JPH0546522B2 - - Google Patents
Info
- Publication number
- JPH0546522B2 JPH0546522B2 JP58120625A JP12062583A JPH0546522B2 JP H0546522 B2 JPH0546522 B2 JP H0546522B2 JP 58120625 A JP58120625 A JP 58120625A JP 12062583 A JP12062583 A JP 12062583A JP H0546522 B2 JPH0546522 B2 JP H0546522B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- base material
- refractive index
- optical transmission
- polymer
- 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.)
- Expired - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 145
- 239000000463 material Substances 0.000 claims description 73
- 238000009792 diffusion process Methods 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 33
- 239000007791 liquid phase Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 230000005540 biological transmission Effects 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 22
- 239000012530 fluid Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 239000000057 synthetic resin Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 2
- 238000009751 slip forming Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 35
- 238000010438 heat treatment Methods 0.000 description 35
- 239000000203 mixture Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 11
- 229920006362 Teflon® Polymers 0.000 description 11
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 5
- 239000004641 Diallyl-phthalate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- -1 allyl ester Chemical class 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- FWICIOVOJVNAIJ-UHFFFAOYSA-N bis(ethenyl) benzene-1,3-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC(C(=O)OC=C)=C1 FWICIOVOJVNAIJ-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4479—Manufacturing methods of optical cables
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0031—Refractive
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
ãã®çºæã¯ãå±æçååžãæããåææš¹èå
äŒ
éäœã補é ããæ¹æ³ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a synthetic resin optical transmission body having a refractive index distribution.
å
äŒéäœãšããŠãäžå¿è»žããã®è·é¢ã®ïŒä¹ã«æ¯
äŸããŠæžå°ããå±æçã®ååžãæããéææ£ç¶äœ
ãç¥ãããŠããããã®éææ£ç¶äœã¯åžã¬ã³ãºäœçš
ãæãããŸããã®å±æçååžã¯(1)åŒã§è¿äŒŒãã
ãã A transparent rod-shaped body having a refractive index distribution that decreases in proportion to the square of the distance from the central axis is known as a light transmission body. This transparent rod-shaped body has a convex lens effect, and its refractive index distribution is approximated by equation (1).
ïœ(r)ïŒn0ïŒïŒâïŒïŒïŒAr2ïŒ âŠâŠ(1)
ïŒåŒäžãïœ(r)ã¯äžå¿è»žããã®è·é¢ïœã®ç¹ã«ãã
ãå±æçãn0ã¯äžå¿è»žã«ãããå±æçãã¯æ£ã®
å®æ°ãããããè¡šãããïŒ
ãã®ãããªéææ£ç¶äœäžãå
æã¯èè¡ããŠäŒæ
ãããã®åšæã¯(2)åŒã§è¡šããããã n(r)=n 0 (1-1/2Ar 2 ) ...(1) (In the formula, n(r) is the refractive index at the point of distance r from the central axis, n 0 is the refractive index at the central axis, (A represents a positive constant.) The light beam propagates in a meandering manner in such a transparent rod-shaped body, and its period L is expressed by equation (2).
ïŒ2ÏïŒâ âŠâŠ(2)
ãŸãã(3)åŒã§è¿äŒŒãããããã«ãäžå¿è»žããã®
è·é¢ã®ïŒä¹ã«æ¯äŸããŠå¢å€§ããå±æçååžãæã
ãå Žåã«ã¯ãéææ£ç¶äœã¯å¹ã¬ã³ãºäœçšãæãã
å
äŒéäœãšãªãã L=2Ï/â...(2) Also, as approximated by equation (3), if the transparent rod-shaped body has a refractive index distribution that increases in proportion to the square of the distance from the central axis, It becomes an optical transmission body with a concave lens effect.
ïœ(r)ïŒn0ïŒïŒïŒïŒïŒïŒBr2ïŒ âŠâŠ(3)
ïŒåŒäžãïœ(r)ããã³n0ã¯åèšã«åãã§ããã
ã¯æ£ã®å®æ°ã§ãããïŒ
ãã®ãããªå±æçååžãæããåææš¹èå
äŒé
äœã®è£œé æ¹æ³ã¯ãç¹å
¬æ52â5857å·å
¬å ±ãç¹éæ
51â16394å·å
¬å ±ãç¹éæ54â119939å·å
¬å ±ãªã©
ã«èšèŒãããŠãããç¹å
¬æ52â5857å·å
¬å ±ããã³
ç¹éæ51â16394å·å
¬å ±ã«èšèŒãããæ¹æ³ã§ã¯ã
ãŸãã網ç¶éåäœPaãçæããæ¶æ©æ§åéäœMa
ã液äœç¶æ
ããæµåæ§ã倱ã€ãã²ã«ç¶æ
ã«ãªããŸ
ã§åæéåãããŠéæãªã²ã«ç¶æ¯æã圢æããã
次ãã§ããã®æ¯æãåéäœMaãšã¯ç°ãªãåéäœ
Mbãããªã液çžäžã«æµžæŒ¬ããŠãæ¯æããã®è¡šé¢
ããå
éšã«åã€ãŠæ¬¡ç¬¬ã«æžå°ãããããªåéäœ
Mbã®æ¿åºŠåŸé
ãæã€ããã«ãåéäœMbãæ¡æ£
ãããããã®ãšããåéäœMbãšããŠã¯ã網ç¶é
åäœPaã®å±æçãšã¯ç°ãªãå±æçãæããéå
äœPbãçæããåéäœãçšãããåéäœMbã¯æ¡
æ£ãšåæã«ããã³ïŒãŸãã¯æ¡æ£åŸã®ç±åŠçå·¥çšäž
ã«éåãããŸããã®æã«åéäœMaã®éåãå®çµ
ãããç¹å
¬æ52â5857å·å
¬å ±ããã³ç¹éæ51â
16394å·å
¬å ±ã«èšèŒãããæ¹æ³ã§ã¯ããã®ããã«
ããŠå±æçååžãæããåææš¹èå
äŒéäœãåŸã
ããã«ããŠããã n(r)=n 0 (1+1/2Br 2 )...(3) (In the formula, n(r) and n 0 are the same as above, and B
is a positive constant. ) A method of manufacturing a synthetic resin optical transmitter having such a refractive index distribution is described in Japanese Patent Publication No. 52-5857 and Japanese Patent Application Laid-Open No.
It is described in JP-A No. 51-16394, Japanese Patent Application Laid-open No. 119939-1980, etc. In the method described in Japanese Patent Publication No. 52-5857 and Japanese Patent Application Laid-open No. 51-16394,
First, the crosslinkable monomer Ma that produces the network polymer Pa
A transparent gel-like matrix is formed by initial polymerization from a liquid state to a gel state that has lost fluidity.
Next, this base material is treated with a monomer different from the monomer Ma.
A monomer that is immersed in a liquid phase consisting of Mb so that the base material gradually decreases from the surface to the inside.
Diffuse monomeric Mb so that there is a concentration gradient of Mb. At this time, as the monomer Mb, a monomer that produces a polymer Pb having a refractive index different from the refractive index of the network polymer Pa is used. The monomer Mb is polymerized simultaneously with the diffusion and/or during the heat treatment step after the diffusion, and the polymerization of the monomer Ma is also completed at this time. Japanese Patent Publication No. 5857/1983 and Japanese Patent Application Publication No. 51/1983
In the method described in Japanese Patent No. 16394, a synthetic resin optical transmission body having a refractive index distribution is thus obtained.
ãšããããäžè¿°ããæ¹æ³ã§ã¯ãæ¯æã液ç¶ã®å
éäœMbäžã«æµžæŒ¬ãããŠæ¯æè¡šé¢ãšæ¶²ç¶ã®åéäœ
MbãšãçŽæ¥æ¥è§Šãããããã«ãäžå©ãªç¹ããã
ã€ããã€ããäŸãã°ãåéäœMbã®æ¡æ£ãšéåãš
ãåæã«è¡ããããªå Žåã«ã¯ã浞挬枩床ãæ¯èŒç
é«æž©ã«ãããããããã³æ¯æäžã«éåžžå«æãããŠ
ããéåéå§å€ã浞挬æéã®çµéãšå
±ã«æ¶²çžã«æº¶
åºããããã液çžäžã§ãåéäœMbã®éåãåŸã
ã«èµ·ã€ãŠç²çš ã«ãªãããã®çµæãæ¡æ£ãçµããŠæ¯
æã液çžäžããåãåºãéã«ããã®ããã«ããŠåœ¢
æãããç²çš å±€ãæ¯æè¡šé¢ã«ä»çãããŸãŸåãåº
ãããŠããŸãããããŠç±åŠçå·¥çšäžã«ããã®ç²çš
å±€ããåéäœMbã浞åºããŠæ¯æå
ã«æ¡æ£ããåŸ
ãããå
äŒéäœã®å€åšéšä»è¿ã®å±æçã«å¥œãŸãã
ãªãæªã¿ãå¢å€§ãããåå ãšãªãããã®ãããªæ¬
ç¹ãé€å»ããããã«ã液çžã§ã®åéäœMbã®éå
ãæå¶ããéåçŠæ¢å€ãå ããŠããããšãèãã
ãããããã®å Žåã«ã¯ããã®éåçŠæ¢å€ãåéäœ
Mbã®æ¡æ£ãšåæã«æ¯æäžã«æ¡æ£ããŠç±åŠçå·¥çš
ã«ãããéåå®çµãé»å®³ãããšããæ°ããªæ¬ ç¹ã
çããã However, in the above method, the base material is immersed in the liquid monomer Mb, and the base material surface and the liquid monomer Mb are immersed.
Direct contact with Mb had several disadvantages. For example, when diffusion and polymerization of the monomer Mb are carried out simultaneously, the dipping temperature must be relatively high, and the polymerization initiator normally contained in the base material will liquefy as the dipping time passes. Since it is eluted into the phase, monomer Mb gradually polymerizes even in the liquid phase and becomes viscous. As a result, when the base material is removed from the liquid phase after diffusion, the viscous layer thus formed remains attached to the surface of the base material. During the heat treatment process, the monomer Mb leaches out of this viscous layer and diffuses into the base material, causing an increase in undesirable distortion in the refractive index near the outer periphery of the resulting light transmitting body. In order to eliminate such drawbacks, it may be possible to add a polymerization inhibitor that suppresses the polymerization of monomer Mb in the liquid phase, but in this case, this polymerization inhibitor may
A new drawback arises in that Mb diffuses simultaneously into the base material and inhibits the completion of polymerization in the heat treatment process.
ãŸããåéäœMbãæ¡æ£åŸã«éåããããããª
å Žåã¯æ¯èŒçäœã浞挬枩床ã§ãããããã®å Žåã«
ã¯æ¡æ£ããåéäœMbãç±åŠçå·¥çšäžã«æ¯æã®å€
åšéšããèžçºããããããã¯ãå€åšéšä»è¿ã®å±æ
çååžã«å¥œãŸãããªãæªã¿ãå¢å€§ãããåå ãšãª
ãã In addition, if the monomer Mb is polymerized after being diffused, a relatively low immersion temperature is required, but in this case, the diffused monomer Mb evaporates from the outer periphery of the base material during the heat treatment process. This causes an increase in undesirable distortion in the refractive index distribution near the outer periphery.
ç¹éæ54â119939å·å
¬å ±ã«èšèŒãããæ¹æ³ã¯äž
è¿°ã®æ¹æ³ãæ¹è¯ããŠå€åšéšä»è¿ã§ã®å±æçååžã®
æªã¿ãåé¿ããããšãããã®ã§ããããã®æ¹æ³ã«
ããã°ãåéäœMbã®æ¡æ£ãæ°çžäžã§è¡ã€ãŠã
ããããªãã¡ãåéäœMbã®èžæ°é°å²æ°äžã«æ¯æ
ãæå®æéé
眮ããŠåéäœMbãæ¯æå
ã«æ¡æ£ã
ãããã®æ¡æ£ãšåæã«åéäœMbãäžéšéåã
ããæåŸã«ç±åŠçã«ãã€ãŠéåãå®çµããããã
ã«ããŠããããã®æ¹æ³ã§ã¯ãæ¯æã¯æ¶²çžã®åéäœ
Mbãšã§ãªããæ°çžã®åéäœMbãšæ¥è§Šããã®ã§
次ã®ãããªå©ç¹ãããã The method described in JP-A-54-119939 is an improvement on the above-mentioned method to avoid distortion of the refractive index distribution near the outer periphery. According to this method, monomeric Mb is diffused in the gas phase. That is, the base material is placed in a vapor atmosphere of monomer Mb for a predetermined period of time to diffuse the monomer Mb into the base material, and at the same time as this diffusion, part of the monomer Mb is polymerized, and finally, by heat treatment. to complete the polymerization. In this method, the base material is monomer in liquid phase.
Because the contact is not with Mb but with monomer Mb in the gas phase, there are the following advantages.
(1) æ¯æã®è¡šé¢ã«äœåã®åéäœMbãä»çããª
ããæ
ã«ãç±åŠçå·¥çšäžã«ä»çããåéäœMb
ãæ¯æã®è¡šé¢ããå
éšãžæ¡æ£ããããšããªãã
ãŸããæ¡æ£ãé«æž©ã§è¡ãããåéäœMbã¯æ¯æ
å
éšã«æ¡æ£ãã€ã€éåããŠåºå®åããããã
ã§ãç±åŠçå·¥çšäžã«åéäœMbãæ¯æã®å€åšéš
ããèžçºããããšããªãããããã€ãŠãå€åšéš
ã§ã®å±æçã®æªã¿ãå°ããã€åæã®å±æçååž
ãåºãç¯å²ã§æããå
äŒéäœãåŸãããã(1) Excess monomer Mb does not adhere to the surface of the base material. Therefore, monomeric Mb deposited during the heat treatment process
does not diffuse into the interior from the surface of the base material.
Furthermore, since the diffusion is carried out at a high temperature, the monomer Mb is polymerized and fixed while diffusing inside the base material. Therefore, the monomer Mb does not evaporate from the outer periphery of the base material during the heat treatment process. Therefore, it is possible to obtain an optical transmission body with little distortion of the refractive index at the outer circumferential portion and having an initial refractive index distribution over a wide range.
(2) åéäœMbã®èžæ°ã®äŸçµŠæºã§ãã液äœã®åé
äœMbäžã«éåçŠæ¢å€ãæ·»å ããããšã«ãã€
ãŠã液çžã§ã®åéäœMbã®éåãé²æ¢ã§ããã
ãã®éãèžæ°å§ã®äœãéåçŠæ¢å€ãçšããã°ã
ããã¯ã»ãšãã©æ°åããªãã®ã§ãæ¯æå
ã«æ¡æ£
ããããšããªãããããã€ãŠç±åŠçå·¥çšã«éå
ãé»å®³ãããªããããã«ãåéäœMbã®äŸçµŠé
床ã調ç¯ããã°éåçŠæ¢å€ãå ããå¿
èŠããªã
ãªããåéäœMbãäœåãç¹°ãè¿ããŠäœ¿çšãã
ããšãå¯èœãšãªã€ãŠãã®ååçãé«ããããã(2) Polymerization of monomer Mb in the liquid phase can be prevented by adding a polymerization inhibitor to liquid monomer Mb, which is a source of vapor of monomer Mb.
At that time, if a polymerization inhibitor with low vapor pressure is used,
Since it hardly evaporates, it does not diffuse into the base material, and therefore, polymerization is not inhibited during the heat treatment process. Furthermore, by adjusting the supply rate of monomer Mb, there is no need to add a polymerization inhibitor, making it possible to use monomer Mb many times and increasing its recovery rate.
ããããªããããã®æ¹æ³ã«ã¯æ¬¡ã®ãããªæ¬ ç¹ã
ãããããªãã¡ãåéäœMbãæ°çžããæ¯æäžã«
æ¡æ£ãããå Žåãæ°çžäžã®åéäœMbæ¿åºŠã¯ãã®
æ°çžæž©åºŠã«ãããèžæ°å§ã«äŸåããããšã«ãªãã
ãããã®æ¡æ£å·¥çšãå¹ççã«é²ããã®ã«é©åœãªå
éäœã®çš®é¡ã¯èžæ°å§ã®é«ãç¹å®ã®åéäœã«å¶çŽã
ããŠããŸããäŸãã°ãç¹éæ51â16394å·ã®æ¹æ³
ã«ãã€ãŠäœè²åå·®ãæããåææš¹èå
äŒéäœã補
é ããéã«äœ¿çšå¯èœãªãžãšãã¬ã³ã°ãªã³ãŒã«ãã¹
ã¢ãªã«ã«ãŒãããŒãïŒåéäœMaïŒãšãïŒïŒïŒïŒ
ïŒâããªãã€ããããŒãã«ãªããããã«ïŒåéäœ
MbïŒãšã®çµåãã¯ãåŸè
ã®èžæ°å§ãäœããŠçŽåŸ
ïŒmmããã以äžã®æ¯æã«æ¡æ£ãããããšãé£ãã
ãããç¹éæ54â119939å·ã®æ¹æ³ã«ã¯é©çšã§ããª
ãã€ãã However, this method has the following drawbacks. In other words, when monomeric Mb is diffused from the gas phase into the base material, the monomeric Mb concentration in the gas phase depends on the vapor pressure at the gas phase temperature. The types of monomers suitable for proceeding are limited to specific monomers with high vapor pressures. For example, 1,1,
3-trihydroperfluoropropyl (monomer
The combination with Mb) could not be applied to the method of JP-A-54-119939 because the latter has a low vapor pressure and is difficult to diffuse into a base material with a diameter of 4 mm or more.
ãã®çºæã¯ããã®ãããªåŸæ¥æè¡ã®æ¬ ç¹ãå
æ
ããäžæ¹ãããããã®é·æãçããããã®ã§ã
ãããããŠãåéäœMaãšåéäœMbãšã®çš®ã
ã®
çµåãã«ã€ããŠããã®äžå¿ããå€åšéšã«è³ãæ¯æ
ã®åºç¯å²ã«äºã€ãŠææã®å±æçååžã圢æã§ãã
åææš¹èå
äŒéäœã®è£œé æ¹æ³ãæäŸãããã®ã§ã
ãã The present invention overcomes the drawbacks of these prior art technologies while taking advantage of their respective strengths. We then developed a method for manufacturing synthetic resin optical transmission bodies that can form desired refractive index distributions over a wide range of the base material from the center to the outer periphery for various combinations of monomer Ma and monomer Mb. This is what we provide.
ããªãã¡ããã®çºæã¯ãå±æçNaã®ç¶²ç¶éå
äœPaãçæããåéäœMaã®äžå®å
šãªéåãè¡ã€
ãŠèªå·±ä¿åœ¢æ§ãæããæ¯æã圢æããå±æçNa
ãšã¯ç°ãªãå±æçNbãæããéåäœPbãçæã
ãã€æ¶²äœç¶æ
ã«ããåéäœMbããåèšæ¯æã®è¡š
é¢ã«æ¥è§ŠãããŠãã®å
éšãžæ¡æ£ããããšå
±ã«ãã
ãã«å ç±éåãããããã«ãããå±æçååžãæ
ããåææš¹èå
äŒéäœã®è£œé æ¹æ³ã«ãããŠãåèš
åéäœMaãçšããŠåŸãããæ圢çšæµäœãæ圢管
å
ã«éã蟌ãã§ãã®æ圢管å
ã§åèšèªå·±ä¿åœ¢æ§æ¯
æãé£ç¶çã«åœ¢æãã次ãã§ãåèšæ圢管ããé£
ç¶çã«åºãŠæ¥ãåèšèªå·±ä¿åœ¢æ§æ¯æã«ã
åèšæ¶²ç¶åéäœMbãå«æãã液çžæ¡æ£å®€ã
åèšåéäœMbãšåäžãŸãã¯ç°ãªãåéäœ
Mcã§ãã€ãŠã
(a) NcïŒNb
(b) NcïŒNaããã³NbïŒNa
(c) NcïŒNaããã³NbïŒNa
ãªã(a)ã(c)ã®æ¡ä»¶ã®äœããïŒã€ãæºè¶³ããå±æ
çNcãæããéåäœPcãçæããã€äžå®æž©åºŠ
ã«å ç±å¶åŸ¡ãããæ°äœç¶ãŸãã¯é§æ»Žç¶ã®åéäœ
Mcãå«æããæ°çžå®€ã
ãé 次ééãããããã«ããããšãç¹åŸŽãšããå
ææš¹èå
äŒéäœã®è£œé æ¹æ³ã«ä¿ããã®ã§ããã That is, this invention performs incomplete polymerization of a monomer Ma that produces a network polymer Pa with a refractive index of Na to form a self-shape-retaining base material, and has a refractive index of Na.
A refraction method that produces a polymer Pb having a refractive index different from that of Nb, and in which a monomer Mb in a liquid state is brought into contact with the surface of the base material and diffused into the interior thereof, and is further heated and polymerized. In the method for manufacturing a synthetic resin light transmission body having a rate distribution, a molding fluid obtained using the monomer Ma is fed into a molding tube to continuously form the self-shape-retaining base material in the molding tube. Then, in the self-shape-retaining base material continuously coming out of the molded tube, a liquid phase diffusion chamber containing the liquid monomer Mb, a monomer that is the same as or different from the monomer Mb.
Refraction that satisfies any one of the conditions (a) to (c) that is Mc and (a) Nc=Nb (b) Nc<Na and Nb<Na (c) Nc>Na and Nb>Na A monomer in the form of gas or droplets that forms a polymer Pc with a ratio Nc and is heated and controlled to a constant temperature.
The present invention relates to a method for manufacturing a synthetic resin optical transmission body, characterized in that the material is sequentially passed through a vapor chamber containing Mc.
ãã®ããã«æ§æãããã®çºæã®è£œé æ¹æ³ã«ãã
ã°ãèªå·±ä¿åœ¢æ§ãæããæ¯æã®åœ¢æããã®æ¯æãž
ã®åéäœMbã®å
éšæ¡æ£åã³åéäœMcã«ããå
èšæ¯æã®å ç±éåãé 次é£ç¶çã«è¡ãããšãã§ã
ããããåäžãªç¹æ§ãæããã€å質ã®äžå®ãªå±æ
çååžååææš¹èå
äŒéäœãç°¡åãªè£œé å·¥çšã§ä»¥
ã€ãŠå€§éã«çç£ããããšãã§ããããŸããæ¯æã«
æ¡æ£ãããåéäœã®å€§éšåãå ããåéäœMbã¯
èžæ°å§ã®é«ããã®ã«éããããŸãåéäœMcãã
æ¯æã®å€åšéšããã®åéäœMbã®èžçºãæå¶ãã
ã ãã§ãããããç¹ã«èžæ°å§ã®é«ããã®ã§ããå¿
èŠããªãããŸããç±åŠçãåéäœMcïŒåéäœMb
ãšåäžã§ãã€ãŠããïŒã®èžæ°ïŒæ°äœç¶ãŸãã¯é§æ»Ž
ç¶ïŒãå«ãé°å²æ°äžã§è¡ããããæ¯æã®å€åšéšä»
è¿ã§ã®å±æçååžã®æªã¿ãé€å»ãŸãã¯åé¿ã§ã
ãã According to the manufacturing method of the present invention configured as described above, formation of a base material having self-shape retention, internal diffusion of monomer Mb into this base material, and heating polymerization of the base material by monomer Mc are performed. Since the process can be carried out sequentially and continuously, it is possible to mass-produce graded index synthetic resin optical transmitters having uniform characteristics and constant quality through a simple manufacturing process. In addition, monomer Mb, which accounts for most of the monomers diffused into the base material, is not limited to those with high vapor pressure, and monomer Mc also has
Since it is only necessary to suppress the evaporation of the monomer Mb from the outer periphery of the base material, it is not necessary to have a particularly high vapor pressure. In addition, heat treatment can be applied to monomer Mc (monomer Mb
Since the process is carried out in an atmosphere containing vapor (which may be the same as the above) (in the form of gas or droplets), distortion of the refractive index distribution near the outer periphery of the base material can be removed or avoided.
次ã«ããã®çºæã«ããåææš¹èå
äŒéäœã®è£œé
æ¹æ³ã®å®æœäŸããå³é¢ã«ç€ºãè£
眮ãçšããå Žåã«
ã€ããŠè¿°ã¹ãã Next, an embodiment of the method for manufacturing a synthetic resin optical transmission body according to the present invention will be described using the apparatus shown in the drawings.
ãŸããåéäœMaãäºåéåãããŠãã²ã«åçŽ
åã§æµåæ§ãä¿æããŠããç²æ§æµäœïŒãã¬ããªã
ãŒïŒãçæãããããã®ãã¬ããªããŒïŒãæŒåºã
åšïŒã«å
¥ããå·åŽæ°Žã«ãã€ãŠäžæŠå·åŽããªããã
é£ç¶çã«æŒåºãã First, the monomer Ma is prepolymerized to produce a viscous fluid (prepolymer) that maintains fluidity just before gelation. This prepolymer 1 is put into an extruder 2, and while being cooled once with cooling water,
Extrude continuously.
ããã§ãã¬ããªããŒã¯äžè¬åŒïŒ
ïŒKÏn âŠâŠ(4)
ïŒåŒäžãã¯ããé床ãÏã¯ããå¿åãã¯å¡
æ§ç²åºŠã®éæ°ãïœã¯å®æ°ãããããè¡šãããïŒ
ã§è¡šããããéããŠãŒãã³æµäœã®äžè¬æ¹çšåŒ
ïŒOstwaldã®ã¹ãæ³åïŒã«ããã20âã§ã®ïœã®å€
ã1.10以äžã§ããå¡æ§æµåã瀺ãããšãæãŸã
ãã以äžã«ãã®çç±ãè¿°ã¹ãã Here, the prepolymer has the following general formula: D=KÏ n ...(4) (In the formula, D is the shear rate, Ï is the shear stress, K is the reciprocal of the plastic viscosity, and n is the constant.) It is desirable to exhibit plastic flow in which the value of n at 20°C in the Newtonian fluid general equation (Ostwald's power law) is 1.10 or more. The reason is explained below.
åéäœãŸãã¯äœç²åºŠãã¬ããªããŒã®ãããªããŠ
ãŒãã³æµäœã«è¿ãæµäœã现é·ã管å
ã«å°å
¥ããã
ã®ç®¡å
ãééãããªããå ç±ããŠéåãããå Ž
åãç±ã¯ç®¡ã®å€åŽããå ããããããã«ã管è¿å
ã®åšèŸºé åããéåãé²ã¿ãããã«äŒŽã€ãŠç²åºŠã
äžæããŠè¡ãã管å
ãæµããæµäœã«ã¯ãäžå¿ãæ
倧ã§åšèŸºã«åããã«åŸã€ãŠæŸç©ç·ç¶ã«æµéãæžå°
ãããšããé床ååžãå
ã
ååšããŠããããéå
ãé²ãã«ã€ããŠããã®åšèŸºé åãšäžå¿é åãšã®é
ã®é床差ã¯ããã«å€§ãããªãããããŠãæçµçã«
ã¯åšèŸºé åã®æµäœãå
ã«ã²ã«åããŠç®¡å
ã«æ»ç
ããäžå¿é åã®æµäœã¯ã»ãšãã©éåããã«ç®¡ãã
æµãåºãããšã«ãªãã When a fluid similar to a Newtonian fluid, such as a monomer or a low-viscosity prepolymer, is introduced into a long and thin tube and is heated and polymerized while passing through the tube, the heat is applied from the outside of the tube, so Polymerization proceeds from the peripheral region, and the viscosity increases accordingly. The fluid flowing inside the tube originally has a velocity distribution in which the flow velocity is maximum at the center and decreases parabolically toward the periphery, but as polymerization progresses, the velocity distribution between the peripheral region and the center region increases. The speed difference becomes even larger. In the end, the fluid in the peripheral region gels first and stays in the tube, while the fluid in the central region flows out of the tube without polymerizing.
ãããæ¯æ£ããããã«ã¯ã管å
ã§ã®æµäœã®é床
ååžããªãã¹ãäžå®ã«ããå¿
èŠããããããªã
ã¡ã管å
ã®æµäœããã³ã¬ã æµäœã«è¿ã¥ããã°ã
ãããã³ã¬ã æµäœã¯äžèš(4)åŒã«ãããŠã¯ïœïŒâã®
å Žåã§ãã€ãŠã管å
ã®æµäœã®æµéã¯äžå®ãšãªãã
ïœãå°ãããªã€ãŠïŒã«è¿ã¥ãã»ã©ãæµäœã¯ããŠãŒ
ãã³æµäœã«è¿ã¥ãããŸãã管ã®å
å£ã«è¿ãåšèŸºä»
è¿ã§ã®æµäœã®æµéã¯ïœã®å€ã«ãã€ãŠã¯ããã»ã©å€
åããããããïœã倧ããã»ã©ãã®æµéã倧ãã
ããïœãïŒã«è¿ã¥ãã»ã©äžå¿ä»è¿ã§ã®æµéã倧ã
ããªãããã®çµæåšèŸºé åãšäžå¿é åãšã®æµéã®
å·®ã倧ãããªã€ãŠé床ååžã®æŸç©ç·ãã·ã€ãŒãã«
ãªãã In order to correct this, it is necessary to make the velocity distribution of the fluid within the pipe as constant as possible. That is, it is sufficient to bring the fluid in the pipe closer to Bingham fluid. In the case of Bingham fluid, n=â in the above equation (4), and the flow rate of the fluid in the pipe is constant.
As n becomes smaller and approaches 1, the fluid approaches a Newtonian fluid. In addition, the flow velocity of the fluid near the periphery near the inner wall of the pipe does not change much depending on the value of n; in fact, the larger n is, the greater the flow velocity is, but as n approaches 1, the flow velocity near the center increases. As a result, the difference in flow velocity between the peripheral region and the central region becomes large, and the parabola of the velocity distribution becomes sharp.
ãã®ãããªèŠ³ç¹ãããäžè¿°ããããã«åéäœ
MaãäºåéåãããŠãïœã®å€ã1.10以äžã§ãã
ç²æ§æµäœãšããŠãã管å
ã«éã蟌ãã®ã奜ãŸã
ããããªãã¡ãïœã®å€ã1.10æªæºã§ã¯ãã¯ããã«
åšèŸºä»è¿ãã²ã«åãããŠããŸããšãäžå¿ä»è¿ã®å
éäœMaã¯éåãããã«ç®¡å
ããæµåºããè¯å¥œãª
æ¯æã圢æã§ããªãããã®å Žåãæµéã極端ã«èœ
ãšãã°æ¯æãã§ããªãããšããªãããçç£æ§ãæª
ããªã€ãŠå®çšçã§ãªãããŸããããã«å¥œãŸããã¯
ïœã®å€ã¯å€§ãããšã1.50ã§ãããããã¯ïœã®å€ã
倧ããããŠã管å
ãžã®æŒã蟌ã¿ãå°é£ã«ãªã€ãã
æ¯æãäžå質ãšãªã€ãŠäžéœåãçããããã§ã
ãã From this point of view, as mentioned above, monomers
It is preferable to prepolymerize Ma to form a viscous fluid with an n value of 1.10 or more before feeding it into the pipe. That is, if the value of n is less than 1.10, if the vicinity of the periphery is first gelled, the monomer Ma in the vicinity of the center will not be polymerized and will flow out of the tube, making it impossible to form a good base material. In this case, if the flow rate is extremely reduced, the base metal will not be formed, but productivity will be poor and this is not practical. Further, more preferably, the value of n is at most 1.50. This is because if the value of n is too large, it becomes difficult to push the material into the pipe, and the base material becomes non-uniform, causing problems.
ãªããäžèš(4)åŒã«ãããã®å€ããã³ïœã®å€ã¯
ããããç²åºŠèšïŒäŸãã°å転åŒç²åºŠèšïŒãçšããŠ
æ±ããããšãã§ãããããªãã¡ç²åºŠèšã®å転æ°
ïŒããã§ïŒ€ã決ãŸãïŒãå€ããŠãããããã®Ïã
枬å®ããåŸããããã°ã©ãã«ããããããŠïŒ«ãã
ã³ïœã®å€ãæ±ããã Note that the value of K and the value of n in the above equation (4) can be determined using a viscometer (for example, a rotational viscometer). That is, after changing the rotational speed of the viscometer (which determines D) and measuring each Ï, this is plotted on a graph to determine the values of K and n.
æŒãåºããããã¬ããªããŒïŒã¯ãåŒãç¶ãé»é
補ãããã¯çã®å ç±ãžã€ã±ããïŒã貫éãããã
ãã³ããŠãŒãïŒäžã«é£ç¶çã«å°å
¥ãããããã®ã
ããã³ããŠãŒãïŒã¯å圢æé¢ãæããçŽåŸïŒã20
mmã®ãã®ã§ãã€ãŠãããããã§ãäºããããã³ã
ãŠãŒãïŒå
ã«äžæ¹ããã¹ãã³ã¬ã¹ç®¡ã®äžç«¯éšãæ¿
å
¥ããŠãããšããã¬ããªããŒïŒã®å
端ããã®ã¹ã
ã³ã¬ã¹ç®¡ã®äžç«¯éšã«æ¥è§Šããç¶æ
ã§ã²ã«åããã®
ã§ãã¹ãã³ã¬ã¹ç®¡ã®äžç«¯éšãšãã¬ããªããŒïŒã®å
端ãšãäžäœçµåãããããã®åŸæŒãåºãé床ãšå
ãé床ã§ã¹ãã³ã¬ã¹ç®¡ãåŒãäžãè£
眮ã§åŒãäžã
ããšãããã«äŒŽããããã¬ããªããŒã¯å
šè£œé å·¥çš
ãçµéããéã«å
äŒéäœãšãªã€ãŠé£ç¶çã«ãã€è£
眮å
ã«æ»ãããšãªãçæãããŠåºãŠãããå ç±ãž
ã€ã±ããïŒã«ã¯ããã®äžéšã«æ¯èŒçé«æž©ã®æž©æ°Ž
ïŒãäžéšã«ããããäœæž©ã®æž©æ°ŽïŒãããããäŸçµŠ
ãããŠããŠãäžéšããäžéšã«åã€ãŠæ¬¡ç¬¬ã«æž©åºŠã
äžæãããããªæž©åºŠåŸé
ã§ãã€ãŠããããã³ããŠ
ãŒãïŒãå ç±ããŠãããããã§ããããã³ããŠãŒ
ãïŒãééãããã¡ã«ãã¬ããªããŒïŒã¯å ç±éå
ããŠã²ã«åãããã®ã²ã«åãããã¬ããªããŒã¯æ¯
æïŒãšãªãããã®å ç±éåã®éã®å ç±é床ã¯0.1
ã10âïŒåã§ããã®ã奜ãŸãããäžè¿°ãããããª
枩床åŸé
ã®ããšã§å ç±ãããå Žåã«ã¯ããã¬ããª
ããŒïŒã®éåããã³ããã«äŒŽãç²åºŠäžæãå
±ã«
åŸã
ã«é²è¡ããããããã³ã¬ã æµäœã«è¿ãæµåç¶
æ
ã«ä¿æãããŸãŸããã¬ããªããŒïŒãæµåããã
ããšãå¯èœãšãªãããã®çµæãååŸæ¹åã«åäžãª
çµæãæã€ãæ¯æïŒãé£ç¶çã«åœ¢æããããšãå¯
èœãšãªãããªããããã§ãããã³ããŠãŒãïŒã¯ã
ãã¬ããªããŒïŒãæ¯æïŒãšã®æ©æŠãå°ããããã«
ç¹ã«æçšã§ããããä»ã®æš¹èãéå±è£œã®ããŠãŒã
ã§ãã€ãŠããã€ãããªãã The extruded prepolymer 1 is then continuously introduced into a Teflon tube 4 passing through a heating jacket 3, such as a brass block. This Teflon tube 4 has a circular cross section with a diameter of 1 to 20 mm.
It may be mm. Here, if the lower end of the stainless steel tube is inserted into the Teflon tube 4 from above in advance, the tip of the prepolymer 1 will gel while in contact with the lower end of the stainless steel tube. and the tip of prepolymer 1 are integrally bonded. When the stainless steel tube is pulled up by a pulling device at the same speed as this push-out speed, the prepolymer accompanying it becomes a light transmitting body and is produced continuously and without stagnation in the device during the entire manufacturing process. It comes out. The heating jacket 3 is supplied with relatively high-temperature hot water 5 at the top and hot water 6 at a lower temperature at the bottom. Tube 4 is being heated. Then, while passing through the Teflon tube 4, the prepolymer 1 is polymerized and gelled by heating, and this gelled prepolymer becomes the base material 7. The heating rate during this thermal polymerization is 0.1
Preferably it is ~10°C/min. When heated under the temperature gradient described above, both the polymerization of prepolymer 1 and the accompanying increase in viscosity proceed gradually. It becomes possible to make it flow. As a result, it becomes possible to continuously form the base material 7 having a uniform composition in the radial direction. In addition, here, the Teflon tube 4 is
This tube is particularly useful because it has low friction with the prepolymer 1 and the base material 7, but tubes made of other resins or metals are also acceptable.
ãã®ããã«ããŠãå ç±ãžã€ã±ããïŒå
ã®ããã
ã³ããŠãŒãïŒããã¯ãã»ãšãã©æµåæ§ã倱ã€ãŠèª
å·±ä¿åœ¢æ§ãæããã²ã«ç¶ã®æ¯æïŒãçæãããŠæ¥
ãããã®æ¯æïŒã¯ãã¢ã»ãã³ã«äžæº¶ãªæåãããª
ãã¡ç¶²ç¶éåäœã®éšåã奜ãŸããã¯ïŒã90éé
ïŒ
ãããã«å¥œãŸããã¯10ã50ééïŒ
å«ãã§ããã
ãã®æåãå°ãªããããšæµåæ§ã倧ãããªãããŸ
ãå€ããããšåŸã®æ¡æ£å·¥çšã§åéäœMbã®æ¡æ£é
床ãé
ããªããããã®ã§å¥œãŸãããªãã In this way, the Teflon tube 4 in the heating jacket 3 produces a gel-like base material 7 that has almost lost its fluidity and has self-shape retention. The base material 7 preferably contains an acetone-insoluble component, ie, a network polymer portion, in an amount of 5 to 90% by weight, more preferably 10 to 50% by weight.
If this component is too small, the fluidity becomes high, and if it is too large, the diffusion rate of monomer Mb becomes too slow in the subsequent diffusion step, which is not preferable.
ç¶ããŠãæ¯æïŒã¯æ¡æ£è£
眮ïŒã«éã蟌ãŸããã
ãã®æ¡æ£è£
眮ïŒã®äžæ¹éšåã¯æ¶²çžæ¡æ£å®€ïŒãšãªã€
ãŠããŠããã®æ¶²çžæ¡æ£å®€ïŒã«æ³šå
¥å£ïŒïŒãã液ç¶
ã®åéäœMbãäŸçµŠãããããã®åéäœMbã¯æ¶²
çžæ¡æ£å®€ïŒã«æºãããããã®äœå°åã¯æåºå£ïŒïŒ
ããæåºãããã液çžæ¡æ£å®€ïŒã«æ»æºããéã«ã
æ¯æïŒã«ã¯åéäœMbããã®ã»ã©äžå¿ãŸã§æ¡æ£
ããäžå¿è»žããã®è·é¢ã®äºä¹ã«ã»ãŒæ¯äŸããŠé£ç¶
çã«å¢å ãããããªåéäœMbã®æ¿åºŠåŸé
ãæ¯æ
ïŒå
ã«åœ¢æãããããŸãããã®æ¶²çžæ¡æ£å®€ïŒã®å
éäœMbäžã«ã¯ãããã«åšïŒïŒãé
眮ãããŠã
ãŠããã®ããã«åšïŒïŒããçªçŽ ã¬ã¹ã®æ°æ³¡ãçºç
ãããããšã«ããåéäœMbã®èžæ°ãçºçãã
ããããããŠæ°äœç¶ãŸãã¯é§æ»Žç¶ã®åéäœMbã®
èžæ°ãã液çžæ¡æ£å®€ïŒã®äžæ¹ã«åŸç¶ããŠããæ°çž
宀ïŒïŒãŸã§äžæããŠãã®æ°çžå®€ïŒïŒã«å
æºããæ°
çžå®€ïŒïŒã«åéäœMbã®èžæ°ãå«ãé°å²æ°ã圢æ
ãããåéäœMbã¯ææ°å£ïŒïŒããç空ãã³ã
ïŒå³ç€ºããïŒã«ãã€ãŠååãããã液çžæ¡æ£å®€ïŒ
ã¯äºãçªçŽ 眮æãããŠããŠãé
žçŽ ã«ããéåé»å®³
ãé²æ¢ããããã«ããŠããã Subsequently, the base material 7 is fed into a diffusion device 8.
The lower part of this diffusion device 8 is a liquid phase diffusion chamber 9, and liquid monomer Mb is supplied to this liquid phase diffusion chamber 9 from an injection port 10. This monomer Mb is stored in the liquid phase diffusion chamber 9, and the surplus is stored at the discharge port 11.
is discharged from. While staying in the liquid phase diffusion chamber 9,
In the base material 7, monomer Mb diffuses to the center, and a concentration gradient of monomer Mb is formed in the base material 7, which increases continuously in approximately proportion to the square of the distance from the central axis. be done. Further, a bubbler 12 is disposed in the monomer Mb of the liquid phase diffusion chamber 9, and vapor of the monomer Mb is generated by generating nitrogen gas bubbles from the bubbler 12. In this way, the vapor of the monomer Mb in the form of gas or droplets rises to the gas phase chamber 13 following the liquid phase diffusion chamber 9, fills this gas phase chamber 13, and enters the gas phase chamber 13. An atmosphere containing monomeric Mb vapor is formed. Monomer Mb is recovered from the exhaust port 17 by a vacuum pump (not shown). Liquid phase diffusion chamber 9
is substituted with nitrogen in advance to prevent inhibition of polymerization by oxygen.
åéäœMbã®æ¡æ£ãçµãã€ãæ¯æïŒã¯ãããã
ãŠåéäœMbã®èžæ°ãå«ãé°å²æ°ã«ãã€ãŠæºãã
ããæ°çžå®€ïŒïŒã«å°å
¥ããããæ°çžå®€ïŒïŒã¯ãã
ããåãå²ãå€åŽç®¡ïŒïŒã«æµãããæž©æ°Žã«ãã€ãŠ
å ç±ãããŠããããã®æ°çžå®€ïŒïŒã«æ»æºããé
ã«ãæ¡æ£ããåéäœMbã®äžéšãåç¬ã§ãããã¯
æ¯æïŒäžã«æ®çããŠããåéäœMaããã¬ããªã
ãŒãšéåãããã®çµæãåéäœMbã®æ¿åºŠåŸé
ã
æ¯æïŒå
ã«åºå®ãããŠããããã®éãæ¯æïŒã¯å
éäœMbã®èžæ°ãå«ãã§ããé°å²æ°ã«å
ãŸããŠã
ããããæ¯æïŒã®å€åšéšããæ°çžäžãžåéäœMb
ãèžçºããã®ãæå¶ããããã²ããŠã¯ãå€åšéšä»
è¿ã«ãããå±æçã®æªã¿ãã»ãšãã©ååšããªãã
ãããã¯çãç¯å²ã§ããååšããªãå
äŒéäœãç
æã§ãããåéäœMbã¯æ°çžäžã«å°ããšããã®é£œ
åæ¿åºŠã®20ïŒ
以äžå«ãŸããã®ã奜ãŸãããããã
ãã°ãåéäœMbã®æ¿åºŠïŒèžæ°å§ïŒãæ¯æïŒã®å€
åšéšã«æ¡æ£ããåéäœMbã®æ¿åºŠïŒèžæ°å§ïŒãšã»
ãŒçããããã以äžãšãªããåéäœMbã®æ¿åºŠã
æ¯æå€åšéšãããæ°çžäžã§å€§ãããã°ãåéäœ
Mbã®å ç±éåãšåæã«åéäœMbã®æ°çžããæ¯
æäžãžã®æ¡æ£ãè¡ãããã The base material 7 in which the monomer Mb has been diffused is thus introduced into the gas phase chamber 13 filled with an atmosphere containing the monomer Mb vapor. The gas phase chamber 13 is heated by hot water flowing through an outer tube 14 surrounding it. While remaining in this gas phase chamber 13, a part of the diffused monomer Mb polymerizes alone or with the monomer Ma or prepolymer remaining in the base material 7, and as a result, the monomer Mb The concentration gradient of body Mb is fixed in the base material 7. At this time, since the base material 7 is surrounded by an atmosphere containing the vapor of the monomer Mb, the monomer Mb flows from the outer periphery of the base material 7 into the gas phase.
evaporation is suppressed. As a result, it is possible to produce an optical transmission body in which distortion in the refractive index near the outer periphery is almost absent or exists only in a narrow range. It is preferable that the monomeric Mb is contained in the gas phase in an amount of at least 20% or more of its saturation concentration. By doing so, the concentration (vapor pressure) of the monomer Mb becomes approximately equal to or higher than the concentration (vapor pressure) of the monomer Mb diffused into the outer peripheral portion of the base material 7. If the concentration of monomer Mb is higher in the gas phase than at the outer periphery of the base material, the monomer Mb
At the same time as the heating polymerization of Mb, the monomer Mb diffuses from the gas phase into the base material.
液çžæ¡æ£å®€ïŒäžã®åéäœMbã®æž©åºŠã¯ãç¹ã«ã
ã®åéäœMbããèžæ°ãçºçããããããªå Žåã
åéäœMbãæ¯èŒçé«ãèžæ°å§ãæããã€æ¯æå
ã«æ¡æ£ã§ããå€ã«ä¿ãããå¿
èŠããããäŸãã°ïŒ
ã90âã«èšå®ãããããã®æž©åºŠãé«ããªãã°ãªã
ã»ã©ãåéäœMbã®æ¡æ£é床ã¯å€§ãããªãããæ¯
æèªäœã®éåé床ãå¢å€§ããŠããŸãããŸãåéäœ
Mbã液çžäžã§éåããŠç²çš ãšãªãã®ã§å¥œãŸãã
ãªãããŸããæ¯æãæ¡æ£å®€ïŒäžã«æ»æºãããŠãã
æéïŒæ¡æ£æéïŒããã³äžèšæ¡æ£æž©åºŠã¯ãåŸãã
ãšããå
äŒéäœã®å±æçåŸé
ããªãã¡åéäœMb
ã®äžèšæ¿åºŠåŸé
ã«ãã€ãŠæ±ºãããããããããã
ã®æ¡æ£æéã極床ã«é·ãã€ããæ¡æ£æž©åºŠãé«ãã
ãããããšãåéäœMbã®æ¿åºŠåŸé
ãå¹³åŠåãã
ããããã¯æ¯æã®å€åšéšä»è¿ã§æ¿åºŠåŸé
ãæ¥ã«å€§
ãããªãæãããããææã®å±æçåŸé
ãåŸãã
ãªãã The temperature of the monomer Mb in the liquid phase diffusion chamber 9 is particularly high when vapor is generated from the monomer Mb.
Monomer Mb has a relatively high vapor pressure and must be maintained at a value that allows it to diffuse into the matrix, for example 5
Set to ~90â. As this temperature increases, the diffusion rate of the monomer Mb increases, but the polymerization rate of the base material itself also increases, and the monomer Mb also increases.
This is not preferred because Mb polymerizes in the liquid phase and becomes viscous. In addition, the time for which the base material is retained in the diffusion chamber 8 (diffusion time) and the above-mentioned diffusion temperature are determined by the refractive index gradient of the optical transmission body to be obtained, that is, the monomer Mb
is determined by the above concentration gradient of . However, if this diffusion time is extremely long or the diffusion temperature is too high, the concentration gradient of the monomer Mb may flatten or suddenly increase near the outer periphery of the base material. refractive index gradient cannot be obtained.
ãã®å®æœäŸã§ã¯ã液çžæ¡æ£å®€ïŒã®åéäœMbã
å©çšããŠæ°çžå®€ïŒïŒã®é°å²æ°ã圢æããŠãããã
ãªãã¡åéäœMcãåéäœMbãšåäžã®å Žåã«ã€
ããŠç€ºããŠããããåéäœMcã¯åéäœMbãšã¯
ç°ãªããã®ããããã®æ··åç©ã§ãã€ãŠãããããŸ
ãåéäœMbãšãããšã¯å¥ã®åéäœãšã®æ··åç©ã§
ãã€ãŠããããåéäœMbãšã¯å
šãç°ãªãæ°äœç¶
ãŸãã¯é§æ»Žç¶ã®åéäœMcãæ°çžäžã«å«æããã
å Žåã«ã¯ãæ°çžå®€ïŒïŒãšæ¶²çžæ¡æ£å®€ïŒãšãä»å
ãã液çžæ¡æ£å®€ïŒäžã®åéäœMbãããã«ããã«
液çžæ¡æ£ã«ã®ã¿çšããããããŠãæ°çžå®€ïŒïŒã«ã¯
æ°äœç¶ãŸãã¯é§æ»Žç¶ã®åéäœMcãèžæ°çºçåšç
ããå°å
¥ããããŸããå®æœäŸã®å Žåãšåæ§ã«ããŠ
åéäœMbã®èžæ°ãæ°çžå®€ã«æºãããããã«å¥ã®
åéäœMcã®èžæ°ãæ°çžå®€ã«å°ããšãæ°çžå®€å
ã¯
åéäœMbã®èžæ°ãšåéäœMcã®èžæ°ãšãæ··åã
ãç³»ã«ãªãããã®ãããªå ŽåãåéäœMcãåžžæž©
ã§æ°äœã§ãããããªååç©ã§ãã€ãŠã䜿çšå¯èœãš
ãªãããã ãããããã®å Žåã«ãããŠããåéäœ
MaïŒMbããã³Mcã®åç¬éåäœPaïŒPbïŒPcã®
å±æçãããããNaïŒNbïŒNcãšããå Žåã«ã
NbãNaããã倧ãããã°NcãNaããã倧ã
ããéã«NbãNaãããå°ããå Žåã«ã¯ãNcã
Naããå°ãããããªçµåããéžã°ãªããã°ãæ
æã®å±æçååžã¯åŸãããªãã In this embodiment, the monomer Mb in the liquid phase diffusion chamber 9 is used to form the atmosphere in the gas phase chamber 13. In other words, the case where monomer Mc is the same as monomer Mb is shown, but monomer Mc may be different from monomer Mb or a mixture thereof, and monomer Mb and this It may also be a mixture with other monomers. When a gaseous or atomized monomer Mc that is completely different from the monomer Mb is contained in the gas phase, the gas phase chamber 13 and the liquid phase diffusion chamber 9 are partitioned, and the liquid phase diffusion chamber 9 is monomeric Mb is used only for liquid phase diffusion without bubbling. Then, a gaseous or mist-like monomer Mc is introduced into the gas phase chamber 13 from a steam generator or the like. In addition, when the vapor of monomer Mb is filled in the gas phase chamber in the same manner as in the example, and the vapor of another monomer Mc is introduced into the gas phase chamber, the vapor of monomer Mb is inside the gas phase chamber. The system is a mixture of the monomer Mc and the monomer Mc vapor. In such a case, even if the monomer Mc is a compound that is a gas at room temperature, it can be used. However, in any case, the monomer
When the refractive index of homopolymers Pa, Pb, and Pc of Ma, Mb, and Mc are Na, Nb, and Nc, respectively,
If Nb is larger than Na, Nc is also larger than Na, and conversely, if Nb is smaller than Na, Nc is also larger than Na.
Unless a combination is selected in which Na is smaller than Na, the desired refractive index distribution cannot be obtained.
æ°çžå®€ïŒïŒã§ã®å ç±éååŸãæ¯æïŒã¯ããã«çª
çŽ çœ®æãããŠããç±åŠç管ïŒïŒã«å°ãããŠãå ç±
éåãå®çµãããããã®ç±åŠç管ïŒïŒã¯ããŒã¿ïŒ
ïŒã«ãã€ãŠå ç±ãããŠãããããã®ããŒã¿ïŒïŒã®
枩床ãè£
眮ã®äžéšããäžéšãžãšæ®µéçã«é«æž©ã«ã
ãŠããããšã«ãã€ãŠã枩床åŸé
ã圢æããããã
ã«ããŠãããããŸããã®ç±åŠç管ïŒïŒã«ãåéäœ
Mbã®èžæ°ãå°å
¥ãããŠããŠããã After heating and polymerizing in the gas phase chamber 13, the base material 7 is further led to a heat treatment tube 15 that is purged with nitrogen, and the heating and polymerization is completed. This heat treatment tube 15 is the heater 1
However, a temperature gradient may be formed by increasing the temperature of the heater 16 stepwise from the bottom to the top of the device. Also, this heat treatment tube 15 also contains a monomer.
Mb vapor may be introduced.
ããããŠåŸãããå
äŒéäœïŒïŒã®å±æçã¯ãåŸ
è¿°ããããã«åéäœMaãšåéäœMbãšã®çµåã
ã«ãã€ãŠãäžå¿è»žããã®è·é¢ã®äºä¹ã«ã»ãŒæ¯äŸã
ãŠååŸæ¹åã«é£ç¶çã«å¢å€§ãããã¯æžå°ããå±æ
çåŸé
ãæããŠããããã®å±æçã¯å
äŒéäœã®é·
ãæ¹åã«ã¯å€åããäžå®ã§ããã As will be described later, the refractive index of the light transmitting body 18 obtained in this way varies continuously in the radial direction approximately in proportion to the square of the distance from the central axis due to the combination of monomer Ma and monomer Mb. It has a refractive index gradient that increases or decreases. This refractive index does not change in the length direction of the optical transmission body and remains constant.
äžè¿°ããå®æœäŸã§ã¯ãæ¯æã圢æãããå·¥çšã
åéäœMbãæ¡æ£ãããå·¥çšããã³ç±åŠçå·¥çšã
ãã¹ãŠé£ç¶çã«è¡ã€ãŠãããããåäžãªç¹æ§ãæ
ããã€å質ã®äžå®ãªå
äŒéäœã補é å¯èœãšãªãã In the embodiments described above, the step of forming the base material,
Since the step of diffusing monomer Mb and the heat treatment step are all carried out continuously, it is possible to manufacture an optical transmission body with uniform characteristics and constant quality.
ãã®çºæã®æ¹æ³ã«ãããŠãåéäœMaãšããŠã¯
éåããŠéæã§å±æçãNaã®ç¶²ç¶éåäœPaãç
æããããšãã§ããåéäœã䜿çšããããããã®
åéäœã¯åäžã®åéäœã§ãã€ãŠãè€æ°åã®åéäœ
ã®æ··åç©ã§ãã€ãŠãããããã®ãããªåéäœMa
ãšããŠã¯ãã¢ãªã«åºãã¢ã¯ãªã«é
žåºãã¡ã¿ã¯ãªã«
é
žåºããã³ããã«åºã®ãããªäºéçµåãå«ãåºã
ããããïŒå以äžæãããããããã®ãã¡ã®ïŒçš®
é¡ä»¥äžãåæã«æããåéäœã奜é©ã§ããã次ã«
åéäœMaã®å
·äœäŸãæããã In the method of this invention, a monomer that can be polymerized to produce a transparent network polymer Pa having a refractive index of Na is used as the monomer Ma, and this monomer is a single monomer. It may be a monomer or a mixture of a plurality of monomers. Such a monomer Ma
As the monomer, monomers each having two or more double bond-containing groups such as an allyl group, an acrylic acid group, a methacrylic acid group, and a vinyl group, or having two or more of these groups at the same time, are preferable. . Next, a specific example of monomer Ma will be given.
(1) ã¢ãªã«ååç©ããã³ãã®æ··åç©ã(1) Allyl compounds and mixtures thereof.
ãã¿ã«é
žãžã¢ãªã«ãã€ãœãã¿ã«é
žãžã¢ãªã«ãã
ã¬ãã¿ã«é
žãžã¢ãªã«ããžãšãã¬ã³ã°ãªã³ãŒã«ãã¹
ã¢ãªã«ã«ãŒãããŒãçã®ãžã¢ãªã«ãšã¹ãã«ïŒããª
ã¡ãªãé
žããªã¢ãªã«ããªã³é
žããªã¢ãªã«ãäºãªã³
é
žããªã¢ãªã«çã®ããªã¢ãªã«ãšã¹ãã«ïŒã¡ã¿ã¯ãª
ã«é
žã¢ãªã«ãã¢ã¯ãªã«é
žã¢ãªã«çã®äžé£œåé
žã¢ãª
ã«ãšã¹ãã«ã Diallyl esters such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and diethylene glycol bisallyl carbonate; triallyl esters such as triallyl trimellitate, triallyl phosphate, and triallyl phosphite; unsaturated materials such as allyl methacrylate and allyl acrylate Acid allyl ester.
(2) R1âR2âR3ã§è¡šããããååç©ããã³ãã®
æ··åç©ã(2) A compound represented by R 1 âR 2 âR 3 and a mixture thereof.
R1ããã³R3ãããããããã«åºãã¢ã¯ãªã«é
ž
åºãããã«ãšã¹ãã«åºããŸãã¯ã¡ã¿ã¯ãªã«é
žåºã§
ããååç©ïŒR1ããã³R3ã®ããããäžæ¹ããã
ã«åºãã¢ã¯ãªã«é
žåºãã¡ã¿ã¯ãªã«é
žåºããã³ãã
ã«ãšã¹ãã«åºã®ïŒã€ã®åºã®ãã¡ã®ããããã§ã
ããä»æ¹ãæ®ãã®ïŒã€ã®åºã®ãã¡ã®ããããã§ã
ãååç©ãããã§R2ã¯ä»¥äžã«ç€ºãããïŒäŸ¡ã®åº
ã®ãã¡ããéžæã§ããã A compound in which R 1 and R 3 are both a vinyl group, an acrylic acid group, a vinyl ester group, or a methacrylic acid group; either one of R 1 and R 3 is a vinyl group, an acrylic acid group, a methacrylic acid group, or a vinyl ester A compound in which the other is any of the remaining three groups. Here, R 2 can be selected from the divalent groups shown below.
R2ïŒ
ïŒïœâãŸãã¯ïœâç°æ§äœïŒ
ïŒïœâãŸãã¯ïœâç°æ§äœïŒ
âïŒCH2CH2OïŒnââCH2CH2âïŒïœïŒïŒã20ïŒ
âïŒCH2ïŒpâ ïŒïœïŒïŒã15ïŒ
ïŒïœïŒïœïŒïŒãïŒïŒ
ïŒïœïŒïŒã20ïŒ
(3) äžèš(1)ãš(2)ã®åéäœã®æ··åç©ããŸãã¯ã¢ãã
ãã«ååç©ãããã«ãšã¹ãã«é¡ãã¢ã¯ãªã«é
žãš
ã¹ãã«é¡ããã³ã¡ã¿ã¯ãªã«é
žãšã¹ãã«é¡ã®ïŒçš®
ã®ãã¡ã®å°ãªããšãïŒçš®ãšäžèš(1)ãŸãã¯(2)ã®å
éäœïŒãŸãã¯ãã®æ··åç©ïŒãšã®æ··åç©ã R2 : (p- or m-isomer) (p- or m-isomer) â(CH 2 CH 2 O) n --CH 2 CH 2 â(m=0 to 20) â(CH 2 ) p â (p=3 to 15) (i,j=1~3) (k=0-20) (3) A mixture of the monomers (1) and (2) above, or at least one of the five monovinyl compounds, vinyl esters, acrylic esters, and methacrylic esters. A mixture of a species and the monomer (1) or (2) above (or a mixture thereof).
ãã®çºæã«ãããŠãåéäœMbãšããŠã¯ããã
éåããæã«ãäžèšå±æçNaããã倧ããããŸ
ãã¯å°ããå±æçNbãæããéæãªéåäœPbã
圢æãããã®ãéžã°ããããã®åéäœMbã¯åäž
ã®åéäœã§ãã€ãŠããè€æ°çš®ã®åéäœã®æ··åç©ã§
ãã€ãŠããããéåäœPbã¯ç¶²ç¶éåäœããã³ç·
圢éåäœã®ãããã§ãã€ãŠããããå±æçNbã
å±æçNaãããå°ããå ŽåãåŸãããå
äŒéäœ
ã¯äžèš(1)åŒã§è¡šãããããããªå±æçååžã圢æ
ãããåžã¬ã³ãºäœçšãæãããã®ãšãªããéã«ã
å±æçNbãå±æçNaããã倧ããå Žåã«ã¯ãäž
èš(3)åŒã§è¡šããããå±æçååžã§å¹ã¬ã³ãºäœçšã
æããå
äŒéäœãåŸãããããããã®å±æçã®å·®
ïŒïœNaâNbïœïŒã¯0.005以äžã§ããã®ã奜ãŸã
ãããã®å·®ãå°ãããããšææã®å±æçåŸé
ãåŸ
ãããªãããŸããåéäœMbã¯ãç¹ã«æ°çžæ¡æ£ã
ããå Žåãæ¯èŒçé«ãèžæ°å§ãæãããã®ã§ãã
ã®ã奜ãŸãããäŸãã°æ¡æ£æž©åºŠã«ãããŠïŒmmHg
ãããé«ã飜åèžæ°å§ãæããã®ã奜ãŸãããã
ã®ãããªåéäœMbã®äŸãšããŠã¯ãã¹ãã¬ã³ãã¡
ã¿ã¯ãªã«é
žãšã¹ãã«ãã¢ã¯ãªã«é
žãšã¹ãã«ãé
¢é
ž
ããã«ãå¡©åããã«ãã¢ã¯ãªããããªã«ããã¿ãž
ãšã³ããã³ãããã®æ··åç©ãæããããã In this invention, the monomer Mb is selected from a monomer which forms a transparent polymer Pb having a refractive index Nb greater than or less than the above-mentioned refractive index Na when it is polymerized. This monomer Mb may be a single monomer or a mixture of multiple types of monomers. The polymer Pb may be either a reticular polymer or a linear polymer. When the refractive index Nb is smaller than the refractive index Na, the resulting optical transmission body has a convex lens action with a refractive index distribution as expressed by the above equation (1). vice versa,
When the refractive index Nb is larger than the refractive index Na, an optical transmission body having a concave lens effect can be obtained with the refractive index distribution expressed by the above equation (3). The difference between these refractive indexes (|NaâNb|) is preferably 0.005 or more, and if this difference is too small, a desired refractive index gradient cannot be obtained. In addition, the monomer Mb preferably has a relatively high vapor pressure, especially when diffused in a gas phase, for example, 5 mmHg at the diffusion temperature.
It is preferred to have a saturated vapor pressure higher than . Examples of such monomers Mb include styrene, methacrylates, acrylates, vinyl acetate, vinyl chloride, acrylonitrile, butadiene and mixtures thereof.
ãã®çºæã®ç¶²ç¶éåäœPaãšåéäœMbãšã®çµå
ãã®å¥œãŸããäŸãšããŠã¯åŸè¿°ãããããªäœè²åå·®
ã®å
äŒéäœã®è£œé ã«é©ãããã®ã®ä»ã«æ¬¡ã®ãããª
çµåããæããããããŸãNaïŒNbã®å Žåããã¿
ã«é
žãžã¢ãªã«éåäœâã¡ã¿ã¯ãªã«é
žã¡ãã«ããã¿
ã«é
žãžã¢ãªã«éåäœâã¢ã¯ãªã«é
žã¡ãã«ãšã¡ã¿ã¯
ãªã«é
žã¡ãã«ãšã®æ··åç©ãã€ãœãã¿ã«é
žãžã¢ãªã«
éåäœâã¡ã¿ã¯ãªã«é
žã¡ãã«ããã¿ã«é
žãžã¢ãªã«
éåäœãšã¹ãã¬ã³ãšã®å
±éåäœâã¡ã¿ã¯ãªã«é
žãš
ã¹ãã«ãã€ãœãã¿ã«é
žãžã¢ãªã«ãšã¹ãã¬ã³ãšã®å
±
éåäœâã¢ã¯ãªã«é
žãšã¹ãã«ããã¿ã«é
žãžããã«
ãšå®æ¯éŠé
žãžããã«ãšã®å
±éåäœâã¡ã¿ã¯ãªã«é
ž
ãšã¹ãã«ãã€ãœãã¿ã«é
žãžããã«ãšå®æ¯éŠé
žãã
ã«ãšã®å
±éåäœâã¡ã¿ã¯ãªã«é
žãšã¹ãã«ãå®æ¯éŠ
é
žããã«ãšã€ãœãã¿ã«é
žãžã¢ãªã«ãšã®å
±éåäœâ
ã¡ã¿ã¯ãªã«é
žãšã¹ãã«ãªã©ã§ããããŸããNaïŒ
Nbã®å Žåã®äŸã¯ããžãšãã¬ã³ã°ãªã³ãŒã«ãã¹ã¢
ãªã«ã«ãŒãããŒãéåäœâã¹ãã¬ã³ããžãšãã¬ã³
ã°ãªã³ãŒã«ãã¹ã¢ãªã«ã«ãŒãããŒãéåäœâã€ãœ
ãã¿ã«é
žãžã¢ãªã«ãªã©ã§ããã Preferred examples of the combinations of the network polymer Pa and the monomer Mb of the present invention include those suitable for producing a light transmitting body with low chromatic aberration as described below, as well as the following combinations. First, in the case of Na > Nb, diallyl phthalate polymer - methyl methacrylate, diallyl phthalate polymer - mixture of methyl acrylate and methyl methacrylate, diallyl isophthalate polymer - methyl methacrylate, diallyl phthalate polymer Copolymer with styrene - methacrylic acid ester, copolymer with diallyl isophthalate and styrene - acrylic acid ester, copolymer with divinyl phthalate and divinyl benzoate - methacrylic acid ester, divinyl isophthalate and vinyl benzoate - Copolymer of methacrylic acid ester, vinyl benzoate and diallyl isophthalate -
Such as methacrylic acid ester. Also, Na<
Examples of Nb include diethylene glycol bisallyl carbonate polymer-styrene, diethylene glycol bisallyl carbonate polymer-diallyl isophthalate, and the like.
ãŸããç¹ã«ãäœè²åå·®ã®åææš¹èå
äŒéäœã補
é ããã«é©ããåéäœMaãšåéäœMbãšã®çµå
ããšããŠã¯ã次ã®ãããªãã®ãäŸç€ºã§ããã In addition, the following combinations of monomer Ma and monomer Mb are particularly suitable for producing a synthetic resin optical transmission body with low chromatic aberration.
(a) MaãšããŠãžãšãã¬ã³ã°ãªã³ãŒã«ãã¹ã¢ãªã«
ã«ãŒãããŒãããŸãã¯ãããšãã¿ã«é
žãžã¢ãª
ã«ãã€ãœãã¿ã«é
žãžã¢ãªã«ãå®æ¯éŠé
žããã«ã
ããã¯ã¹ãã¬ã³ãšã®æ··åç©ïŒãã ãããã®æ··å
ç©äžã®ãžãšãã¬ã³ã°ãªã³ãŒã«ãã¹ã¢ãªã«ã«ãŒã
ããŒãã®éã¯50ééïŒ
以äžã§ããã®ã奜ãŸã
ãããã奜ãŸããã¯70ééïŒ
以äžã§ããïŒã
MbãšããŠãååç©(A)ïŒ
ãåŒäžãã¯æ°ŽçŽ ååãŸãã¯ã¡ãã«åºãã¯
ããšãã«åºãã¡ãã«ããšãã«åºãããã«åºãïœ
âãããã«åºãïœâããã«åºãïœâããã«åºã
ïœâããã«åºã
ïŒïœïŒïŒãïŒïŒã
ïŒïœïŒïŒãïŒïŒããã³
ïŒâCH2CH2OïŒzCH3ïŒïœïŒïŒãïŒïŒãããªã矀ã
ãéžã°ããåºãè¡šãããã
ã§è¡šããããååç©ãŸãã¯ãã®æ··åç©ã(a) Diethylene glycol bisallyl carbonate as Ma, or a mixture thereof with diallyl phthalate, diallyl isophthalate, vinyl benzoate or styrene (provided that the amount of diethylene glycol bisallyl carbonate in this mixture is not less than 50% by weight) (more preferably 70% by weight or more).
Compound (A) as Mb: [Wherein, X is a hydrogen atom or a methyl group, Y is a phenyl group, a methylphenyl group, a vinyl group, i
-propyl group, i-butyl group, s-butyl group,
t-butyl group, (x=0~2), Represents a group selected from the group consisting of (y=0-2) and (-CH 2 CH 2 O) z CH 3 (z=1-3). ] A compound represented by or a mixture thereof.
(b) MaãšããŠãžãšãã¬ã³ã°ãªã³ãŒã«ãã¹ã¢ãªã«
ã«ãŒãããŒãããŸãã¯ãããšã¢ã¯ãªã«é
žã¡ã
ã«ãã¢ã¯ãªã«é
žãšãã«ãã¡ã¿ã¯ãªã«é
žïœâãã
ã«ãããã¯ã¡ã¿ã¯ãªã«é
žïœâããã«ãšã®æ··åç©
ïŒãã ãããã®æ··åç©äžã®ãžãšãã¬ã³ã°ãªã³ãŒ
ã«ãã¹ã¢ãªã«ã«ãŒãããŒãã®éã¯10ééïŒ
以äž
ã§ããã®ã奜ãŸããïŒãMbãšããŠãååç©(B)
ãåŒäžãã¯æ°ŽçŽ ååãŸãã¯ã¡ãã«åºã§ã
ããã¯âïŒCF2ïŒiïŒïœïŒïŒãïŒïŒãâCH2
ïŒCF2ïŒjïŒïœïŒïŒãïŒïŒãâCH2CH2OCH2CF3ã
âïŒCH2CH2OïŒkCF2CF2HïŒïœïŒïŒãïŒïŒã
âïŒCH2CH2OCH2ïŒCF2ïŒlïŒïœïŒïŒãïŒïŒã
âCH2ïŒCF2ïŒnïŒCF2ïŒoïŒïœïŒïŒãïŒãïœïŒïŒ
ãïŒïŒããæã矀ããéžã°ããåºãè¡šãããã
ã§è¡šããããã¡ã¿ã¯ãªã«é
žãŸãã¯ã¢ã¯ãªã«é
žã®
å«ããçŽ ã¢ã«ã³ãŒã«ãšã¹ãã«ããäžèšäžè¬åŒ(B)
ã«ãããŠïŒ¹ãâSiïŒOC2H5ïŒ3ã§ããååç©(C)ã(b) Diethylene glycol bisallyl carbonate as Ma, or a mixture thereof with methyl acrylate, ethyl acrylate, n-butyl methacrylate or t-butyl methacrylate (however, the amount of diethylene glycol bisallyl carbonate in this mixture is 10 % by weight or more). Compound (B) as Mb [In the formula, X is a hydrogen atom or a methyl group, and Y is -(CF 2 ) i F (i = 1 to 6), -CH 2
(CF 2 ) j H (j = 1 to 8), -CH 2 CH 2 OCH 2 CF 3 , -(CH 2 CH 2 O) k CF 2 CF 2 H (k = 1 to 4), -(CH 2 CH 2 OCH 2 (CF 2 ) l F (l = 1 to 6), -CH 2 (CF 2 ) n O (CF 2 ) o F (m = 1 to 2, n = 1
~4) represents a group selected from the group consisting of ] Fluorine-containing alcohol ester of methacrylic acid or acrylic acid, or the above general formula (B)
A compound (C) in which Y is -Si( OC2H5 ) 3 .
(c) åéäœMaãšããŠãžãšãã¬ã³ã°ãªã³ãŒã«ãã¹
ã¢ãªã«ã«ãŒãããŒããšäžèšååç©(B)ãŸãã¯(C)ãš
ã®æ··åç©ïŒãã ãããã®æ··åç©äžã®ãžãšãã¬ã³
ã°ãªã³ãŒã«ãã¹ã¢ãªã«ã«ãŒãããŒãã®éã¯10é
éïŒ
以äžã§ããã®ã奜ãŸããïŒãåéäœMbãš
ããŠäžèšååç©(A)ã(c) A mixture of diethylene glycol bisallyl carbonate as the monomer Ma and the above compound (B) or (C) (however, the amount of diethylene glycol bisallyl carbonate in this mixture is preferably 10% by weight or more). The above compound (A) as monomer Mb.
ãã®çºæã®åéäœMcã¯ãåéäœMbãšåäžãŸ
ãã¯ç°ãªãåéäœã§ãã€ãŠå±æçNcã®éåäœPc
ãçæãããã®ã§ããããã®åéäœMcãåäžã®
åéäœããã³è€æ°çš®ã®åéäœã®æ··åç©ã®ãããã§
ãã€ãŠãããããŸãåéäœMbãšããŠäŸç€ºããã
äžèšååç©ã®äœããåéäœMcãšããŠäœ¿çšå¯èœã§
ããããããŠãç¹ã«èžæ°å§ãé«ããã®ã奜é©ã§ã
ãã The monomer Mc of this invention is a polymer Pc which is the same or different from the monomer Mb and has a refractive index Nc.
is generated. This monomer Mc may be either a single monomer or a mixture of multiple types of monomers, and any of the above compounds exemplified as monomer Mb can be used as monomer Mc. It is. In particular, those with high vapor pressure are suitable.
次ã«ããã®çºæã®å ·äœäŸã瀺ãã Next, a specific example of this invention will be shown.
å
·äœäŸ ïŒ
éåéå§å€ãšããŠ3.0ééïŒ
ã®éé
žåãã³ãŸã€
ã«ïŒBPOïŒã溶解ããããžãšãã¬ã³ã°ãªã³ãŒã«
ãã¹ã¢ãªã«ã«ãŒãããŒãïŒCRâ39ïŒã75âã§65
åéå ç±ããŠäºåéåããã²ã«åçŽåã§æµåæ§ã
ä¿æããŠãããã¬ããªããŒãåŸãããã®ãã¬ããª
ããŒã®ç²åºŠã¯20âã§1015cpã§ãããäžèš(4)åŒã«
ãããããã³ïœã®å€ã¯ãããã2.57Ã10-2cm2
dyne-1sec-1ããã³1.21ã§ãã€ãããã®ãã¬ããª
ããŒïŒã第ïŒå³ã«ç€ºãè£
眮ã®æŒåºãåšïŒã«å
¥ãã
å ç±ãžã€ã±ããïŒã貫éããŠãããããã³ããŠãŒ
ãïŒïŒçŽåŸïŒmmãé·ã200mmïŒã®äžãž6.3Ã10-2
mlïŒminã®äžå®æµéã§é£ç¶çã«éã蟌ãã ãå ç±
ãžã€ã±ããïŒã«ã¯äžéšã«78âã®æž©æ°ŽïŒãäžéšã«58
âã®æž©æ°ŽïŒãããããæµãããšã«ãã€ãŠæž©åºŠåŸé
ã圢æãããããããã³ããŠãŒãïŒäžã40åéã§
ééããéã«ããã¬ããªããŒïŒã¯ã²ã«åããïŒmm
Ïã®æ¯æïŒã«æ圢ãããããã®æ¯æïŒã¯ã¢ã»ãã³
ã«äžæº¶ãªæåïŒç¶²ç¶éåäœéšåïŒ25ééïŒ
ãã¢ã»
ãã³ã«å¯æº¶ã ãã¡ã¿ããŒã«ã«äžæº¶ã®æåïŒç·åœ¢é
åäœéšåïŒïŒééïŒ
ãã¢ã»ãã³ãšã¡ã¿ããŒã«ã®äž¡
æ¹ã«å¯æº¶ãªæåïŒåéäœããã³äœååéãã¬ããª
ããŒéšåïŒ70ééïŒ
ããæã€ãŠãããSpecific example 1 Diethylene glycol bisallyl carbonate (CR-39) in which 3.0% by weight of benzoyl peroxide (BPO) was dissolved as a polymerization initiator was heated at 75â for 65 minutes.
The mixture was prepolymerized by heating for a minute to obtain a prepolymer that maintained fluidity just before gelation. The viscosity of this prepolymer is 1015 cp at 20°C, and the values of K and n in the above equation (4) are each 2.57 à 10 -2 cm 2
dyne -1 sec -1 and 1.21. This prepolymer 1 is put into an extruder 2 of the apparatus shown in FIG.
6.3Ã10 -2 into the Teflon tube 4 (diameter 4 mm, length 200 mm) passing through the heating jacket 3.
It was fed continuously at a constant flow rate of ml/min. Heating jacket 3 has 78â hot water 5 on the top and 58â on the bottom.
A temperature gradient was created by flowing hot water 6 at a temperature of .degree. While passing through Teflon tube 4 for 40 minutes, prepolymer 1 gels and becomes 4 mm thick.
It was molded into a base material 7 of Ï. This base material 7 consists of 25% by weight of a component insoluble in acetone (reticular polymer portion), 5% by weight of a component soluble in acetone but insoluble in methanol (linear polymer portion), and a component soluble in both acetone and methanol. It consisted of 70% by weight (monomers and low molecular weight prepolymer parts).
次ãã§ãæ¯æïŒãåŒãäžãè£
眮ã«ãã€ãŠ0.25
cmïŒåã®äžå®é床ã§æ¡æ£è£
眮ïŒã«å°å
¥ããã液çž
æ¡æ£å®€ïŒã«ã¯ãã¡ã¿ã¯ãªã«é
žâïŒïŒïŒïŒïŒâããª
ãã€ããããŒãã«ãªããããã«ïŒ4FMAïŒã1.0
mlïŒåã®äžå®æµéã§æµå
¥ãããããã®4FMAã¯é
åçŠæ¢å€ãæ·»å ããªãã§çšããããŸãããã®
4FMAäžã«200mlïŒåã®æµéã§çªçŽ ãããã«ãã
ãããšã«ããã4FMAã®èžæ°ãçºçãããŠãæ°çž
宀ïŒïŒã4FMAã®èžæ°ã§æºãããã液çžæ¡æ£å®€ïŒ
ã®æž©åºŠã¯70âãšãããŸãæ°çžå®€ïŒïŒã¯80âã®æž©æ°Ž
ãå€åŽç®¡ã«æµãããšã«ããå æž©ãããŠããã
4FMAã®èžæ°ã¯ç空ãã³ãã«ãã€ãŠ800mlïŒåã®
æµéã§ååããããã©ããäžã§æ¶²åãããã液å
ãã4FMAããã³æ¶²çžæ¡æ£å®€ïŒïŒããæµåºãã
4FMAã¯ã»ãšãã©éåããŠãããããã®ãŸãŸç¹°è¿
ã䜿çšã§ããããªããæ°çžå®€ïŒïŒã«ã¯äºã1000
mlïŒåã®æµéã§çªçŽ ã¬ã¹ãæµå
¥ãããŠçªçŽ 眮æã
ãŠãããã Next, the base material 7 is pulled up to 0.25
It was introduced into the diffuser 8 at a constant speed of cm/min. The liquid phase diffusion chamber 9 contains 1.0% of 1,1,3-trihydroperfluoropropyl methacrylate (4FMA).
A constant flow rate of ml/min was applied. This 4FMA was used without adding a polymerization inhibitor. Also, this
The vapor of 4FMA was generated by bubbling nitrogen into the 4FMA at a flow rate of 200 ml/min, and the gas phase chamber 13 was filled with the vapor of 4FMA. Liquid phase diffusion chamber 9
The temperature was 70°C, and the gas phase chamber 13 was heated by flowing hot water at 80°C through the outer tube.
The 4FMA vapor was collected by a vacuum pump at a flow rate of 800 ml/min and liquefied in the trap. Liquefied 4FMA and liquid phase diffusion chamber 19 flowed out.
4FMA was hardly polymerized and could be used repeatedly as is. In addition, the gas phase chamber 13 is filled with 1000
Nitrogen gas was introduced at a flow rate of ml/min for nitrogen replacement.
æ¯æïŒã液çžæ¡æ£å®€ïŒã«çŽïŒåéãæ°çžå®€ïŒïŒ
ã«çŽ30åéæ»çãããéã«ã4FMAãæ¡æ£ããã
ãã®äžéšãå ç±éåãããã The base material 7 is placed in the liquid phase diffusion chamber 9 for about 5 minutes, and then placed in the gas phase chamber 13.
While staying for about 30 minutes, 4FMA is diffused,
A part of it was polymerized by heating.
æ¡æ£è£
眮ïŒãçµãæ¯æïŒããç¶ããŠçªçŽ 眮æã
ãç±åŠç管ïŒïŒã«éã蟌ãã ããã®ç±åŠç管ïŒïŒ
ããããŒã¿ïŒã«ãã€ãŠäžéšãããé 次90âã110
âã120âã130âã«å ç±ãã枩床åŸé
ã圢æãã
ãããã®ç±åŠç管ïŒïŒå
ã§æ¯æãïŒæéç±åŠçã
ãŠéåãå®çµãããã The base material 7 that had passed through the diffusion device 8 was then fed into a heat treatment tube 14 that was purged with nitrogen. This heat treatment tube 14
are heated to 90â and 110â sequentially from the bottom by heater 6.
â, 120â, and 130â to form a temperature gradient. The base material was heat treated in this heat treatment tube 14 for 6 hours to complete polymerization.
ãã®ããã«ããŠé£ç¶çã«äœè£œããçŽåŸïŒmmã®æ£
ç¶äœããã¯ãåäžãªå
åŠæ§èœãæããæ£ç¶åžã¬ã³
ãºãããªãã¡ææã®å
äŒéäœãåŸãããããã®æ£
ç¶äœã¯ãäžèš(1)åŒäžã®ïŒ¡ã®å€ã2.22Ã10-2mm-2ã®
å
äŒéäœã§ããããã®æ£ç¶äœäžãèè¡ããŠé²è¡ã
ãå
æã®åšæïŒåŒ(2)ïŒã¯42.5mmã§ãã€ãããŸãã
ãã®æ£ç¶äœã«ã¯ã»ãšãã©å€åšéšãŸã§åŒ(1)ã§è¡šãã
ãããããªå±æçååžã圢æãããŠããã®ã§ãåš
蟺éšãåãèœãšãå¿
èŠããªãã€ããããã«ãåžã¬
ã³ãºãšããŠã®è©äŸ¡ã®å€ãéå£æ°NAã0.45ãšå€§ã
ãã€ãã From the rod-shaped bodies having a diameter of 4 mm that were continuously produced in this manner, a rod-shaped convex lens having uniform optical performance, that is, a desired light transmission body was obtained. This rod-shaped body is an optical transmission body in which the value of A in the above equation (1) is 2.22Ã10 -2 mm -2 , and the period L of the light flux that meanders through this rod-shaped body (equation (2) ) was 42.5mm. Also,
Since this rod-shaped body had a refractive index distribution expressed by equation (1) almost up to the outer periphery, there was no need to shave off the periphery. Furthermore, the evaluation value as a convex lens, the numerical aperture NA, was large at 0.45.
å
·äœäŸ ïŒ
0.10ééïŒ
ã®BPOåã³0.50ééïŒ
ã®åèåççŽ
ïŒCBr4ïŒã溶解ããããšãã¬ã³ã°ãªã³ãŒã«ãžã¡ã¿
ã¯ãªã¬ãŒãïŒEDMAïŒãçªçŽ é°å²æ°äž45âã§50
åéå ç±ããŠã20âã§ã®ç²åºŠã930cpãïŒ3.23
Ã10-2cm2dyne-1sec-1ãããã³ïœïŒ1.19ã®ãã¬ã
ãªããŒãåŸããSpecific Example 2 Ethylene glycol dimethacrylate (EDMA) in which 0.10% by weight of BPO and 0.50% by weight of carbon tetrabromide (CBr 4 ) were dissolved was heated at 45°C under a nitrogen atmosphere for 50 minutes.
Viscosity at 20â after heating for 930cp, K=3.23
A prepolymer with x10 -2 cm 2 dyne -1 sec -1 and n=1.19 was obtained.
åŸããããã¬ããªããŒïŒããå
·äœäŸïŒãšåæ§ã«
æŒåºãåšïŒã«å
¥ããããã«ãäžéšã«60âã®æž©æ°Ž
ïŒãäžéšã«30âã®æž©æ°ŽïŒãããããæµããå ç±ãž
ã€ã±ããïŒã貫éããŠãããããã³ããŠãŒãïŒå
åŸïŒmmãé·ã96mmïŒïŒã«6.0Ã10-2mlïŒåã®äžå®
æµéã§é£ç¶çã«éã蟌ãã ããã®ãããã³ããŠãŒ
ãïŒãééããéã«ããã¬ããªããŒïŒã¯ã²ã«åã
ãŠçŽåŸïŒmmã®åçç¶ã§éæãªæ¯æïŒã«æ圢ãã
ãããã®æ¯æïŒã¯ã¢ã»ãã³ã«äžæº¶ã®æåïŒç¶²ç¶é
åäœéšåïŒ15.5ééïŒ
ãã¢ã»ãã³ã«å¯æº¶ã§ãã€ã¡
ã¿ããŒã«ã«äžæº¶ã®æåïŒç·åœ¢éåäœéšåïŒ0.3é
éïŒ
ãããã³ã¢ã»ãã³ãšã¡ã¿ããŒã«ã®äž¡æ¹ã«å¯æº¶
ã®æåïŒåéäœããã³äœååéãã¬ããªããŒïŒ
84.2ééïŒ
ãããªã€ãŠããã The obtained prepolymer 1 was placed in an extruder 2 in the same manner as in Example 1, and a Teflon tube was inserted through a heating jacket 3 in which hot water 5 at 60°C was poured into the upper part and hot water 6 at 30°C was poured into the lower part. It was continuously fed into a tube (inner diameter 4 mm, length 96 mm) 4 at a constant flow rate of 6.0 x 10 -2 ml/min. While passing through this Teflon tube 4, the prepolymer 1 was gelled and formed into a transparent cylindrical base material 7 with a diameter of 4 mm. This matrix 7 contains 15.5% by weight of a component insoluble in acetone (reticular polymer portion), 0.3% by weight of a component soluble in acetone and insoluble in methanol (linear polymer portion), and soluble in both acetone and methanol. Components (monomers and low molecular weight prepolymers)
It consisted of 84.2% by weight.
ãã®æ¯æïŒããç¶ããŠ4FMAã1.0mlïŒåã®äž
å®æµéã§æ³šå
¥ãããŠãã液çžæ¡æ£å®€ïŒã«éã蟌ã
ã ããã®æ¶²çžæ¡æ£å®€ïŒã®æž©åºŠã¯60âã§ãã€ããã
ã®æ¶²çžæ¡æ£å®€ïŒã«çŽïŒåéæ»çãããéã«ãæ¯æ
ïŒã«4FMAãæ¡æ£ãããããŸãã4FMAäžïŒæ·±ã
24mmïŒã«ã200mlïŒåã®æµéã§çªçŽ ãããã«ãã
ãããšã«ããã4FMAãèžçºãããŠæ°çžå®€ïŒïŒã
4FMAã®èžæ°ã§æºããããããã«ããã®4FMAã®
èžæ°ã800mlïŒåã®æµéã§ååãããæ°çžå®€ïŒïŒ
ã¯å€åŽç®¡ïŒé·ã72mmïŒã«æµãã65âã®æž©æ°Žã§å ç±
ãããŠããããã®æ°çžå®€ïŒïŒã«ãæ¯æïŒãçŽ15å
éæ»çãããã This base material 7 was then fed into a liquid phase diffusion chamber 9 into which 4FMA was injected at a constant flow rate of 1.0 ml/min. The temperature of this liquid phase diffusion chamber 9 was 60°C. While staying in this liquid phase diffusion chamber 9 for about 5 minutes, 4FMA was diffused into the base material 7. Also, in 4FMA (depth
24mm) at a flow rate of 200ml/min to evaporate 4FMA and fill the gas phase chamber 13.
Filled with 4FMA steam. Furthermore, this 4FMA vapor was collected at a flow rate of 800 ml/min. Gas phase chamber 13
was heated with 65°C hot water flowing through an outer tube (72 mm long). The base material 7 was allowed to stay in this gas phase chamber 13 for about 15 minutes.
4FMAãæ¡æ£ããäžéšéåãããåŸãæ¯æïŒã
ç±åŠç管ïŒïŒã«å°ããŠå ç±éåãå®çµããããã
ã®ç±åŠç管ããããŒã¿ãŒïŒïŒã«ãã€ãŠã65âã70
âã85âããã³100âã«å ç±ããããšã«ãã€ãŠæž©
床åŸé
ã圢æãããããã®ããã«ããŠææã®æ£ç¶
å
äŒéäœãé£ç¶çã«è£œé ã§ããããã®å
äŒéäœã§
ã¯ãå±æçååžãæããéšåã®ååŸã1.68mmïŒå
š
äœã®69ïŒ
ïŒã§ãããïŒ3.03Ã10-2mm-2ãïŒ
36.1mmã§ãã€ãããŸãäžå¿ã®çŽåŸ2.7mmã®éšåã¯
éå£æ°NAïŒ0.36ã®æ£ç¶åžã¬ã³ãºã§ãã€ãã After 4FMA was diffused and partially polymerized, the base material 7 was introduced into the heat treatment tube 14 to complete the heat polymerization. This heat-treated tube was heated to 65°C and 70°C by the heater 16.
A temperature gradient was created by heating to 100°C, 85°C and 100°C. In this way, desired rod-shaped light transmitters could be continuously manufactured. In this optical transmission body, the radius of the part with refractive index distribution is 1.68 mm (69% of the whole), A = 3.03 à 10 -2 mm -2 , L =
It was 36.1mm. The central portion with a diameter of 2.7 mm was a rod-shaped convex lens with a numerical aperture NA of 0.36.
第ïŒå³ã¯ãã®çºæã®è£œé æ¹æ³ãå®æœããã®ã«äœ¿
çšå¯èœãªè£œé è£
眮ã®äžäŸã瀺ã瞊æé¢å³ã第ïŒå³
ã¯ç¬¬ïŒå³ã«ç€ºãã補é è£
眮ã®éšåæ¡å€§å³ã§ããã
ãªãå³é¢ã«çšãã笊å·ã«ãããŠãïŒâŠãã¬ããª
ããŒãïŒâŠæŒåºãåšãïŒâŠå ç±ãžã€ã±ãããïŒâŠ
ãããã³ããŠãŒããïŒâŠæ¯æãïŒâŠæ¡æ£è£
眮ãïŒ
âŠæ¶²çžæ¡æ£å®€ãïŒïŒâŠæ°çžå®€ãïŒïŒâŠç±åŠç管ã
ïŒïŒâŠå
äŒéäœãã§ããã
FIG. 1 is a longitudinal sectional view showing an example of a manufacturing apparatus that can be used to carry out the manufacturing method of the present invention, and FIG. 2 is a partially enlarged view of the manufacturing apparatus shown in FIG. 1. In addition, in the symbols used in the drawings, 1...prepolymer, 2...extruder, 3...heating jacket, 4...
Teflon tube, 7... Base material, 8... Diffusion device, 9
...liquid phase diffusion chamber, 13...vapor phase chamber, 14...heat treatment tube,
18... Optical transmission body.
Claims (1)
Maã®äžå®å šãªéåãè¡ã€ãŠèªå·±ä¿åœ¢æ§ãæãã
æ¯æã圢æãã å±æçNaãšã¯ç°ãªãå±æçNbãæããéåäœ
Pbãçæããã€æ¶²äœç¶æ ã«ããåéäœMbããå
èšæ¯æã®è¡šé¢ã«æ¥è§ŠãããŠãã®å éšãžæ¡æ£ããã
ãšå ±ã«ãããã«å ç±éåãããããã«ãããå±æ
çååžãæããåææš¹èå äŒéäœã®è£œé æ¹æ³ã«ã
ããŠã åèšåéäœMaãçšããŠåŸãããæ圢çšæµäœã
æ圢管å ã«éã蟌ãã§ãã®æ圢管å ã§åèšèªå·±ä¿
圢æ§æ¯æãé£ç¶çã«åœ¢æãã 次ãã§ãåèšæ圢管ããé£ç¶çã«åºãŠæ¥ãåèš
èªå·±ä¿åœ¢æ§æ¯æã«ã åèšæ¶²ç¶åéäœMbãå«æãã液çžæ¡æ£å®€ã åèšåéäœMbãšåäžãŸãã¯ç°ãªãåéäœ
Mcã§ãã€ãŠã (a) NcïŒNb (b) NcïŒNaããã³NbïŒNa (c) NcïŒNaããã³NbïŒNa ãªã(a)ã(c)ã®æ¡ä»¶ã®äœããïŒã€ãæºè¶³ããå±æ
çNcãæããéåäœPcãçæããã€äžå®æž©åºŠ
ã«å ç±å¶åŸ¡ãããæ°äœç¶ãŸãã¯é§æ»Žç¶ã®åéäœ
Mcãå«æããæ°çžå®€ã ãé 次ééãããããã«ããããšãç¹åŸŽãšããå
ææš¹èå äŒéäœã®è£œé æ¹æ³ã ïŒ åèšæ°çžå®€ã«ã¯ãåèšåéäœMcããå°ããš
ããã®é£œåæ¿åºŠã®20ïŒ ã«çžåœããéå«æãããŠã
ãããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ã«èšèŒ
ã®åææš¹èå äŒéäœã®è£œé æ¹æ³ã ïŒ åèšåéäœMcãåèšåéäœMbãšåäžã§ã
ãããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ã«èšèŒ
ã®åææš¹èå äŒéäœã®è£œé æ¹æ³ã[Claims] 1. Monomer that produces a network polymer Pa having a refractive index of Na
A polymer that undergoes incomplete polymerization of Ma to form a matrix with self-shape retention, and has a refractive index of Nb different from the refractive index of Na.
A synthetic resin optical transmission body having a refractive index distribution, in which the monomer Mb that generates Pb and is in a liquid state is brought into contact with the surface of the base material and diffused into the interior thereof, and is further heated and polymerized. In the manufacturing method, the molding fluid obtained using the monomer Ma is fed into a molding tube to continuously form the self-shape-retaining base material in the molding tube, and then the self-shape-retaining base material is continuously formed from the molding tube. a liquid phase diffusion chamber containing the liquid monomer Mb; a monomer that is the same as or different from the monomer Mb;
Refraction that satisfies any one of the conditions (a) to (c) that is Mc and (a) Nc=Nb (b) Nc<Na and Nb<Na (c) Nc>Na and Nb>Na A monomer in the form of gas or droplets that forms a polymer Pc with a ratio Nc and is heated and controlled to a constant temperature.
A method for manufacturing a synthetic resin optical transmission body, characterized in that the material is sequentially passed through a vapor phase chamber containing Mc. 2. The synthetic resin optical transmission according to claim 1, wherein the gas phase chamber contains the monomer Mc in an amount corresponding to at least 20% of its saturation concentration. How the body is manufactured. 3. The method for manufacturing a synthetic resin optical transmission body according to claim 1, wherein the monomer Mc is the same as the monomer Mb.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58120625A JPS6012507A (en) | 1983-07-02 | 1983-07-02 | Manufacture of synthetic resin optical transmission body |
US06/626,697 US4587065A (en) | 1983-07-02 | 1984-07-02 | Method for producing light transmitting article of synthetic resin |
DE8484304531T DE3466660D1 (en) | 1983-07-02 | 1984-07-02 | Method and apparatus for producing light transmitting article of synthetic resin |
EP84304531A EP0130838B1 (en) | 1983-07-02 | 1984-07-02 | Method and apparatus for producing light transmitting article of synthetic resin |
US06/827,468 US4689000A (en) | 1983-07-02 | 1986-02-10 | Apparatus for producing light transmitting article of synthetic resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58120625A JPS6012507A (en) | 1983-07-02 | 1983-07-02 | Manufacture of synthetic resin optical transmission body |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6012507A JPS6012507A (en) | 1985-01-22 |
JPH0546522B2 true JPH0546522B2 (en) | 1993-07-14 |
Family
ID=14790855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58120625A Granted JPS6012507A (en) | 1983-07-02 | 1983-07-02 | Manufacture of synthetic resin optical transmission body |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6012507A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS525857A (en) * | 1975-07-01 | 1977-01-17 | Nippon Zeon Co Ltd | Cross-linkable halogen-containing polymecomposition |
-
1983
- 1983-07-02 JP JP58120625A patent/JPS6012507A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS525857A (en) * | 1975-07-01 | 1977-01-17 | Nippon Zeon Co Ltd | Cross-linkable halogen-containing polymecomposition |
Also Published As
Publication number | Publication date |
---|---|
JPS6012507A (en) | 1985-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4587065A (en) | Method for producing light transmitting article of synthetic resin | |
JPH08244130A (en) | Manufacture of transparent article with refractive index gradient | |
JPS60175009A (en) | Production of plastic optical element having refractive index distribution | |
WO1994015005A1 (en) | Shaped articles of graduated refractive index | |
JPH0576602B2 (en) | ||
JPH0546522B2 (en) | ||
JPH0259961B2 (en) | ||
JPH0614125B2 (en) | Method for manufacturing synthetic resin optical transmitter | |
JPWO2004068202A1 (en) | Fabrication method of refractive index distribution type optical transmitter by spontaneous frontal polymerization using heat storage effect | |
JPH0225484B2 (en) | ||
JPH0629885B2 (en) | Method for manufacturing synthetic resin optical transmitter | |
JPH0727928A (en) | Production of plastic optical transmission body | |
JPH0355801B2 (en) | ||
JPH0614124B2 (en) | Method for manufacturing synthetic resin optical transmitter | |
JPH0237561B2 (en) | ||
JPH0621886B2 (en) | Method for manufacturing synthetic resin optical transmitter | |
JPH0546523B2 (en) | ||
JPH0579962B2 (en) | ||
KR0170480B1 (en) | Preparation process of polymeric rod and gradient-index rod lens using free radical bulk polymerization with temperature gradient | |
JPH0252241B2 (en) | ||
JPH06186442A (en) | Distributed refractive index type plastic optical transmission body | |
JPH0621885B2 (en) | Diffusion processing device for synthetic resin objects | |
JPH08201637A (en) | Continuous production of synthetic resin light transmission body | |
JPH09178959A (en) | Production of preform for distributed refractive index plastic optical fiber | |
JPH11153717A (en) | Production of graded index optical fiber |