度0.05モル/L)3.7部とを添加し、この溶液を80℃で3時間加熱攪拌することにより開環重合反応させて、開環重合体を含む溶液を得た。
<Synthesis of cyclic olefin resin>
[Synthesis Example 1]
As a cyclic olefin, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 250 parts, 1-hexene 41 parts as a molecular weight regulator, and toluene 750 parts as a ring-opening polymerization reaction solvent were charged into a nitrogen-substituted reaction vessel,
The solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (concentration: 1.5 mol / L) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. .35 mol: 0.3 mol: 1 mol) of a toluene solution (concentration 0.05 mol / L) 3.7 parts was added, and this solution was heated and stirred at 80 ° C. for 3 hours to effect ring-opening polymerization reaction. To obtain a solution containing a ring-opening polymer.
この重合反応における重合転化率は97%であった。
このようにして得られた開環重合体の溶液4,000部をオートクレーブに仕込み、この開環重合体溶液に、RuHCl(CO)[P(C6H5)3]3を0.48部添加し、水素ガス圧100kg/cm2、反応温度165℃の条件下で3時間加熱攪拌することにより
水素添加反応を行った。得られた反応溶液(水素添加重合体を含む溶液)を冷却した後、水素ガスを放圧した。
The polymerization conversion rate in this polymerization reaction was 97%.
The autoclave was charged with 4,000 parts of the ring-opening polymer solution thus obtained, and 0.48 part of RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 was added to the ring-opening polymer solution. The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of hydrogen gas pressure of 100 kg / cm 2 and reaction temperature of 165 ° C. After cooling the obtained reaction solution (solution containing a hydrogenated polymer), the hydrogen gas was released.
次いで、この反応溶液を多量のメタノール中に注いで水素添加重合体を凝固させ、回収した。
その後、回収した水素添加重合体をトルエンに溶解して濃度20%の溶液を調製し、孔径1μmのフィルターでろ過した後、再度、多量のメタノール中に注いで水素添加重合体を凝固させ、回収した。この再溶解/析出/回収操作を3回繰り返し、最後に得られた水素添加重合体を、減圧下、100℃で12時間乾燥した後、溶融押出機を用いて造粒してペレットを得た。
Subsequently, this reaction solution was poured into a large amount of methanol to coagulate the hydrogenated polymer and collect it.
Thereafter, the recovered hydrogenated polymer is dissolved in toluene to prepare a solution having a concentration of 20%, filtered through a filter having a pore size of 1 μm, and then poured again into a large amount of methanol to coagulate and recover the hydrogenated polymer. did. This re-dissolution / precipitation / recovery operation was repeated three times, and the finally obtained hydrogenated polymer was dried at 100 ° C. under reduced pressure for 12 hours and then granulated using a melt extruder to obtain pellets. .
このようにして得られた水素添加重合体(以下、「環状オレフィン系樹脂1」という。)の水素添加率を1H−NMRにより400MHzの条件で測定した。水素添加率は実質的に100%であった。
The hydrogenation rate of the hydrogenated polymer thus obtained (hereinafter referred to as “
また、環状オレフィン系樹脂A1の28℃における屈折率は1.51、ηinhは0.5
2、Mwは75,000、Mw/Mnは3.5、Tgは164℃であった。
図7に示すように溶融粘度を測定し、フィッティングを行って定数を計算した。n=0.462、τ*=1.55×104、B=4.09×10-10、Tb=16920であった。
The refractive index of cyclic olefin-based resin A1 at 28 ° C. is 1.51, and η inh is 0.5.
2, Mw was 75,000, Mw / Mn was 3.5, and Tg was 164 ° C.
As shown in FIG. 7, the melt viscosity was measured and fitting was performed to calculate the constant. n = 0.462, τ * = 1.55 × 10 4 , B = 4.09 × 10 −10 , Tb = 16920.
[合成例2]
環状オレフィンとして8−メチル−8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン225部とビシクロ[2.2.1]ヘプト−2−エン25部とを使用し、分子量調節剤として1−ヘキセンを43部を使用した以外は、合成例1と同様にして水素添加重合体を得た。得られた水素添加重合体(以下、「環状オレフィン系樹脂2」という。)の水素添加率は、実質的に100%であった。
[Synthesis Example 2]
As a cyclic olefin, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . Synthesis Example, except that 225 parts of 17,7 ] -3-dodecene and 25 parts of bicyclo [2.2.1] hept-2-ene were used and 43 parts of 1-hexene was used as a molecular weight regulator. In the same manner as in Example 1, a hydrogenated polymer was obtained. The hydrogenation rate of the obtained hydrogenated polymer (hereinafter referred to as “cyclic olefin resin 2”) was substantially 100%.
環状オレフィン系樹脂2の28℃における屈折率は1.51、ηinhは0.50、Mw
は62,000、Mw/Mnは3.5、Tgは141℃であった。
図8に示すように溶融粘度を測定し、フィッティングを行って定数を計算した。n=0.393、τ*=7.12×104、B=6.96×10-9、Tb=14030であった。
The refractive index of cyclic olefin resin 2 at 28 ° C. is 1.51, η inh is 0.50, Mw
Was 62,000, Mw / Mn was 3.5, and Tg was 141 ° C.
As shown in FIG. 8, the melt viscosity was measured and fitting was performed to calculate the constant. n = 0.393, τ * = 7.12 × 10 4 , B = 6.96 × 10 −9 , and Tb = 14030.
[合成例3]
環状オレフィンとして8−エチリデンテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン250部を使用し、開環重合反応用溶媒としてシクロヘキサン750部を使用した以外は、合成例1と同様にして水素添加重合体を得た。得られた水素添加重合体(以下、「環状オレフィン系樹脂3」という。)の水素添加率は、実質的に100%であった。
[Synthesis Example 3]
As a cyclic olefin, 8-ethylidenetetracyclo [4.4.0.1 2,5 . A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that 250 parts of 1 7,10 ] -3-dodecene was used and 750 parts of cyclohexane was used as a solvent for the ring-opening polymerization reaction. The hydrogenation rate of the obtained hydrogenated polymer (hereinafter referred to as “cyclic olefin resin 3”) was substantially 100%.
環状オレフィン系樹脂3の28℃における屈折率は1.52、ηinhは0.50、Mw
は65,000、Mw/Mnは3.0、Tgは145℃であった。
図9に示すように溶融粘度を測定し、フィッティングを行って定数を計算した。n=0.264、τ*=2.04×105、B=6.13×10-7、Tb=11160であった。
The refractive index of cyclic olefin resin 3 at 28 ° C. is 1.52, η inh is 0.50, Mw
Was 65,000, Mw / Mn was 3.0, and Tg was 145 ° C.
As shown in FIG. 9, the melt viscosity was measured and fitting was performed to calculate the constant. n = 0.264, τ * = 2.04 × 10 5 , B = 6.13 × 10 −7 , Tb = 11160.
[実施例1〜10、比較例1〜5]
<光学レンズ成形体の製造>
(環状オレフィン樹脂の乾燥)
環状オレフィン系樹脂を予め100℃で4時間真空乾燥し、窒素雰囲気下で常圧に戻した後、窒素を封入したアルミニウム製の袋に密封して保管した。
[Examples 1 to 10, Comparative Examples 1 to 5]
<Manufacture of optical lens molding>
(Drying of cyclic olefin resin)
The cyclic olefin-based resin was previously vacuum-dried at 100 ° C. for 4 hours, returned to normal pressure in a nitrogen atmosphere, and then sealed and stored in an aluminum bag filled with nitrogen.
(金型)
表1および2に示すように、図10−1〜10−2および図11−1〜11−9に示す金型装置を用いた。これらの金型装置のキャビティーは、光学レンズ成形体の鍔部、凹部およびレンズ部それぞれに対応する空間部を有する。なお、実施例および比較例で用いた金型装置において、図10−1〜10−2はキャビティー部分を示しており、図11−1〜11−9はゲート部分を示している。
(Mold)
As shown in Tables 1 and 2, the mold apparatuses shown in FIGS. 10-1 to 10-2 and FIGS. 11-1 to 11-9 were used. The cavities of these mold apparatuses have space portions corresponding to the flange portion, the concave portion, and the lens portion of the optical lens molded body. In the mold apparatus used in the examples and comparative examples, FIGS. 10-1 to 10-2 show cavity portions, and FIGS. 11-1 to 11-9 show gate portions.
また、キャビティー周囲には、ゲートを除く全面に100μm深さのガスベント(図示せ
ず)を2mm長で設けた。
(射出成形)
射出成形機(ファナック社製α2000iB、シリンダー径25mm、型締め100ton)を用いて、環状オレフィン樹脂を射出成形した。成形条件は表1〜3に示すとおりであった。
Around the cavity, a gas vent (not shown) having a depth of 100 μm was provided on the entire surface excluding the gate with a length of 2 mm.
(injection molding)
The cyclic olefin resin was injection molded using an injection molding machine (FANUC α2000iB, cylinder diameter 25 mm, mold clamping 100 ton). Molding conditions were as shown in Tables 1-3.
なお、計量時のスクリュー回転数は40rpm、背圧は60kgf/cm2、成形サイクルは45sec
で行った。また成形条件設定後30ショット成形を行い、その後得られたレンズの成形品10個を製品とした。
Note that the screw rotation speed during measurement is 40 rpm, the back pressure is 60 kgf / cm 2 , and the molding cycle is 45 sec.
I went there. Further, 30 shot molding was performed after setting the molding conditions, and then 10 lens molded products obtained were used as products.
<評価方法>
上記射出成形により得られた成形体(光学レンズ成形体)を下記の方法により評価した。その結果を表1〜3に示す。
<Evaluation method>
The molded body (optical lens molded body) obtained by the injection molding was evaluated by the following method. The results are shown in Tables 1-3.
(面精度)
テーラーホブソン社製、フォームタリサーフS6を用いて、得られた光学レンズ成形体の基準面からの乖離の最大値および最小値の差、Pv値を測定した。図12および13に示すように、r1面およびr2面それぞれにおいて、x方向およびy方向で測定した。このPv値が0.5μm未満の場合を◎、0.5μm以上1.0μm未満の場合を○、1.0μm以上2.0μm未満を△、2.0μm以上の場合を×とした。
(Surface accuracy)
The difference between the maximum value and the minimum value of the deviation from the reference surface of the obtained optical lens molding and the Pv value were measured using Foam Talysurf S6 manufactured by Taylor Hobson. As shown in FIGS. 12 and 13, the measurement was performed in the x direction and the y direction on the r1 plane and the r2 plane, respectively. When the Pv value was less than 0.5 μm, ◎, when 0.5 μm or more and less than 1.0 μm, ◯, when 1.0 μm or more and less than 2.0 μm, Δ, and when 2.0 μm or more, ×.
(光学歪み)
王子計測社製のCCD-コブラを用いて、得られた光学レンズ成形体の面内の位相差分布を測定した。有効面内で観測されるもっとも大きな位相差が100nm未満の場合を◎、100nm以上140nm未満の場合を○、140nm以上160nm未満の場合を△、160nm以上の場合を×とした。
(Optical distortion)
The in-plane retardation distribution of the obtained optical lens molded body was measured using a CCD-cobra manufactured by Oji Scientific. The case where the largest phase difference observed in the effective plane is less than 100 nm is indicated by ◎, the case where it is 100 nm or more and less than 140 nm is indicated by ○, the case where 140 nm or more and less than 160 nm is indicated by Δ, and the case where it is 160 nm or more is indicated by ×.
(フローマーク)
オリンパス製の実態顕微鏡でレンズ表面の観察を行った。フローマークが観察されない場合を○、フローマークが観察される場合を×とした。
(Flow mark)
The lens surface was observed with an Olympus microscope. The case where the flow mark was not observed was marked as ◯, and the case where the flow mark was observed as x.
実施例1〜10は、上述した形状を備えた金型装置によって射出成形した場合であり、比較例1〜5は、上述した形状を備えていない金型装置によって射出成形した場合である。 Examples 1 to 10 are cases where injection molding is performed using a mold apparatus having the above-described shape, and Comparative Examples 1 to 5 are cases where injection molding is performed using a mold apparatus not including the above-described shape.
表1および2より、比較例の光学レンズ成形体は、光学歪みおよび面精度のバランスがとれていないが、実施例の光学レンズ成形体は、光学歪みおよび面精度のバランスがよい。 From Tables 1 and 2, the optical lens molding of the comparative example is not balanced between optical distortion and surface accuracy, but the optical lens molding of the example has a good balance between optical distortion and surface accuracy.
本発明に係る薄型の光学レンズ成形体は、携帯電話のカメラモジュル、パーソナルコンピューターのカメラモジュルなどの光学レンズとして有用である。 The thin optical lens molding according to the present invention is useful as an optical lens for a camera module of a mobile phone, a camera module of a personal computer, or the like.
Claims (5)
鍔部とレンズ部とが、凹部を介して結合しており、該鍔部の厚みが0.5mm以下、該凹部
の厚みが該鍔部の厚み以下かつ0.4mm以下であり、直径が10mm以下の光学レンズ成形体を
製造する方法であって、
上記ゲート開口部における上記キャビティーの高さ方向のゲートの厚みt1と、上記ゲ
ート開口部における上記キャビティーの高さ方向の鍔部の厚みt2とが、下記式(1)を
満たし、かつ、上記ゲートが、上記ゲート開口部に向かって、上記キャビティーの高さ方向の一方が狭まっており、該高さ方向に狭まる傾斜角度βが、下記式(2)を満たす上記金型装置により、上記環状オレフィン系樹脂を射出成形することを特徴とする光学レンズ成形体の製造方法。
t2×0.1≦t1≦t2×0.8 (1)
20°≦β≦60° (2) Cyclic olefin-based resin is injection-molded by a mold device in which a cavity and a gate corresponding to an optical lens molded body are bonded through a gate opening,
The collar part and the lens part are connected through a recess, the thickness of the collar part is 0.5 mm or less, the thickness of the recess is less than the thickness of the collar part and 0.4 mm or less, and the diameter is 10 mm or less. A method for producing an optical lens molded body, comprising:
The thickness t 1 of the gate in the height direction of the cavity in the gate opening and the thickness t 2 of the flange in the height direction of the cavity in the gate opening satisfy the following formula (1): In addition, the mold apparatus is such that one of the cavities in the height direction is narrowed toward the gate opening, and the inclination angle β narrowed in the height direction satisfies the following formula (2): The method for producing an optical lens molded body, wherein the cyclic olefin-based resin is injection molded.
t 2 × 0.1 ≦ t 1 ≦ t 2 × 0.8 (1)
20 ° ≦ β ≦ 60 ° (2)
30°≦α≦60° (3) The gate is characterized in that both the width direction of the cavity is uniformly narrowed toward the gate opening, and the inclination angle α narrowing in the width direction satisfies the following formula (3). The manufacturing method of the optical lens molded object of Claim 1.
30 ° ≦ α ≦ 60 ° (3)
30°≦α≦60° (4) The gate is characterized in that both the width direction of the cavity is uniformly spread toward the gate opening, and the inclination angle α spreading in the width direction satisfies the following formula (4). The manufacturing method of the optical lens molded object of Claim 1.
30 ° ≦ α ≦ 60 ° (4)
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JP2016112867A (en) * | 2014-12-18 | 2016-06-23 | 日本ゼオン株式会社 | Producing method of resin forming product |
JP2016147502A (en) * | 2016-05-16 | 2016-08-18 | 日本ゼオン株式会社 | Mold for molding optical lens and method for producing optical lens |
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JP7198010B2 (en) * | 2018-07-19 | 2022-12-28 | 株式会社小糸製作所 | resin parts |
CN116653235B (en) * | 2023-07-31 | 2023-10-24 | 成都宝利根创科电子有限公司 | Ejection separation structure in full-periphery large nozzle mold and injection mold |
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WO2012043190A1 (en) * | 2010-09-30 | 2012-04-05 | コニカミノルタオプト株式会社 | Method for manufacturing lens |
JP2016112867A (en) * | 2014-12-18 | 2016-06-23 | 日本ゼオン株式会社 | Producing method of resin forming product |
JP2016147502A (en) * | 2016-05-16 | 2016-08-18 | 日本ゼオン株式会社 | Mold for molding optical lens and method for producing optical lens |
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TWI432787B (en) | 2014-04-01 |
TW200829959A (en) | 2008-07-16 |
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CN101177032A (en) | 2008-05-14 |
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