JPS6237505B2 - - Google Patents
Info
- Publication number
- JPS6237505B2 JPS6237505B2 JP54173444A JP17344479A JPS6237505B2 JP S6237505 B2 JPS6237505 B2 JP S6237505B2 JP 54173444 A JP54173444 A JP 54173444A JP 17344479 A JP17344479 A JP 17344479A JP S6237505 B2 JPS6237505 B2 JP S6237505B2
- Authority
- JP
- Japan
- Prior art keywords
- sio
- manufacturing
- group
- units
- silicone
- 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
Links
- 229920001296 polysiloxane Polymers 0.000 claims description 29
- -1 siloxanes Chemical class 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229920002050 silicone resin Polymers 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 77
- 238000001723 curing Methods 0.000 description 31
- 229920002379 silicone rubber Polymers 0.000 description 16
- 238000000576 coating method Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LYVYUAHSSSHKHC-UHFFFAOYSA-N butyl(trimethyl)silane Chemical compound CCCC[Si](C)(C)C LYVYUAHSSSHKHC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FJWRGPWPIXAPBJ-UHFFFAOYSA-N diethyl(dimethyl)silane Chemical compound CC[Si](C)(C)CC FJWRGPWPIXAPBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- FBZANXDWQAVSTQ-UHFFFAOYSA-N dodecamethylpentasiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C FBZANXDWQAVSTQ-UHFFFAOYSA-N 0.000 description 1
- 229940087203 dodecamethylpentasiloxane Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01K—ELECTRIC INCANDESCENT LAMPS
- H01K1/00—Details
- H01K1/28—Envelopes; Vessels
- H01K1/32—Envelopes; Vessels provided with coatings on the walls; Vessels or coatings thereon characterised by the material thereof
Landscapes
- Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
Description
本発明は、シリコーン弾性体膜およびシリコー
ン樹脂膜を有する管球の製造方法に関し、破損し
にくく、破損してもガラス破片が飛散せず、かつ
塵埃で汚損されないガラス製管球を提供するもの
である。こゝで管球とは、白熱電球、螢光灯、水
銀灯、水銀整流器、電子管のように、主としてガ
ラス製の外殻の中を真空または希薄ガス雰囲気と
し、電極、フイラメントなどを存在せしめて、発
光、電子線の送受、整流などを行うものの総称で
ある。
ガラス製の外殻をもつ管球は、衝撃により破損
しやすく、また破損した場合、管球内と外気との
間に圧力差があるため、ガラス破片が飛散して危
険である。特に屋外、船舶上、水辺などで使用さ
れる管球、例えば屋外灯、集魚灯は、点灯中に雨
水、波の飛沫などを受けて内外の温度差によつて
破損したり、投石、車両による敷石の飛散などに
よる機械的衝撃によつて破損することが多い。そ
のため、従来から、管球のガラス外表面に、耐熱
性と耐紫外線に富むシリコーンワニス（シリコー
ン樹脂を溶剤に溶かしたもの）を塗布し、乾燥、
硬化させてシリコーン樹脂膜を形成することが行
われている。しかし、このようなシリコーン樹脂
膜も、組成中のケイ素原子に対する有機基の比が
小さいものは、保護膜として必要な可撓性に乏し
く、また脆いので、使用中に亀裂や剥離を生じ
て、保護効果の永続性がなく、一方、ケイ素原子
に対する有機基の比が大きくなると、高温で長時
間の乾燥工程を必要とするばかりでなく、使用中
の温度でシリコーン樹脂膜が軟化し、塵埃による
汚損を受けるという問題がある。この問題の解決
策として、特公昭43−29553号公報には、特定の
組成範囲のシリコーンワニスを選択し、かつ、ニ
ツケル、クロム、銅、コバルトなどの錯化合物を
乾燥促進剤として添加することにより、100〜150
℃、30〜60分間という比較的低温、短時間の加熱
で硬化し、かつ熱軟化や亀裂、剥離などを生じな
い良好な保護膜を得ている。この技術は、それま
でのシリコーン樹脂保護膜の欠点を克服し、かな
りすぐれた保護膜を与えたが、さらに大型の管球
に適用しても破損防止効果のある、または、さら
に大きな衝撃にも耐えられるような、より柔軟で
弾性に富んだ保護膜が望まれていた。
室温ないし若干の加熱でゴム状弾性体となるシ
リコーン組成物、特にそれを溶剤に溶かしたもの
を塗布し、硬化、乾燥させることにより、きわめ
て柔軟で弾力性に富む、透明なシリコーン弾性体
皮膜が得られることは知られている。特に、空気
中の水分により硬化する型のものは、密着性にす
ぐれ、剥離しにくいので、永続的な皮膜を基材表
面に与える。そこで、このような皮膜を管状の保
護膜として用いることが試みられたが、塵埃によ
る汚損が著しいという欠点がある。
このことの解決策として、ガラス外表面にまず
シリコーン弾性体の膜を形成し、ついでさらにそ
の表面にシリコーン樹脂膜を形成することが考え
られたが、成功しなかつた。それは、シリコーン
ワニスがシリコーン弾性体膜を十分に濡らさない
ので、シリコーン弾性体膜の表面に完全に連続し
たシリコーン樹脂膜が得られないためであつた。
本発明者らはこの問題を解決すべく研究を重ね
た結果、シリコーン樹脂の溶剤として、常圧にお
ける沸点が70〜250℃の有機ケイ素化合物を炭化
水素とともに用いることにより、シリコーン弾性
体膜の表面にシリコーン樹脂膜を形成しうること
を見出し、かつ、このような複層の保護膜によつ
て、破損しにくく、破損しても破片が飛散せず、
かつ汚損されない管球を得る方法を完成して、本
発明をなすに至つた。
すなわち本発明は、ガラス製管球の外表面に、
常温ないし若干の加熱でゴム状に硬化しうるシリ
コーン組成物を塗布し、硬化してシリコーン弾性
体としたのち、その外表面に
(A) 平均組成式Ｒ１ ａSi（OR2）bO〓〓〓〓〓（たゞ
し、R1、ａは上記に同じ、R2は水素原子また
は炭素数１〜４のアルキル基、ｂは0.01〜２の
数を示し、ａ＋ｂは３を越えない）で表わされ
るベンゼン可溶性ポリオルガノシロキサン樹
脂、
(B) 分子式Ｒ３ ４Si、Ｒ４ ３SiO〔Ｒ５ ２SiO〕nSiR４
３、また
は〔Ｒ６ ２SiO〕o（たゞし、式中R3〜R6はそれぞ
れ互に同一または相異なるアルキル基、ｍは０
または正の数、ｎは正の数を示す）で表わさ
れ、かつ常圧における沸点が70〜250℃の範囲
である揮発性有機ケイ素化合物、および
(C) 炭化水素系溶媒
から成り、(B)の量が(B)と(C)の合計量の５〜75重量
％である、樹脂状に硬化しうる組成物を塗布し、
(B)及び(C)を揮散せしめた後硬化せしめ平均組成式
Ｒ１ ａSiO〓〓〓（たゞし、R1、ａは上記に同じ）
で表わされるシリコーン樹脂膜を形成させること
を特徴とする、保護膜付管球の製造方法に関す
る。
本発明において、ガラスの外表面に形成される
シリコーン弾性体膜は、分子骨格がシロキサン結
合から成るものであれば、いかなる反応機構のも
のでもよい。薄い均一な皮膜を得るには、未硬化
の状態では流動性、ペースト状、またはパテ状
の、ベースポリマーとして流動性のポリオルガノ
シロキサンを用いたシリコーン組成物か、それを
溶剤に希釈したシリコーン組成物を用いる。すな
わち、該組成物ないしそれを溶剤で希釈したもの
をガラスの外表面に塗布し、乾燥後、常温ないし
若干の加熱で硬化して形成される。塗布は、刷毛
塗り、ロールコート、スプレー、流し塗り、回転
滴下法、その他、公知のいかなる方法を用いても
さしつかえない。硬化手段は、後述するシリコー
ン組成物の反応機構と構成比によつて、次のいず
れかによつてなされる。
架橋剤および／または触媒を流動性かつ反応
性のポリオルガノシロキサンとは別の容器に保
存しておき、均一に混合して塗布すると、室温
で放置することによつて硬化する。
と同じであるが、70〜150℃の温度に加熱
することにより、短時間硬化する。
全成分をあらかじめ均一に混合しておき、塗
布後、同様の加熱によつて硬化する。
全成分を、水分を遮断した容器中に均一に混
合して保存し、塗布後、空気中の水分との接触
によつて室温で硬化する。
シリコーン弾性体膜の厚さは、特に制限される
ものではないが、１μ〜１mmの範囲が好ましい。
該弾性体膜は、第１図に示されるように、管球の
ガラス部分の全面に施される。
このようなシリコーン組成物は、反応性ポリオ
ルガノシロキサン、架橋剤、および必要に応じて
触媒および／または無機質微粉末から成る。反応
機構は大別して次の２つが公知であり、そのいず
れも本発明に用いることができる。
〔1〕 反応性ポリオルガノシロキサンとして、ケ
イ素原子に結合せるビニル基が１分子中に少く
とも２個存在する直鎖状または分岐状のもの、
架橋剤として、ケイ素原子に結合せる水素原子
が１分子中に平均２個を越える数存在するポリ
オルガノハイドロジエンシロキサン、触媒とし
て微量の白金化合物を用いるもので、通常は前
記の硬化方法が用いられるが、も可能であ
り、また公知の反応抑制剤を共存させることに
より、をとることもできる。
〔2〕 反応性ポリオルガノシロキサンとして、両
末端にシラノール基が存在する直鎖状ポリジオ
ルガノシロキサン、架橋剤として、ケイ素原子
に結合せる加水分解性基が１分子中に平均２個
を越える数存在するケイ素化合物を用いるもの
で、加水分解性基としては、アセトキシ基、ア
ルコキシ基、アルケニルオキシ基、ジオルガノ
ケトオキシム基、ジオルガノアミノキシ基、ジ
オルガノアミノ基、Ｎ−メチルアセトアミド基
などが例示される。このうちジオルガノアミノ
キシ基を用いるものは、触媒は不要であり、硬
化方法は通常が用いられるが、イソシアネー
ト化合物を共存させる硬化方法を用いること
も可能となる。その他の加水分解性基を用いる
ものは、アミン類、スズの脂肪酸塩、有機スズ
化合物、チタン化合物のような触媒を用いて硬
化方法により容易にシリコーン弾性体膜が得
られる。またアルコキシ基を用いるもののう
ち、比較的多重のアルキルシリケートおよびそ
の部分縮合物を用いるものは、硬化方法ない
しを採用しうることが公知である。
反応機構〔１〕、〔２〕のいずれをとるにして
も、ポリジオルガノシロキサンのケイ素原子に結
合せる有機基は、〔１〕におけるビニル基は別と
して、公知技術に示されるように１価の炭化水素
基が用いられるが、合成のしやすさ、耐熱性、耐
候性、耐水性、およびシリコーン弾性体膜として
の諸性質からメチル基が最も好ましく、耐熱性、
耐寒性、耐放射線性、光の透過率などが要求され
るとき、必要に応じて30モル％までのフエニル基
が共用される。
無機質微粉末としては、公知のいかなるものも
用いられるが、薄くて平滑なシリコーン弾性体膜
を得るには、粒径１μ以下の微細な粉末であるこ
とが好ましい。反応機構〔１〕の場合や、Ｘ線管
のように電磁波の透過性が必要な場合は重金属を
含むものは避けなければならない。また、集魚灯
のように光の透過性が必要な場合は、粒径100ｍ
μ以下のシリカ、特に煙霧質シリカを用いること
が好ましい。シリカは公知の疎水化剤、たとえば
ヘキサメチルジシラザンのような有機ケイ素化合
物で表面処理を行つたものを用いてもよい。
使用直前にシリコーン組成物中の特定成分を混
合する煩雑さを避けるには、硬化方法としてま
たはを用いることが好ましい。は抑制剤を必
要とし、高価な添加剤を用いないかぎりガラス表
面への密着性が悪く、かつ安定性と硬化条件の制
御がむずかしいが、その点ではの方が実施が容
易で、ガラスへの密着性もすぐれている。硬化方
法を用いる場合、加水分解性基としては、硬化
速度が大きい点ではアセトキシ基とアルケニルオ
キシ基、その中でも架橋剤の合成が容易な点でア
セトキシ基が好ましい。また、適度の硬化速度を
もち、硬化の際に腐食性副生物の発生がなく、か
つ得られた弾性体膜が耐熱性に富むことでは、ジ
アルケニルケトオキシム基が好ましい。
管球が比較的小型で、かつ耐熱性の著しく悪い
材料を用いていないものは加熱が容易なので、
またはの方法が好ましい。特に量産品には、こ
の方法により硬化時間を短縮することが推奨され
る。前述のように、この方法には、ケイ素原子に
それぞれ結合せるビニル基と水素原子の間の反応
によつて硬化する組成物が適している。
本発明の特徴は、ベンゼン可溶性ポリオルガノ
シロキサン樹脂を揮発性有機ケイ素化合物および
炭化水素系溶媒とともにシリコーン弾性体膜の表
面に塗布し、乾燥、硬化せしめることにあり、そ
のことによつてシリコーン弾性体膜の表面に均一
なシリコーン樹脂膜を得ることが、はじめて可能
になつた。シリコーン樹脂膜の厚さは任意であ
り、特に限定はないが、きわめて薄い皮膜でも効
果がある。また光の透過性が必要な電球類では、
あまり厚くない方が好ましい。塗布方法は、前述
のシリコーン組成物の場合と同様の各種の方法が
用いられる。硬化は加熱によつて行われるが、硬
化触媒をあらかじめ組成物中に添加することに和
より、150℃以下の比較的低い温度の加熱、ない
し常温で硬化せしめることも可能である。このシ
リコーン樹脂膜は第１図に示されるように、シリ
コーン弾性体膜の全表面を掩うように形成され
る。
本発明で用いられる(A)のベンゼン可溶性ポリオ
ルガノシロキサン樹脂は、平均組成式Ｒ１ ａSi
（OR2）bO〓〓〓〓〓（たゞしR1、R2、ａ、ｂは
前述のとおり）で表わされる比較的分子量の小さ
いもので、R1／Siは0.85〜1.55の範囲から選ばれ
る。R1としては、メチル基、エチル基、プロピ
ル基、ブチル基、アミル基、ヘキシル基、オクチ
ル基、デシル基などのアルキル基、ビニル基など
のアルケニル基、β−エチルフエニル基などのア
ラルキル基、フエニル基などのアリール基、およ
びこれらの水素原子の一部が塩素原子、フツ素原
子、ニトリル基などで置換されたものが例示され
るが、常温ないし比較的低い温度の加熱で硬化し
て皮膜を形成すること、その皮膜が耐熱性および
耐候性に富むことから、メチル基およびR1中の
０〜50モル％のフエニル基から成ることが好まし
い。R1／Siが0.85未満では、保存中の安定性が悪
く、また硬化は早いが皮膜が脆くなつて剥離や亀
裂が入りやすく、R1／Siが1.55を越えると、管球
の点灯、作動による高温で軟化して、防埃効果を
発揮しなくなる。またR1中のフエニル基の量が
50モル％を越えると、硬化が遅くなり、また皮膜
が脆くなる。このようなベンゼン可溶ポリオルガ
ノシロキサン樹脂は、分子が巨大化して不溶不融
性の皮膜を形成するために、ケイ素原子あたり
0.01〜２個の水酸基および／または低級アルコキ
シ基が存在しなければならない。低級アルコキシ
基としては、容易に加水分解、縮合して皮膜を形
成することから、メトキシ基、エトキシ基など、
せいぜい炭素数４までのものが選ばれる。
このようなベンゼン可溶性ポリオルガノシロキ
サン樹脂は、SiO2単位とＲ１ ３SiO1/2単位から構
成され、ケイ素原子に結合せる水酸基をもつも
の、R1SiO3/2単位とＲ１ ２SiO単位から構成さ
れ、ケイ素原子に結合せる水酸基または低級アル
コキシ基もつもの、実質的にR1SiO3/2単位か
ら成り、ケイ素原子に結合せる低級アルコキシ基
のみ、または低級アルコキシ基と水酸基をもつも
のが例示される。
はシリコーン弾性体膜への密着性が優れてお
り、防埃効果も良い。Ｒ１ ３SiO1/2単位の比は、
SiO2単位１モルに対して0.4〜1.0モルの間が好ま
しく、0.5〜0.8モルの間がさらに好ましい。Ｒ１ ３
SiO1/2単位が少ないとベンゼン可溶性の低分子
量のものを安定に得にくく、Ｒ１ ３SiO1/2単位が多
いと防埃効果が低下する。合成が容易なことか
ら、R1はメチル基であることが好ましい。
は合成しやすく、特に任意のR1／Siならびに
メチル基とフエニル基の割合のものを合成しやす
いので、必要な硬化性、防埃性、柔軟性のものを
得ることができる。管球は点灯ないし作動中の発
熱を伴うので、防埃皮膜の表面もかなりの高温、
時として200℃前後の温度にさらされる。この場
合、R1／Siが1.55を越えると、皮膜が高温時に軟
化するので防埃効果がない。また、R1／Siが1.05
未満では、皮膜が脆くなり、剥離や亀裂を生じや
すい。従つてR1／Siは1.05〜1.55の間が好まし
く、柔軟性の点で1.35〜1.55の間がさらに好まし
いが、特にこの用途には1.55を越えてはならな
い。R1中のフエニル基の量は25〜50モル％の間
が好ましい。フエニル基が25モル％未満では耐熱
性が十分でなく、50モル％を越する皮膜が脆くな
り、かつシリコーン弾性体膜への密着性が劣つて
剥離しやすくなるからである。は硬化性のすぐ
れたものが得られるが、に比べて皮膜の柔軟性
で劣る。
(A)の濃度は、(A)、(B)、(C)の合計量に対して５〜
80重量％の範囲が好ましく、10〜50重量％がさら
に好ましい。濃度が低すぎると１回の塗布で得ら
れる皮膜の厚さが小さく、何回も塗布を行うこと
が必要で、濃度が高すぎると粘度が高くなり、取
扱が不便で、皮膜が厚くなりすぎたり、不均一に
なつたりする。
本発明で用いられる(B)の揮発性有機ケイ素化合
物は、不安定な基を含まないシランまたはシロキ
サンであり、適度の揮発性をもつこと、換言すれ
ば沸点が70〜250℃の範囲であることが必要であ
る。沸点がこれより低いと保存中または塗布時に
揮散して有効に作用せず、高すぎると乾燥性が悪
くなり、皮膜の形成が遅くなるからである。ジメ
チルジエチルシラン、トリメチルブチルシラン、
のようなシラン、ヘキサメチルジシロキサン、オ
クタメチルトリシロキサン、デカメチルテトラシ
ロキサン、ドデカメチルペンタシロキサンのよう
な鎖状シロキサン、ヘキサメチルシクロトリシロ
キサン、オクタメチルシクロテトラシロキサン、
デカメチルシクロペンタシロキサンのような環状
シロキサンが例示されるが、合成の容易なことか
ら、メチル系シロキサン、特にオクタメチルシク
ロテトラシロキサンが好ましい。
(B)の量は(B)と(C)の合計量に対して５〜75重量
％、好ましくは10〜65重量％の範囲であることが
必要である。(B)の量が少ないとシリコーン弾性体
表面に対して良好な濡れ性が得られず、また多す
ぎると製造中や保存中に(A)が析出して白濁した
り、硬化後の皮膜が透明、平滑、かつ強靭なもの
として得られないからである。
(C)の炭化水素系溶液は、(A)の溶解性から、ベン
ゼン、トルエン、キシレン、ｎ−ヘキサン、ｎ−
ヘプタン、シクロヘキサン、ガソリンのような炭
化水素であることが好ましい。また、若干の１価
アルコール、１価エーテルアルコール、アセトン
などを併用してもよい。これらのうち、適度の揮
発性、(A)の溶解性、および取扱いやすさから、ト
ルエンおよび／またはキシレンが好ましい。
(A)は常温において、(B)、(C)が揮散したのち、ケ
イ素原子に結合したOR2（たゞし、R2は前述のと
おり）同士の縮合で硬化が進み、表面がべとつか
ない、平均組成式Ｒ１ ａSiO〓〓〓（ただし、R1、
ａは前述の通り）で表わされる防埃性の皮膜を形
成するが、加熱が可能な場合は、150〜200℃に加
熱して硬化を促進させることが推奨される。しか
し加熱が困難ないし不可能な場合や、効率よく硬
化を行いたい場合には、硬化を促進するために、
硬化触媒および／またはケイ素原子に結合した加
水分解性基が分子中に少なくとも２個存在するオ
ルガノシランないしオルガノシロキサンを添加す
る。硬化触媒としてはスズなどの金属の有機酸
塩、アルキルチタネート、チタンキレート化合
物、ニツケルキレート化合物、コバルトキレート
化合物、アミン化合物などが例示される。加水分
解性基としてはメトキシ基、エトキシ基、イソプ
ロポキシ基のようなアルコキシ基、アセトキシ基
のようなアシロキシ基、ジエチルアミノキシ基の
ようなオルガノアミノキシ基、ジエチルアミノ基
のようなアミノ基、アセトンオキシム基、メチル
エチルケトンオキシム基のようなオキシム基が例
示される。γ−アミノプロピルトリエトキシシラ
ンは、前述の硬化触媒を兼ねた加水分解性シラン
の例である。なお、R1／Siが小さい場合には、単
に溶媒(B)、(C)が揮散したのち、常温で防埃性の皮
膜を形成することができる。
本発明により、機械的衝撃や熱的衝撃によつて
破損しにくく、また万一破損した場合にもガラス
破片が飛散しない安全性に富んだ、しかも塵埃に
よつて汚損しないガラス製管球を得ることができ
た。
本発明は、屋外で使用される屋外灯、水辺や船
舶に使用される集魚灯をはじめ、衝撃の危険性が
あつたり、特に安全性が要求される箇所に使用さ
れる安全な管球として、有用である。
以下、本発明を実施例によつて説明する。実施
例中、部はすべて重量部を意味する。
参考例 １
25℃における粘度が20000cStのシラノール末端
ポリジメチルシロキサン100部に、ヘキサメチル
ジシラサンで表面処理した煙霧質シリカ10部を均
一に混練してベースコンパウンドを得た。これに
ジブチルスズジアセテート0.05部、およびメチル
トリアセトキシシランの部分加水分解物５部を順
次添加して均一に混練し、これに脱水キシレン
115部を加えて混合し、試料Ｅ−１を調製した。
これを密閉構造の金属缶に密栓して保存した。
参考例 ２
25℃における粘度が10000cStのシラノール末端
ポリジメチルシロキサン100部に、ポリジメチル
シロキサンで表面処理した煙霧質シリカ10部を均
一に混練してベースコンパウンドを得た。これに
メチルトリス（ブタノンオキシム）シラン８部、
ジブチルスズジラウレート0.2部、γ−アミノプ
ロピルトリエトキシシラン２部の混合物を添加し
て均一に混練し、さらに脱水トルエン120部を加
えて試料Ｅ−２を調製した。これを密閉構造の金
属缶に密栓して保存した。
参考例 ３
両末端がジメチルビニルシロキシ単位で、12モ
ル％のジフエニルシロキサン単位と残余のジメチ
ルシロキサン単位から成り、25℃における粘度が
12000cStのポリジオルガノシロキサン100部に、
煙霧質シリカ24部を加えてベースコンパウンドと
した。ついで、塩化白金酸とテトラメチルテトラ
ビニルシクロテトラシロキサンを加熱して得られ
た錯体をベースコンパウンドに対して10ppm添
加し、均一に混合した。別に、上記のポリジオル
ガノシロキサン100部、両末端がトリメチルシロ
キシ単位で25℃における粘度が30cStのポリメチ
ルハイドロジエンシロキサン60部、および３−メ
チル−１−ブチン−３−オール1.4部を加え、均
一に混合した。この両者を、配合比が10：１にな
るように混合して試料Ｅ−３を調製した。なお、
この最終段階の混合は、管球に処理を行う直前に
行つた。
実施例 １
5KWの集魚灯用ハロゲンランプのガラス外表
面に、参考例１で調製した試料Ｅ−１を刷毛塗り
し、溶剤を揮散させたのち、常温で２昼夜放置し
て、シリコーン弾性体膜を形成させた。下記のベ
ンゼン可溶性ポリオルガノシロキサン樹脂溶液を
用いて、第１表に示される樹脂状に硬化しうる試
料11〜14を調製した。たゞし試料11および13は比
較例試料である。
Ｒ−１ R1SiO3/2単位とＲ１ ２SiO単位から成り、
R1／Siが1.45で、R1中フエニル基が50モル％で
残余がメチル基であり、ケイ素原子に結合せる
水酸基を有するポリメチルフエニルシロキサン
樹脂溶液の50％キシレン溶液
Ｒ−２ SiO2単位とＲ１ ３SiO1/2単位から成り、
SiO2単位に対するＲ１ ３SiO1/2単位の割合が0.65
モルで、ケイ素原子に結合せる水酸基を有する
ポリメチルシロキサン樹脂の50％トルエン溶液
これらの試料をシリコーン弾性体膜の表面に刷
毛で塗布して、濡れ性をみた。その結果は第１表
に示すとおりである。塗布された樹脂試料は、溶
剤揮散後、第１表に示す硬化条件で硬化してシリ
コーン樹脂膜を形成した。なお、比較のために何
の処理もしない同種のハロゲンランプと、シリコ
ーン弾性体膜のみを形成させたハロゲンランプを
用意した。これらの処理および未処理のハロゲン
ランプについて、次のような実験を行つた。
実験 15分間点灯し、点灯したまゝ５℃の冷水
を側面からノズルを通して吹きつけ、破損の有
無などを観察する。
実験 24時間連続して点灯したのち、表面の状
態を観察する。
実験 屋外に180日間放置して、表面の状態を
観察する。
これらの結果を第１表にまとめた。
The present invention relates to a method of manufacturing a tube having a silicone elastic film and a silicone resin film, and provides a glass tube that is hard to break, does not scatter glass fragments even if broken, and is not contaminated by dust. be. A tube, like an incandescent light bulb, fluorescent lamp, mercury lamp, mercury rectifier, or electron tube, is mainly made of a glass shell with a vacuum or diluted gas atmosphere, and with electrodes, filaments, etc. A general term for things that emit light, transmit and receive electron beams, and rectify them. A tube having an outer shell made of glass is easily damaged by impact, and if it breaks, glass fragments may scatter due to the pressure difference between the inside of the tube and the outside air, which is dangerous. In particular, tube bulbs used outdoors, on ships, near the water, etc., such as outdoor lights and fishing lights, are exposed to rainwater, wave spray, etc. while they are on, and can be damaged due to the temperature difference between the inside and outside, or can be damaged by stones or vehicles. Often damaged by mechanical shock caused by flying stones, etc. For this reason, traditionally, heat-resistant and ultraviolet-resistant silicone varnish (a silicone resin dissolved in a solvent) is applied to the outer glass surface of the tube, dried, and
A silicone resin film is formed by curing. However, such silicone resin films, which have a small ratio of organic groups to silicon atoms in their composition, lack the flexibility required as a protective film and are brittle, resulting in cracks and peeling during use. On the other hand, the high ratio of organic groups to silicon atoms not only requires a long drying process at high temperatures, but also softens the silicone resin film at the temperature during use and prevents dust from forming. There is a problem of staining. As a solution to this problem, Japanese Patent Publication No. 43-29553 proposes to select a silicone varnish with a specific composition range and add a complex compound such as nickel, chromium, copper, or cobalt as a drying accelerator. , 100-150
It cures by heating at a relatively low temperature of 30 to 60 minutes at a temperature of 30 to 60 minutes, and provides a good protective film that does not undergo thermal softening, cracking, or peeling. This technology overcame the shortcomings of previous silicone resin protective films and provided a fairly excellent protective film, but it was also effective in preventing breakage even when applied to large tubes, and even resistant to even greater impact. There was a desire for a more flexible and highly elastic protective film that would withstand the effects of this. By applying a silicone composition that becomes a rubber-like elastomer at room temperature or with slight heating, especially when it is dissolved in a solvent, and curing and drying it, a transparent silicone elastomer film that is extremely flexible and highly elastic can be created. It is known that it can be obtained. In particular, those of the type that harden due to moisture in the air have excellent adhesion and are difficult to peel off, so they provide a permanent film on the surface of the substrate. Attempts have therefore been made to use such a film as a tubular protective film, but this method has the drawback of being significantly contaminated by dust. As a solution to this problem, it was considered to first form a silicone elastic film on the outer surface of the glass, and then to further form a silicone resin film on the surface, but this was not successful. This was because the silicone varnish did not sufficiently wet the silicone elastic film, so a completely continuous silicone resin film could not be obtained on the surface of the silicone elastic film. As a result of repeated research by the present inventors to solve this problem, we found that by using an organosilicon compound with a boiling point of 70 to 250°C at normal pressure together with a hydrocarbon as a solvent for silicone resin, the surface of the silicone elastomer film can be improved. discovered that it is possible to form a silicone resin film on the surface of the material, and that such a multi-layered protective film makes it difficult to damage and does not scatter fragments even if it is damaged.
The inventors have completed a method for obtaining a tube that does not become contaminated, leading to the present invention. That is, the present invention provides the outer surface of the glass tube,
A silicone composition that can be cured into a rubbery state at room temperature or by slight heating is applied and cured to form a silicone elastomer, and then the outer surface is coated with (A) average compositional formula R 1 a Si (OR 2 ) b O〓 〓〓〓〓 (However, R 1 and a are the same as above, R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, b is a number of 0.01 to 2, and a+b does not exceed 3) Benzene-soluble polyorganosiloxane resin represented by (B) molecular formula R 3 4 Si, R 4 3 SiO [R 5 2 SiO] n SiR 4
3 , or [R 6 2 SiO] o (in the formula, R 3 to R 6 are each the same or different alkyl group, m is 0
or a positive number, n is a positive number), and has a boiling point in the range of 70 to 250°C at normal pressure, and (C) a hydrocarbon solvent, ( applying a resinously curable composition in which the amount of B) is 5 to 75% by weight of the total amount of (B) and (C);
Cured after volatilizing (B) and (C), average compositional formula R 1 a SiO〓〓〓 (R 1 and a are the same as above)
The present invention relates to a method for manufacturing a tube with a protective film, which is characterized by forming a silicone resin film represented by: In the present invention, the silicone elastic film formed on the outer surface of the glass may have any reaction mechanism as long as the molecular skeleton is composed of siloxane bonds. To obtain thin, uniform films, silicone compositions that are free-flowing, paste-like, or putty-like in the uncured state, using a free-flowing polyorganosiloxane as the base polymer, or diluted in a solvent. use things That is, the composition or a diluted version thereof with a solvent is applied to the outer surface of glass, dried, and then cured at room temperature or with slight heating. The coating may be applied by brushing, roll coating, spraying, flow coating, rotary dropping, or any other known method. The curing means may be carried out by one of the following methods, depending on the reaction mechanism and composition ratio of the silicone composition, which will be described later. The crosslinking agent and/or catalyst are stored in a separate container from the fluid and reactive polyorganosiloxane, mixed uniformly and applied, and cured by standing at room temperature. Same as , but cures for a short time by heating to a temperature of 70-150°C. All components are mixed uniformly in advance, and after coating, the coating is cured by heating in the same manner. All components are stored homogeneously mixed in a moisture-tight container and, after application, are cured at room temperature by contact with moisture in the air. The thickness of the silicone elastic film is not particularly limited, but is preferably in the range of 1 μm to 1 mm.
The elastic membrane is applied to the entire surface of the glass portion of the bulb, as shown in FIG. Such silicone compositions consist of a reactive polyorganosiloxane, a crosslinking agent, and optionally a catalyst and/or an inorganic fine powder. The following two reaction mechanisms are generally known, and either of them can be used in the present invention. [1] Reactive polyorganosiloxanes that are linear or branched and have at least two vinyl groups bonded to silicon atoms in one molecule;
A polyorganohydrodiene siloxane in which an average of more than two hydrogen atoms bond to silicon atoms exist in each molecule as a crosslinking agent, and a trace amount of a platinum compound as a catalyst, and the curing method described above is usually used. However, this can also be achieved by coexisting with a known reaction inhibitor. [2] As a reactive polyorganosiloxane, a linear polydiorganosiloxane with silanol groups at both ends, and as a crosslinking agent, an average of more than 2 hydrolyzable groups bonded to silicon atoms in one molecule. Examples of hydrolyzable groups include acetoxy group, alkoxy group, alkenyloxy group, diorganoketoxime group, diorganoaminoxy group, diorganoamino group, and N-methylacetamide group. be done. Among these, those using a diorganoaminoxy group do not require a catalyst, and the curing method used is the usual one, but it is also possible to use a curing method in which an isocyanate compound is coexisting. When using other hydrolyzable groups, a silicone elastomer film can be easily obtained by a curing method using a catalyst such as an amine, a tin fatty acid salt, an organic tin compound, or a titanium compound. Among those using alkoxy groups, it is known that curing methods can be employed for those using relatively multiple alkyl silicates and their partial condensates. Regardless of the reaction mechanism [1] or [2], the organic group bonded to the silicon atom of the polydiorganosiloxane, apart from the vinyl group in [1], is a monovalent group as shown in the known technology. Hydrocarbon groups are used, but methyl groups are most preferred from the viewpoint of ease of synthesis, heat resistance, weather resistance, water resistance, and various properties as a silicone elastomer film.
When cold resistance, radiation resistance, light transmittance, etc. are required, up to 30 mol% of phenyl groups may be used as needed. Any known inorganic fine powder can be used, but in order to obtain a thin and smooth silicone elastic film, a fine powder with a particle size of 1 μm or less is preferable. In the case of reaction mechanism [1] or when transparency of electromagnetic waves is required such as in an X-ray tube, materials containing heavy metals must be avoided. In addition, if light transparency is required such as a fishing light, a particle size of 100m is recommended.
It is preferred to use subμ silica, especially fumed silica. The silica may be surface-treated with a known hydrophobizing agent, for example, an organosilicon compound such as hexamethyldisilazane. To avoid the complexity of mixing specific components in the silicone composition immediately before use, it is preferred to use or as the curing method. requires an inhibitor, has poor adhesion to the glass surface unless expensive additives are used, and is difficult to control stability and curing conditions; It also has excellent adhesion. When using the curing method, the hydrolyzable group is preferably an acetoxy group or an alkenyloxy group because of its high curing rate, and among these, an acetoxy group is preferred because it facilitates the synthesis of a crosslinking agent. In addition, dialkenyl ketoxime groups are preferred because they have an appropriate curing speed, do not produce corrosive by-products during curing, and the resulting elastic film has high heat resistance. If the tube is relatively small and does not use materials with extremely poor heat resistance, it is easy to heat it.
or method is preferred. Especially for mass-produced products, this method is recommended to shorten the curing time. As mentioned above, compositions that cure by reaction between vinyl groups and hydrogen atoms, each bonded to a silicon atom, are suitable for this method. The feature of the present invention is that a benzene-soluble polyorganosiloxane resin is applied to the surface of a silicone elastomer film together with a volatile organosilicon compound and a hydrocarbon solvent, and then dried and cured. For the first time, it has become possible to obtain a uniform silicone resin film on the surface of the film. The thickness of the silicone resin film is arbitrary and is not particularly limited, but even a very thin film is effective. In addition, for light bulbs that require light transparency,
It is preferable that it is not too thick. As the coating method, various methods similar to those for the silicone composition described above can be used. Curing is carried out by heating, but by adding a curing catalyst to the composition in advance, it is also possible to cure by heating at a relatively low temperature of 150° C. or lower or at room temperature. As shown in FIG. 1, this silicone resin film is formed so as to cover the entire surface of the silicone elastic film. The benzene-soluble polyorganosiloxane resin (A) used in the present invention has an average composition formula R 1 a Si
(OR 2 ) b O〓〓〓〓〓〓 (R 1 , R 2 , a, b are as described above), and has a relatively small molecular weight, and R 1 /Si is in the range of 0.85 to 1.55. selected from. R 1 is an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, or decyl group, an alkenyl group such as a vinyl group, an aralkyl group such as β-ethylphenyl group, or a phenyl group. Examples include aryl groups such as aryl groups, and those in which some of these hydrogen atoms are substituted with chlorine atoms, fluorine atoms, nitrile groups, etc., but they can be cured and form a film by heating at room temperature or relatively low temperature. It is preferable that the phenyl group is composed of a methyl group and 0 to 50 mol % of phenyl group in R 1 because the film is excellent in heat resistance and weather resistance. If R 1 /Si is less than 0.85, the stability during storage will be poor, and although the film will harden quickly, it will become brittle and easily peel or crack. If R 1 /Si exceeds 1.55, the lamp will not light up or operate properly. It softens at high temperatures and loses its dust-proofing effect. Also, the amount of phenyl group in R 1 is
If it exceeds 50 mol%, curing will be slow and the film will become brittle. In such benzene-soluble polyorganosiloxane resin, the molecules become large and form an insoluble and infusible film, so each silicon atom
0.01 to 2 hydroxyl and/or lower alkoxy groups must be present. Lower alkoxy groups include methoxy groups, ethoxy groups, etc. because they easily hydrolyze and condense to form a film.
Those having at most 4 carbon atoms are selected. Such benzene-soluble polyorganosiloxane resins are composed of SiO 2 units and R 1 3 SiO 1/2 units and have hydroxyl groups bonded to silicon atoms, and R 1 SiO 3/2 units and R 1 2 SiO units. , and has a hydroxyl group or lower alkoxy group bonded to the silicon atom, and one consisting essentially of R 1 SiO 3/2 units and has only a lower alkoxy group bonded to the silicon atom, or a lower alkoxy group and a hydroxyl group. Illustrated. has excellent adhesion to silicone elastomer membranes and has good dustproofing effects. The ratio of R 1 3 SiO 1/2 units is
It is preferably between 0.4 and 1.0 mol, more preferably between 0.5 and 0.8 mol, per mol of SiO 2 units. R 1 3
If there are too few SiO 1/2 units, it will be difficult to stably obtain a benzene-soluble low molecular weight product, and if there are too many R 13 SiO 1/2 units, the dust-proofing effect will decrease. R 1 is preferably a methyl group for ease of synthesis. is easy to synthesize, especially one with arbitrary R 1 /Si and the ratio of methyl groups to phenyl groups, so it is possible to obtain the required hardenability, dust resistance, and flexibility. Since the bulb generates heat when it is lit or in operation, the surface of the dustproof coating can also reach a high temperature.
Sometimes exposed to temperatures around 200℃. In this case, if R 1 /Si exceeds 1.55, the film will soften at high temperatures and will not have any dust-proofing effect. Also, R 1 /Si is 1.05
If it is less than that, the film becomes brittle and tends to peel or crack. Therefore, R 1 /Si is preferably between 1.05 and 1.55, more preferably between 1.35 and 1.55 from the viewpoint of flexibility, but especially for this use it should not exceed 1.55. The amount of phenyl groups in R 1 is preferably between 25 and 50 mol%. If the phenyl group content is less than 25 mol%, the heat resistance will not be sufficient, and if the content exceeds 50 mol%, the film will become brittle and have poor adhesion to the silicone elastomer film, making it easy to peel off. Although a product with excellent curing properties can be obtained, the flexibility of the film is inferior to that of . The concentration of (A) is 5 to 5 to the total amount of (A), (B), and (C).
A range of 80% by weight is preferred, and a range of 10 to 50% by weight is more preferred. If the concentration is too low, the thickness of the film obtained with one application will be small, requiring multiple applications; if the concentration is too high, the viscosity will be high, making it inconvenient to handle and making the film too thick. or become uneven. The volatile organosilicon compound (B) used in the present invention is a silane or siloxane that does not contain unstable groups and has appropriate volatility, in other words, the boiling point is in the range of 70 to 250°C. It is necessary. If the boiling point is lower than this, it will volatilize during storage or during application and will not work effectively, whereas if it is too high, drying properties will be poor and the formation of a film will be delayed. Dimethyldiethylsilane, trimethylbutylsilane,
Silanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, linear siloxanes such as dodecamethylpentasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
Examples include cyclic siloxanes such as decamethylcyclopentasiloxane, but methyl-based siloxanes, particularly octamethylcyclotetrasiloxane, are preferred because they are easy to synthesize. The amount of (B) should range from 5 to 75% by weight, preferably from 10 to 65% by weight, based on the total amount of (B) and (C). If the amount of (B) is too small, good wettability to the surface of the silicone elastomer will not be obtained, and if it is too large, (A) will precipitate during manufacturing or storage, resulting in a cloudy coating or a hardened film. This is because it cannot be obtained as a transparent, smooth, and strong material. Due to the solubility of (A), the hydrocarbon solution of (C) is benzene, toluene, xylene, n-hexane, n-
Hydrocarbons such as heptane, cyclohexane, gasoline are preferred. Further, some monohydric alcohol, monohydric ether alcohol, acetone, etc. may be used in combination. Among these, toluene and/or xylene are preferred because of their appropriate volatility, solubility of (A), and ease of handling. At room temperature, after (B) and (C) have volatilized, (A) is cured by the condensation of OR 2 (R 2 is as described above) bonded to silicon atoms, and the surface does not become sticky. , average composition formula R 1 a SiO〓〓〓 (however, R 1 ,
(a is as described above) to form a dust-proof film, but if heating is possible, it is recommended to accelerate curing by heating to 150 to 200°C. However, if heating is difficult or impossible, or if you want to cure efficiently, use
A curing catalyst and/or an organosilane or organosiloxane in which at least two hydrolyzable groups bonded to silicon atoms are present in the molecule are added. Examples of the curing catalyst include organic acid salts of metals such as tin, alkyl titanates, titanium chelate compounds, nickel chelate compounds, cobalt chelate compounds, and amine compounds. Hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, and isopropoxy groups, acyloxy groups such as acetoxy, organoaminoxy groups such as diethylaminoxy, amino groups such as diethylamino, and acetone oxime. and oxime groups such as methyl ethyl ketone oxime group. γ-Aminopropyltriethoxysilane is an example of the aforementioned hydrolyzable silane that also serves as a curing catalyst. Note that when R 1 /Si is small, a dustproof film can be formed at room temperature simply after the solvents (B) and (C) are volatilized. ADVANTAGE OF THE INVENTION According to the present invention, it is possible to obtain a glass tube that is not easily damaged by mechanical shock or thermal shock, has a high level of safety in that glass fragments do not scatter even if it is broken, and is not contaminated by dust. I was able to do that. The present invention is a safe tube to be used in places where there is a risk of impact and where safety is particularly required, such as outdoor lights used outdoors, fishing lights used on waterside and ships, etc. Useful. Hereinafter, the present invention will be explained with reference to Examples. In the examples, all parts mean parts by weight. Reference Example 1 A base compound was obtained by uniformly kneading 10 parts of silanol-terminated polydimethylsiloxane having a viscosity of 20,000 cSt at 25°C with 10 parts of fumed silica surface-treated with hexamethyldisilane. To this, 0.05 parts of dibutyltin diacetate and 5 parts of a partial hydrolyzate of methyltriacetoxysilane were sequentially added and kneaded uniformly.
115 parts were added and mixed to prepare sample E-1.
This was sealed and stored in a metal can with an airtight structure. Reference Example 2 A base compound was obtained by uniformly kneading 10 parts of silanol-terminated polydimethylsiloxane having a viscosity of 10,000 cSt at 25°C with 10 parts of fumed silica surface-treated with polydimethylsiloxane. To this, 8 parts of methyltris(butanone oxime)silane,
A mixture of 0.2 parts of dibutyltin dilaurate and 2 parts of γ-aminopropyltriethoxysilane was added and kneaded uniformly, and 120 parts of dehydrated toluene was further added to prepare sample E-2. This was sealed and stored in a metal can with an airtight structure. Reference example 3 Both ends are dimethylvinylsiloxy units, consisting of 12 mol% diphenylsiloxane units and the remaining dimethylsiloxane units, and the viscosity at 25°C is
100 parts of 12000cSt polydiorganosiloxane,
24 parts of fumed silica was added to form the base compound. Next, a complex obtained by heating chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane was added at 10 ppm to the base compound and mixed uniformly. Separately, 100 parts of the above polydiorganosiloxane, 60 parts of polymethylhydrodiene siloxane with trimethylsiloxy units at both ends and a viscosity of 30 cSt at 25°C, and 1.4 parts of 3-methyl-1-butyn-3-ol were added, and the mixture was homogenized. mixed with. Sample E-3 was prepared by mixing these two at a blending ratio of 10:1. In addition,
This final mixing step was performed just before processing the tubes. Example 1 Sample E-1 prepared in Reference Example 1 was applied with a brush to the outer surface of the glass of a 5KW halogen lamp for a fish-collecting lamp, and after the solvent was volatilized, it was left at room temperature for two days and nights to form a silicone elastic film. was formed. Using the benzene-soluble polyorganosiloxane resin solutions described below, samples 11 to 14 that can be cured into resins shown in Table 1 were prepared. Samples 11 and 13 are comparative samples. R-1 consists of R 1 SiO 3/2 units and R 1 2 SiO units,
50% xylene solution of polymethylphenylsiloxane resin solution R-2 SiO 2 where R 1 /Si is 1.45, phenyl group in R 1 is 50 mol%, remainder is methyl group, and has hydroxyl group bonded to silicon atom. unit and R 1 3 SiO 1/2 unit,
The ratio of R 1 3 SiO 1/2 units to SiO 2 units is 0.65
A 50% toluene solution of a polymethylsiloxane resin having hydroxyl groups bonded to silicon atoms in moles These samples were applied with a brush to the surface of a silicone elastomer membrane to examine wettability. The results are shown in Table 1. After volatilizing the solvent, the applied resin sample was cured under the curing conditions shown in Table 1 to form a silicone resin film. For comparison, we prepared a halogen lamp of the same type without any treatment and a halogen lamp with only a silicone elastic film formed thereon. The following experiments were conducted on these treated and untreated halogen lamps. Experiment: Turn on the light for 15 minutes, then spray cold water at 5°C from the side through the nozzle and observe whether there is any damage. Experiment After turning on the lights continuously for 24 hours, observe the surface condition. Experiment Leave it outdoors for 180 days and observe the surface condition. These results are summarized in Table 1.
【表】【table】
【表】
実施例 ２
940Wのクリヤー型高圧ナトリウムランプのガ
ラス外表面に、参考例２で調製した試料Ｅ−２を
エアガンで吹付け、溶剤を揮散させたのち、常温
で３昼夜放置して、シリコーン弾性体膜を形成さ
せた。ついで、実施例１で用いたベンゼン可溶性
ポリオルガノシロキサン樹脂溶液を含む試料11〜
14をシリコーン弾性体膜の表面に流し塗りして、
濡れ性をみた。この結果を第２表に示す。なお、
比較のために、Ｅ−２の塗布によるシリコーン弾
性体膜の形成を行わずに、直接、試料11および14
をガラス外表面に塗布した比較供試品も作成し
た。これらのナトリウムランプについて、第２表
に示す硬化条件で硬化することによりシリコーン
樹脂膜を形成させたのち、実施例１と同様の実験
を行つた。これらの結果を第２表にまとめた。[Table] Example 2 Sample E-2 prepared in Reference Example 2 was sprayed on the glass outer surface of a 940W clear high-pressure sodium lamp with an air gun, the solvent was evaporated, and the lamp was left at room temperature for 3 days and nights. A silicone elastic film was formed. Next, samples 11 to 10 containing the benzene-soluble polyorganosiloxane resin solution used in Example 1 were prepared.
14 on the surface of the silicone elastic membrane,
I looked at the wettability. The results are shown in Table 2. In addition,
For comparison, samples 11 and 14 were directly coated without forming a silicone elastomer film by applying E-2.
A comparison sample was also created in which the coating was applied to the outer surface of the glass. These sodium lamps were cured under the curing conditions shown in Table 2 to form silicone resin films, and then experiments similar to those in Example 1 were conducted. These results are summarized in Table 2.
【表】
実施例 ３
実施例２で用いたナトリウムランプ２個をと
り、うち１個は実施例２と同様に、試料Ｅ−２を
用いてシリコーン弾性体膜をガラス外表面に形成
した。ついで、双方のナトリウムランプに、実施
例２と同様にして、試料12を用いてシリコーン樹
脂膜を形成した。このようにして得られた２個の
供試ナトリウムランプを屋外の照明灯器具に取付
け、日没より日の出まで自動的に点灯するように
して90日間放置した。本発明による二重の保護膜
を有するナトリウムランプの保護膜は全く異常が
なかつたのに対し、比較供試ランプのシリコーン
樹脂膜には亀裂の発生が認められた。
実施例 ４
1KWの集魚灯用ナトリウムランプのガラス外
表面に、参考例３で調製した試料Ｅ−３を刷毛塗
りし、溶剤を揮発させたのち、120℃で１時間加
熱を行つてシリコーン弾性体膜を形成させた。つ
いで、実施例１で用いた試料11〜14をシリコーン
弾性体膜の表面に刷毛塗りして、濡れ性をみた。
その結果を第３表に示す。第３表に硬化条件で硬
化することにより、シリコーン樹脂膜を形成させ
たのち、実施例１と同様の実験を行つた。これら
の結果を第３表にまとめた。また、うち試料12を
施したナトリウムランプについて、実施例３と同
様の点灯屋外放置を120日間行つたが、異常は認
められなかつた。[Table] Example 3 Two sodium lamps used in Example 2 were taken, and in one of them, a silicone elastic film was formed on the outer surface of the glass using Sample E-2 in the same manner as in Example 2. Next, a silicone resin film was formed on both sodium lamps using Sample 12 in the same manner as in Example 2. The two test sodium lamps thus obtained were attached to an outdoor lighting fixture and left for 90 days so that they would automatically turn on from sunset to sunrise. While there was no abnormality in the protective film of the sodium lamp having a double protective film according to the present invention, cracks were observed in the silicone resin film of the comparative lamp. Example 4 Sample E-3 prepared in Reference Example 3 was applied with a brush to the glass outer surface of a 1KW sodium lamp for a fishing lamp, and after the solvent was evaporated, heating was performed at 120°C for 1 hour to form a silicone elastomer. A film was formed. Next, Samples 11 to 14 used in Example 1 were applied with a brush to the surface of the silicone elastomer film to examine wettability.
The results are shown in Table 3. After forming a silicone resin film by curing under the curing conditions shown in Table 3, the same experiment as in Example 1 was conducted. These results are summarized in Table 3. In addition, the sodium lamp prepared with Sample 12 was left lit outdoors for 120 days in the same manner as in Example 3, but no abnormality was observed.
【表】【table】
【表】
実施例 ５
100Wの反射型投光電球のガラス外表面に、参
考例３で調製した試料Ｅ−３を用い、実施例４と
同様にしてシリコーン弾性体膜を形成させた。実
施例１で用いたベンゼン可溶性ポリメチルフエニ
ルシロキサン樹脂溶液Ｒ−１を用い、第４表に示
すような試料51〜54を調製した。これらの試料を
シリコーン弾性体膜の表面に流し塗りし、その濡
れ性をみた。ついで、溶剤を揮散させたのち、第
４表に示す硬化条件で硬化を行つてシリコーン樹
脂膜を形成した。このようにして得られた被層保
護膜つきの電球について、実施例１と同様の実験
を行つた。その結果は第４表に示すとおりであつ
た。[Table] Example 5 A silicone elastic film was formed on the outer glass surface of a 100W reflective floodlight bulb in the same manner as in Example 4 using Sample E-3 prepared in Reference Example 3. Using the benzene-soluble polymethylphenylsiloxane resin solution R-1 used in Example 1, samples 51 to 54 as shown in Table 4 were prepared. These samples were flow-coated onto the surface of the silicone elastomer membrane and their wettability was examined. Then, after volatilizing the solvent, curing was performed under the curing conditions shown in Table 4 to form a silicone resin film. The same experiment as in Example 1 was conducted on the light bulb with the protective film thus obtained. The results were as shown in Table 4.
【表】【table】
【表】
実施例 ６
1KWのけい光水銀ランプのガラス外表面に、
参考例１で調製した試料Ｅ−１を用い、実施例１
と同様にしてシリコーン弾性体皮膜を形成させ
た。下記のベンゼン可溶性ポリメチルフエニルシ
ロキサンＲ−３〜Ｒ−５を用いて、第５表に示さ
れる樹脂状に硬化しうる試料61〜64を調製した。
Ｒ−３ R1SiO3/2単位とＲ１ ２SiO単位から成り、
R1／Siが1.52、R1中フエニル基が42モル％で残
余がメチル基であり、ケイ素原子に結合せる水
酸基を有するポリメチルフエニルシロキサン樹
脂の50％キシレン溶液
Ｒ−４ R1SiO3/2単位とＲ１ ２SiO単位から成り、
R1／Siが1.38、R1中フエニル基が28モル％で残
余がメチル基であり、ケイ素原子に結合せる水
酸基を有するポリメチルフエニルシロキサン樹
脂の50％キシレン溶液
Ｒ−５ 12.5モル％のC6H5SiO3/2単位と残余の
CH3SiO3/2単位から成り、ケイ素原子に結合
せるイソプロポキシ基を有するポリメチルフエ
ニルシロキサンの30％トルエン溶液
これらの試料をシリコーン弾性体膜の表面に刷
毛塗りし、その濡れ性をみた。ついで溶剤を揮散
せしめ、第５表に示す硬化条件で硬化を行つてシ
リコーン樹脂膜を形成した。このようにして得ら
れた複層保護膜つきけい光水銀ランプについて、
実施例１と同様の実験を行つた。その結果は第５
表に示すとおりであつた。[Table] Example 6 On the outer surface of the glass of a 1KW fluorescent mercury lamp,
Example 1 using sample E-1 prepared in Reference Example 1
A silicone elastomer film was formed in the same manner as above. Using benzene-soluble polymethylphenylsiloxanes R-3 to R-5 shown below, resin-curable samples 61 to 64 shown in Table 5 were prepared. R-3 Consists of R 1 SiO 3/2 units and R 1 2 SiO units,
50% xylene solution R-4 of polymethylphenylsiloxane resin with R 1 /Si of 1.52, phenyl groups in R 1 being 42 mol%, the remainder being methyl groups, and hydroxyl groups bonded to silicon atoms R 1 SiO 3 /2 unit and R 1 2 SiO unit,
R 1 /Si is 1.38, phenyl group in R 1 is 28 mol %, remainder is methyl group, 50% xylene solution R-5 of polymethylphenylsiloxane resin having hydroxyl group bonded to silicon atom 12.5 mol % C 6 H 5 SiO 3/2 units and the remaining
A 30% toluene solution of polymethylphenylsiloxane, which is composed of CH 3 SiO 3/2 units and has isopropoxy groups bonded to silicon atoms. These samples were applied with a brush to the surface of the silicone elastomer film, and their wettability was observed. . The solvent was then volatilized and curing was performed under the curing conditions shown in Table 5 to form a silicone resin film. Regarding the fluorescent mercury lamp with a multilayer protective film obtained in this way,
An experiment similar to Example 1 was conducted. The result is the fifth
It was as shown in the table.
【表】【table】
第１図は本発明による電球の概念図で、１はガ
ラス、２はシリコーン弾性体膜、３はシリコーン
樹脂膜を示す。
FIG. 1 is a conceptual diagram of a light bulb according to the present invention, in which 1 is glass, 2 is a silicone elastic film, and 3 is a silicone resin film.
Claims (1)
加熱でゴム状に硬化しうるシリコーン組成物を塗
布し、硬化してシリコーン弾性体としたのち、そ
の外表面に (A) 平均組成式R1 aSi（OR2）bO〓〓〓〓〓（たゞ
し、R1は互に同一または相異なる置換または
非置換の１価炭化水素基、R2は水素原子また
は炭素数１〜４のアルキル基、ａは0.85〜1.55
の数、ｂは0.01〜２の数を示し、ａ＋ｂは３を
越えない）で表わされるベンゼン可溶性ポリオ
ルガノシロキサン樹脂、 (B) 分子式R3 4Si、R4 3SiO〔R5 2SiO〕nSiR4 3、ま
たは〔R6 2SiO〕o（たゞし、式中R3〜R6はそれ
ぞれ互に同一または相異なるアルキル基、ｍは
０または正の数、ｎは正の数を示す）で表わさ
れ、かつ常圧における沸点が70〜250℃の範囲
である揮発性有機ケイ素化合物、および (C) 炭化水素系溶媒 から成り、(B)の量が(B)と(C)の合計量の５〜75重量
％である、樹脂状に硬化しうる組成物を塗布し、
(B)及び(C)を揮散させ、硬化せしめて平均組成式
R1 aSiO〓〓〓（たゞし、R1、ａは上記に同じ）
で表わされるシリコーン樹脂膜を形成させること
を特徴とする、保護膜付管球の製造方法。 ２ (A)が実質的にSiO2単位とR1 3SiO1/2単位から
成り、R2が水素原子で、SiO2単位１モルに対す
るR1 3SiO1/2単位の割合が0.4〜1.0モルである、
特許請求の範囲第１項記載の製造方法。 ３ (A)が実質的にR1SiO3/2単位とR1 2SiO単位か
ら成り、R1がメチル基およびフエニル基から成
る群より選ばれた１価の炭化水素基である、特許
請求の範囲第１項記載の製造方法。 ４ R1／Siが1.05〜1.55であり、かつR1中のフエ
ニル基が25〜50モル％である、特許請求の範囲第
３項記載の製造方法。 ５ (A)の量が、(A)、(B)、(C)の合計に対して５〜80
重量％である、特許請求の範囲第１項記載の製造
方法。 ６ (B)のR3〜R6がメチル基である、特許請求の
範囲第１項記載の製造方法。 ７ (B)が〔（CH3）2SiO〕4である、特許請求の範囲
第６項記載の製造方法。 ８ (B)の量が(B)と(C)の合計に対して10〜65重量％
である、特許請求の範囲第１項記載の製造方法。 ９ (C)がトルエンおよびキシレンから選ばれた芳
香族炭化水素である、特許請求の範囲第１項記載
の製造方法。 １０ オルガノシロキサン樹脂組成物に硬化触媒
を添加して硬化せしめる、特許請求の範囲第１項
記載の製造方法。 １１ 常温でゴム状に硬化しうるシリコーン組成
物が、シラノール末端ポリジオルガノシロキサン
と、ケイ素原子に結合せる加水分解性基が１分子
中に平均２個を越える数存在する有機ケイ素化合
物から成る、特許請求の範囲第１項記載の製造方
法。 １２ 加水分解性基がアセトキシ基である、特許
請求の範囲第１１項記載の製造方法。 １３ 加水分解性基がジオルガノケトオキシム基
である、特許請求の範囲第１１項記載の製造方
法。 １４ 常温でゴム状に硬化しうるシリコーン組成
物が、ケイ素原子に結合せるビニル基が１分子中
に少くとも２個存在するポリオルガノシロキサン
と、ケイ素原子に結合せる水素原子が１分子中に
平均２個を越える数存在するポリオルガノハイド
ロジエンシロキサンから成る、特許請求の範囲第
１項記載の製造方法。[Claims] 1. A silicone composition that can be cured into a rubber-like state at room temperature or by slight heating is applied to the outer surface of a glass tube, and after curing to form a silicone elastic body, the outer surface is coated with ( A) Average compositional formula R 1 a Si (OR 2 ) b O〓〓〓〓〓 or an alkyl group having 1 to 4 carbon atoms, a is 0.85 to 1.55
Benzene-soluble polyorganosiloxane resin (B) Molecular formula: R 3 4 Si, R 4 3 SiO [R 5 2 SiO] n SiR 4 3 or [R 6 2 SiO] o (in the formula, R 3 to R 6 are the same or different alkyl groups, m is 0 or a positive number, and n is a positive number) ) and has a boiling point in the range of 70 to 250°C at normal pressure, and (C) a hydrocarbon solvent, where the amount of (B) is equal to (B) and (C). applying a resinously curable composition in an amount of 5 to 75% by weight of the total amount of
After volatilizing (B) and (C) and curing, the average composition formula
R 1 a SiO〓〓〓ゞ (R 1 and a are the same as above)
A method for manufacturing a tube with a protective film, the method comprising forming a silicone resin film represented by: 2 (A) substantially consists of SiO 2 units and R 1 3 SiO 1/2 units, R 2 is a hydrogen atom, and the ratio of R 1 3 SiO 1/2 units to 1 mole of SiO 2 units is 0.4 to 1.0. is a mole,
A manufacturing method according to claim 1. 3. A patent claim in which (A) consists essentially of R 1 SiO 3/2 units and R 1 2 SiO units, and R 1 is a monovalent hydrocarbon group selected from the group consisting of a methyl group and a phenyl group. The manufacturing method according to item 1. 4. The manufacturing method according to claim 3, wherein R1 /Si is 1.05 to 1.55 and the phenyl group in R1 is 25 to 50 mol%. 5 The amount of (A) is 5 to 80 relative to the total of (A), (B), and (C).
% by weight, the manufacturing method according to claim 1. 6. The manufacturing method according to claim 1, wherein R3 to R6 in (B) are methyl groups. 7. The manufacturing method according to claim 6, wherein (B) is [(CH 3 ) 2 SiO] 4 . 8 The amount of (B) is 10 to 65% by weight based on the total of (B) and (C)
The manufacturing method according to claim 1. 9. The manufacturing method according to claim 1, wherein (C) is an aromatic hydrocarbon selected from toluene and xylene. 10. The manufacturing method according to claim 1, wherein the organosiloxane resin composition is cured by adding a curing catalyst. 11 A patent in which a silicone composition that can be cured into a rubbery state at room temperature is composed of a silanol-terminated polydiorganosiloxane and an organosilicon compound in which each molecule has an average of more than two hydrolyzable groups that bond to silicon atoms. The manufacturing method according to claim 1. 12. The manufacturing method according to claim 11, wherein the hydrolyzable group is an acetoxy group. 13. The manufacturing method according to claim 11, wherein the hydrolyzable group is a diorganoketoxime group. 14 A silicone composition that can be cured into a rubbery state at room temperature is a polyorganosiloxane in which at least two vinyl groups bonded to silicon atoms exist in one molecule, and an average number of hydrogen atoms bonded to silicon atoms in one molecule. The manufacturing method according to claim 1, comprising more than two polyorganohydrodiene siloxanes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17344479A JPS5696441A (en) | 1979-12-28 | 1979-12-28 | Tubular bulb having double protective film and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17344479A JPS5696441A (en) | 1979-12-28 | 1979-12-28 | Tubular bulb having double protective film and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5696441A JPS5696441A (en) | 1981-08-04 |
| JPS6237505B2 true JPS6237505B2 (en) | 1987-08-12 |
Family
ID=15960580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17344479A Granted JPS5696441A (en) | 1979-12-28 | 1979-12-28 | Tubular bulb having double protective film and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5696441A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459506A (en) * | 1982-11-08 | 1984-07-10 | Premier Industrial Corporation | Incandescent illuminating device with antifragility coating |
| JPS61114457A (en) * | 1984-09-26 | 1986-06-02 | ゼネラル・エレクトリツク・カンパニイ | Reduction of ultraviolet rays radiation from lamp and product manufactured thereby |
| JPH084684Y2 (en) * | 1991-07-29 | 1996-02-07 | 株式会社押野電気製作所 | Very small colored indicator lamp |
| JPH0628985U (en) * | 1992-09-08 | 1994-04-15 | 大明電話工業株式会社 | light bulb |
| WO2019150518A1 (en) * | 2018-01-31 | 2019-08-08 | 株式会社ライフエレックス | Automotive light bulb, manufacturing method for automotive light bulb, and manufacturing device for automotive light bulb |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS47298U (en) * | 1971-10-22 | 1972-06-26 |
-
1979
- 1979-12-28 JP JP17344479A patent/JPS5696441A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS47298U (en) * | 1971-10-22 | 1972-06-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5696441A (en) | 1981-08-04 |
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