JPH0333056A - Refractories - Google Patents
RefractoriesInfo
- Publication number
- JPH0333056A JPH0333056A JP1166534A JP16653489A JPH0333056A JP H0333056 A JPH0333056 A JP H0333056A JP 1166534 A JP1166534 A JP 1166534A JP 16653489 A JP16653489 A JP 16653489A JP H0333056 A JPH0333056 A JP H0333056A
- Authority
- JP
- Japan
- Prior art keywords
- refractories
- refractory
- chloride
- parts
- refractory aggregate
- 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.)
- Pending
Links
- 239000011819 refractory material Substances 0.000 title abstract description 20
- 239000011134 resol-type phenolic resin Substances 0.000 claims abstract description 18
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000001119 stannous chloride Substances 0.000 claims abstract description 5
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 5
- 239000011820 acidic refractory Substances 0.000 claims abstract description 4
- 239000011821 neutral refractory Substances 0.000 claims abstract description 4
- 229920003987 resole Polymers 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009970 fire resistant effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011823 monolithic refractory Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical group O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野〉 本発明は、耐火物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to refractories.
（従来の技術）
転炉、電気炉、取鍋、混銑車等の熔融金属の容器は、−
船釣にマグネシア、アル處す、炭素質等を主体とした耐
火性骨材と、レゾール型フェノール樹脂をバインダーと
から生産される。(Prior art) Containers for molten metal such as converters, electric furnaces, ladles, and pig iron trucks are -
For boat fishing, it is produced from fire-resistant aggregate mainly made of magnesia, alkaline, carbonaceous, etc., and a resol type phenolic resin as a binder.
特にレゾール型フェノール樹脂の熱硬化性、高に広く使
用されている。In particular, resol type phenolic resins are highly thermosetting and widely used.
ところがバインダーとして利用されるレゾール型フェノ
ール樹脂は、一般に比較的低温（５０〜１００℃）にお
ける熱硬化速度が緩慢であり、特に形状の大きい耐火物
においては乾燥工程の初期段階に於いて耐火物の素地の
軟化、膨れ、亀裂などの欠陥が度々見受けられる。However, resol-type phenolic resins used as binders generally have a slow heat curing rate at relatively low temperatures (50 to 100°C), and in the early stage of the drying process, especially for large-sized refractories, Defects such as softening, blistering, and cracking of the base material are often observed.
乾燥工程における強度を高めた耐火物としては、特開昭
５６−３２３６７号公報にレゾール型フェノール樹脂に
亜鉛、ニッケル、コバルト、銅、マグネシウム、鉄等の
塩化物を添加した耐火物が開示されている。As a refractory with increased strength in the drying process, JP-A-56-32367 discloses a refractory made by adding chlorides such as zinc, nickel, cobalt, copper, magnesium, iron, etc. to a resol type phenolic resin. There is.
（発明が解決しようとする課題）
しかしながら、特開昭５６−３２３６７号公報に具体的
に示されている金属塩化物をレゾール型フェノール樹脂
に添加した耐火物は、比較的低温（約５０〜１００℃）
における硬化性が未だ緩慢であり、乾燥工程の初期段階
における強度が未だ充分に発現しなかった。(Problem to be Solved by the Invention) However, the refractory material specifically shown in JP-A No. 56-32367, in which a metal chloride is added to a resol type phenolic resin, has a relatively low temperature (approximately 50 to 100 ℃)
The curing properties were still slow, and the strength at the initial stage of the drying process was not yet fully developed.
（課題を解決するための手段）
本発明者等は、上記実情に鑑み鋭意検討したところ、金
属塩化物の中でも特に塩化第二鉄、塩化アルミニウムお
よび塩化第一錫を用いた耐火物が、比較的低温において
も充分な硬化速度を有し、乾燥工程初期段階における圧
縮強度に優れ、膨れ、亀裂等の発生が少ない耐火物とな
ることを見い出し本発明を充放するに至った。(Means for Solving the Problems) The inventors of the present invention have made extensive studies in view of the above circumstances, and have found that refractories using ferric chloride, aluminum chloride, and stannous chloride among metal chlorides are comparatively The present inventors have discovered that the refractory material has a sufficient curing rate even at extremely low temperatures, has excellent compressive strength in the initial stage of the drying process, and is less prone to blistering, cracking, etc., and has developed the present invention.
即ち本発明は、塩化第二鉄、塩化アルミニウムおよび塩
化第一錫から選ばれる少なくとも一種の金属塩化物（Ａ
）、耐火性骨材（Ｂ）並びにレゾール型フェノール樹脂
（Ｃ）からなる耐火物を提供するものである。That is, the present invention provides at least one metal chloride (A
), a refractory comprising a refractory aggregate (B) and a resol type phenolic resin (C).
本発明に係る金属塩化物（Ａ）は、塩化第二鉄、塩化ア
ル柔ニウムおよび塩化第一錫であり、これらは無水物で
あってもよいし、水和物であってもよい。The metal chlorides (A) according to the present invention are ferric chloride, aluminum chloride, and stannous chloride, and these may be anhydrous or hydrated.
本発明に係る耐火性骨材（Ｂ）としてはマグネシア、カ
ルシア、ドロマイト、アルξす、バイアルξす、炭化ケ
イ素、炭素質、シャモット、ジルコンおよびシリカ等の
公知慣用の塩基性、中性または酸性のいずれの骨材も使
用できる。As the refractory aggregate (B) according to the present invention, known and commonly used basic, neutral or acidic aggregates such as magnesia, calcia, dolomite, aluminum ξ, vial ξ, silicon carbide, carbonaceous, chamotte, zircon and silica are used. Any of the following aggregates can be used.
本発明に係るレゾール型フェノール樹脂（Ｃ）とは、フ
ェノール類とホルムアルデヒド類とを塩基性触媒の存在
下で、反応させた樹脂であり、例の条件で反応せしめた
ものが挙げられ、中でも数平均分子ｉ１３００〜１００
０のものが好ましい。The resol type phenolic resin (C) according to the present invention is a resin obtained by reacting phenols and formaldehyde in the presence of a basic catalyst, including those reacted under the conditions of the example, among which several Average molecular i1300~100
0 is preferred.
本発明に係るレゾール型フェノール樹脂（Ｃ）の製造方
法は、上記条件で反応させることを除いて特に限定され
るものではなく、公知慣用の方法がいずれも採用できる
。The method for producing the resol type phenolic resin (C) according to the present invention is not particularly limited, except that the reaction is carried out under the above conditions, and any known and commonly used method can be employed.
レゾール型フェノール樹脂（Ｃ）の製造の際に用いるこ
とのできるフェノール類としては例えば、フェノール、
クレゾール、キシレノール、レゾールシン、カテコール
、ハイドロキノン、クロロフェノール、ブロモフェノー
ル、ビスフェノールＡおよびビスフェノールＦ等が、ホ
ルムアルデヒド類としては例えば、ホルムアルデヒド、
パラホルム等か、塩基性触媒としては水酸化ナトリウム
、炭酸ナトリウム、アンモニア、ジエチルアミン、トリ
エチルアミン等が挙げられる。Examples of phenols that can be used in the production of the resol type phenolic resin (C) include phenol,
Cresol, xylenol, resorcin, catechol, hydroquinone, chlorophenol, bromophenol, bisphenol A, bisphenol F, etc., and formaldehydes include, for example, formaldehyde,
Examples of the basic catalyst include paraform, sodium hydroxide, sodium carbonate, ammonia, diethylamine, and triethylamine.
本発明の耐火物は、上記金属塩化物（Ａ）、耐火骨材（
Ｂ）およびレゾール型フェノール樹脂（Ｃ）を適宜混合
、混練して調製することができる。その際の該（Ａ）、
（Ｂ）および（Ｃ）の混合割合は特に限定されるもので
はないが、通常その耐火物はレゾール型フェノール樹脂
（Ｃ） １００重量部と金属塩化物（Ａ）０．５〜１
２０重量部と耐火性骨材（Ｂ）５００〜５０００重量部
とからなる。The refractory of the present invention comprises the metal chloride (A), the refractory aggregate (
It can be prepared by appropriately mixing and kneading B) and the resol type phenolic resin (C). In that case, (A),
The mixing ratio of (B) and (C) is not particularly limited, but usually the refractory is 100 parts by weight of resol type phenolic resin (C) and 0.5 to 1 part by weight of metal chloride (A).
20 parts by weight and 500 to 5,000 parts by weight of the refractory aggregate (B).
該（Ａ）、（Ｂ）および（Ｃ）の混合順序は特に限定さ
れることはなく、例えば■該（Ａ）と（Ｂ）を予め充分
に混合した後、８’ｌ （Ｃ）を混合する、■該（Ｂ）
と（Ｃ）を予め混合した後、該（Ａ）を混合する方法等
が挙げられる。The order of mixing (A), (B), and (C) is not particularly limited, and for example, (1) (A) and (B) are sufficiently mixed in advance, and then 8'l (C) is mixed. Do, ■Applicable (B)
Examples include a method of pre-mixing (C) and then mixing (A).
該（Ａ）、（Ｂ）および（Ｃ）を充分に混合するために
、必要に応じて水、有機溶剤を適宜添加してもよい。In order to sufficiently mix (A), (B) and (C), water and an organic solvent may be appropriately added as necessary.
この際用いることのできる有機溶剤としては、エチレン
グリコール、プロピレングリコール、ブチレンゲリコー
ル、エチレングリコールモノメチルエーテル、エチレン
グリコールジメチルエーテル、エチレングリコールジエ
チルエーテル、ジエチレングリコールモノメチルエーテ
ル、ジエチレングリコールジメチルエーテル、ジエチレ
ングリコールジエチルエーテル、メタノール、エタノー
ル、ｎ−プロピルアルコール、イソプロピルアルコール
、アセトン、メチルエチルケトン、メチルイソブチルケ
トン、酢酸エチル、酢酸ブチル、トルエン、キシレン、
ターペン等が例示される。Examples of organic solvents that can be used in this case include ethylene glycol, propylene glycol, butylene gellicol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene,
Turpent etc. are exemplified.
本発明の耐火物は、目的必要に応して定型耐火物または
不定型耐火物のどちらの用途にも用いることができる。The refractory of the present invention can be used as either a regular refractory or a monolithic refractory depending on the purpose.
本発明の耐火物を定型耐火物用として用いる際は、耐火
性骨材（Ｂ）として前記した酸性ないしは中性の耐火性
骨材を用いることが好ましく、中でも該レゾール型フェ
ノール樹脂（Ｃ）１００重量部と、金属塩化物（Ａ）２
〜１００重量部と、酸性ないしは中性の耐火性骨材２０
００〜３０００重量部とからなるものが特に好ましい。When using the refractory of the present invention for regular refractories, it is preferable to use the above-mentioned acidic or neutral refractory aggregate as the refractory aggregate (B), especially the resol type phenolic resin (C) 100 Weight parts and metal chloride (A) 2
~100 parts by weight and 20 parts by weight of acidic or neutral refractory aggregate
00 to 3000 parts by weight are particularly preferred.
本発明の耐火物を定型耐火物とするには、それを型に充
填し、圧力をかけて成形をすればよい。In order to make the refractory of the present invention into a regular refractory, it may be filled into a mold and molded under pressure.
その際の温度、圧力は特に限定されるものではないが、
通常１５〜３０℃、０．８〜１．５ ｔ ／ｃｍ２の条
件でプレス成形が行われる。The temperature and pressure at that time are not particularly limited, but
Press forming is usually performed under conditions of 15 to 30°C and 0.8 to 1.5 t/cm2.
こうして得られる定型耐火物は、乾燥硬化することによ
り不焼成の定型耐火物を得ることができる。その際の乾
燥硬化の条件は特に限定されないが、通常それは、５０
〜１００℃の雰囲気下２〜３時間保持した後、更に２０
０〜３００℃に昇温しその雰囲気下で２０〜４５時間保
持することにより行われる。又、焼成された耐火物が必
要な場合には、更に１２００〜１５００℃に昇温しその
雰囲気下で２４〜４８時間保持すればよい。一方、不定
型耐火物用として用いる際は、耐火骨材（Ｂ）として前
記した塩基性の耐火性骨材を用いることが好ましく、中
でも該レゾール型フェノール樹脂（Ｃ）１００重量部と
金属塩化物（Ａ）３〜６０重量部と、塩基性耐火性骨材
６７０〜２０００重量部とからなるものが特に好ましい
。By drying and curing the thus obtained regular refractory, an unfired regular refractory can be obtained. The conditions for drying and curing at that time are not particularly limited, but usually it is 50%
After holding for 2 to 3 hours in an atmosphere of ~100°C,
This is carried out by raising the temperature to 0 to 300°C and holding it in that atmosphere for 20 to 45 hours. If a fired refractory is required, the temperature may be further raised to 1200 to 1500°C and held in that atmosphere for 24 to 48 hours. On the other hand, when used for monolithic refractories, it is preferable to use the above-mentioned basic fire-resistant aggregate as the fire-resistant aggregate (B), among which 100 parts by weight of the resol type phenolic resin (C) and metal chloride. Particularly preferred is one comprising 3 to 60 parts by weight of (A) and 670 to 2,000 parts by weight of basic fire-resistant aggregate.
上記！戒からなる耐火物は、定型耐火物用の様に圧力を
かけて成形して定型耐火物とした後、そのまま不焼成の
定型耐火物として用いてもよいし、焼成して用いてもよ
いが、常温において短時間で硬化でき、硬化後の強度や
加熱時の施工体の保型力が充分であるので通常加熱して
硬化させるのが容易でない用途に用いられる。例えばそ
の用途としては前記定型耐火物を用いて作られる転炉、
電気炉、取鍋、混銑車等の溶融金属容器の冷却時の補修
等が挙げられる。the above! The refractories made of pre-coated refractories may be molded under pressure to form a regular refractory as for regular refractories, and then used as is as an unfired regular refractory, or they may be used after firing. It can be cured in a short time at room temperature, and has sufficient strength after curing and ability to retain the shape of the construction body when heated, so it is used in applications where it is not easy to cure by heating. For example, its uses include converters made using the above-mentioned regular refractories;
Examples include repairs during cooling of molten metal containers such as electric furnaces, ladles, and pig iron mixers.
上記組成からなる不定型の用途に適した耐火物は、常温
硬化性を有しているので施工現場で混合、混練して用い
ることが好ましい。Since the refractory having the above composition and suitable for amorphous uses has room temperature curability, it is preferable to mix and knead the refractory at the construction site.
その施工方法は特に制限されるものではないが、例えば
流し込み施工、振動成形施工、ラミング（スタンプも含
む）施工などが挙げられ、補修箇所の大小、形状により
適宜選択して施行を行えばよい。The construction method is not particularly limited, but examples include pouring construction, vibration molding construction, ramming (including stamping) construction, etc., and the method may be selected as appropriate depending on the size and shape of the repaired area.
次に本発明を実施例により説明するが、以下「部」は「
重量部」を、「％」は「重量％」を意味するものとする
。Next, the present invention will be explained with reference to Examples.
"parts by weight" and "%" mean "% by weight".
製造例１ レゾール樹脂の製造
フェノール１００部、３７％ホルマリン８６部、４８％
苛性ソーダ水溶液１．８部をフラスコに投入し、９０℃
で３時間反応させた後５０％ｐ−１−ルエンスルホン酸
水溶液を加えｐＨ５に調整後、遊離のフェノール、遊離
のホルムアルデヒド、遊離水を除去しレゾール樹脂（１
）を得た。Production Example 1 Production of resol resin Phenol 100 parts, 37% Formalin 86 parts, 48%
Pour 1.8 parts of caustic soda aqueous solution into a flask and heat to 90°C.
After reacting for 3 hours with 50% p-1-luenesulfonic acid aqueous solution and adjusting the pH to 5, free phenol, free formaldehyde, and free water were removed and the resol resin (1
) was obtained.
レゾール樹脂（１）は濃度７８％、粘度２．０００ｃｐ
ｓ 、 ｐＨ５、数平均分子量４００、固定炭素４５％
であった。Resol resin (1) has a concentration of 78% and a viscosity of 2.000 cp.
s, pH 5, number average molecular weight 400, fixed carbon 45%
Met.
製造例２（同上）
フェノール１００部、３７％ホルマリン８６部、４８％
苛性ソーダ水溶液１．８部をフラスコに投入し、９０℃
で５時間反応させた後、５０％ｐ−トルエンスルホン酸
水溶液を加えｐＨ５に調整後、遊離のフェノール、遊離
のホルムアルデヒド、遊離水を除去した。これにエチレ
ングリコールを加えレゾール樹脂（２〉を得た。Production example 2 (same as above) phenol 100 parts, 37% formalin 86 parts, 48%
Pour 1.8 parts of caustic soda aqueous solution into a flask and heat to 90°C.
After reacting for 5 hours, 50% p-toluenesulfonic acid aqueous solution was added to adjust the pH to 5, and free phenol, free formaldehyde, and free water were removed. Ethylene glycol was added to this to obtain resol resin (2).
レゾール樹脂（２）は、濃度７８％、粘度１００００ｃ
ｐｓ 、 ｐＨ５、数平均分子ｉ１８００．固定炭素４
７％であった。Resol resin (2) has a concentration of 78% and a viscosity of 10000c.
ps, pH 5, number average molecular i1800. fixed carbon 4
It was 7%.
製造例３ （同上）
フェノール１００部、３７％ホルマリン８６部、４８％
苛性ソーダ水溶液１．８部をフラスコに投入し、８０℃
で５時間反応させた後５０％ｐ−）ルエンスルホン酸水
溶液を加えｐＨ５に調整し、遊離のフェノール、ホルム
アルデヒド及び水を除去し、エチルセロソルブで希釈し
レゾール樹脂（３）を得た。レゾール樹脂（３）は、濃
度６０％、粘度１００ｃｐｓ 、 ｐＨ５、数平均分子
ｆｆ１３００、固定炭素３５％であった。Production example 3 (same as above) 100 parts of phenol, 37% formalin 86 parts, 48%
Pour 1.8 parts of caustic soda aqueous solution into a flask and heat to 80°C.
After reacting for 5 hours, a 50% p-)luenesulfonic acid aqueous solution was added to adjust the pH to 5, free phenol, formaldehyde and water were removed, and the mixture was diluted with ethyl cellosolve to obtain a resol resin (3). The resol resin (3) had a concentration of 60%, a viscosity of 100 cps, a pH of 5, a number average molecular weight of 1300, and a fixed carbon of 35%.
実施例１〜５
アルξす骨材（粗粒２０部、中粒２５部、細粒３０部、
微粒１０部）８５部、黒鉛１５部に第１表に示す如き塩
化第二鉄・六水和物各部混合分散し、更にレゾール樹脂
（１）または（２）を各部添加し十分に混練し坏土を得
た。Examples 1 to 5 Aggregates (20 parts of coarse grains, 25 parts of medium grains, 30 parts of fine grains,
Each part of ferric chloride hexahydrate as shown in Table 1 was mixed and dispersed in 85 parts of fine particles (10 parts) and 15 parts of graphite, and further each part of resol resin (1) or (2) was added and thoroughly kneaded. I got soil.
次いでその坏土を金型に型込めして常温、圧力ｌｔ／ａ
ｓ”で、直径２５ｍｍの円柱状テストースを作成した。Next, the clay is put into a mold and kept at room temperature and pressure lt/a.
A cylindrical test piece with a diameter of 25 mm was prepared.
実施例６
実施例３の塩化第二鉄・六水和物を塩化第二スズ・二水
和物に置換した以外は実施例１と同一の方法で坏土を得
、テストピースを作成した。Example 6 A clay was obtained in the same manner as in Example 1, except that ferric chloride hexahydrate in Example 3 was replaced with stannic chloride dihydrate, and a test piece was prepared.
比較例１
実施例３の塩化第二鉄・六水和物を塩化第一鉄・四水和
物に置換した以外は同一の方法で坏土を得、テストピー
スを作成した。Comparative Example 1 A clay was obtained and a test piece was prepared in the same manner as in Example 3 except that ferrous chloride hexahydrate was replaced with ferrous chloride tetrahydrate.
実施例１〜６および比較例１で作成したテストピースを
７０℃で５時間または、１５０℃で５時間乾燥させただ
けの不焼成のテストピース、あるいはＸ０００℃で２時
間焼成したテストピースにつき、圧縮強度、見掛は比重
および気孔率を測定した。その結果を第１表に示した。For unfired test pieces prepared by drying the test pieces prepared in Examples 1 to 6 and Comparative Example 1 at 70 °C for 5 hours or at 150 °C for 5 hours, or for test pieces fired at X000 °C for 2 hours, Compressive strength, apparent specific gravity and porosity were measured. The results are shown in Table 1.
尚試験方法は以下の通り。The test method is as follows.
圧縮強度：常温においてアムスラー試験機を用いテスト
ピース円柱方向に圧縮した際の
圧力の最高値を測定した。Compressive strength: The highest value of pressure was measured when the test piece was compressed in the cylindrical direction using an Amsler tester at room temperature.
見掛は比重：テストピースを用いＪＩＳ Ｒ２２０５に
基いて測定した。Apparent specific gravity: Measured using a test piece based on JIS R2205.
気孔率： 同上。Porosity: Same as above.
／
実施例７〜１０
マグネシア骨材（粗粒と中粒の合計５５部、細粒と微粒
の合計４０部）９５部、黒鉛５部に第１表に示す如き塩
化第二鉄・六水和物各部を混合分散し、更に製造例３の
レゾール樹脂（３）を添加し十分に混練し、モルタルを
得た。/ Examples 7 to 10 95 parts of magnesia aggregate (55 parts in total of coarse grains and medium grains, 40 parts in total of fine grains and fine grains), 5 parts of graphite, and ferric chloride hexahydrate as shown in Table 1. Each part of the product was mixed and dispersed, and the resol resin (3) of Production Example 3 was further added and thoroughly kneaded to obtain a mortar.
実施例１１
実施例１の塩化第二鉄・６水和物を塩化第一スズ・二水
和物に置換した以外は実施例７と同一の方法でモルタル
を得た。Example 11 A mortar was obtained in the same manner as in Example 7 except that ferric chloride hexahydrate in Example 1 was replaced with stannous chloride dihydrate.
比較例２
実施例１から塩化第二鉄・六水和物を除去した以外は実
施例７と同一の方法でモルタルを得た。Comparative Example 2 A mortar was obtained in the same manner as in Example 7 except that ferric chloride hexahydrate was removed from Example 1.
比較例３
実施例７の塩化第二鉄・六水和物を塩化第一鉄・四水和
物に置換した以外は実施例７と同一の方法でモルタルを
得た。Comparative Example 3 A mortar was obtained in the same manner as in Example 7 except that ferric chloride hexahydrate in Example 7 was replaced with ferrous chloride tetrahydrate.
実施例７〜１１および比較例２〜３で得たモルタルを実
施例１と同様な条件でプレス底形し、テストピースを得
、焼成あるいは不焼成のテストピ・−スにつぎ、前記し
たのと同様の方法で圧縮強度、見掛は比重および気孔率
を測定した。その結果を第２表に示した。The mortars obtained in Examples 7 to 11 and Comparative Examples 2 to 3 were press-bottomed under the same conditions as in Example 1 to obtain test pieces. Compressive strength, apparent specific gravity and porosity were measured in the same manner. The results are shown in Table 2.
また、実施例７〜１１のテストピースの常温く２５℃〉
における硬化性を見るためにスプリング式硬さ試験機シ
ョアーＡ型またはＤ型を用いて、プレス成形してテスト
ピースを得てから３時間後、８時間後、２４時間後の表
面硬度を各々測定した。In addition, the test pieces of Examples 7 to 11 at room temperature of 25°C>
In order to check the hardenability of the test pieces, we used a spring-type hardness tester, Shore A type or D type, to measure the surface hardness 3 hours, 8 hours, and 24 hours after press molding to obtain a test piece. did.
その結果もあわせて第２表に示した。The results are also shown in Table 2.
ノ
／
／
（発明の効果）
本発明のレゾール型フェノール樹脂と耐火性骨材と特定
の金属塩化物からなる耐火物は、実施例から明らかな様
に比較的低温における硬化性が優れているので、乾燥工
程初期において耐火物の軟化、膨れ、亀裂などの欠陥が
起こりに＜＜、高強度である。中でも、塩基性の耐火性
骨材を用いた耐火物は、常温で短時間で硬化し、充分な
強度を発現できるという優れた効果を奏するものである
。/ / (Effects of the Invention) As is clear from the examples, the refractory made of the resol-type phenolic resin, fire-resistant aggregate, and specific metal chloride of the present invention has excellent curing properties at relatively low temperatures. , defects such as softening, blistering, and cracking of the refractory occur at the early stage of the drying process. Among these, refractories using basic refractory aggregates have excellent effects in that they harden in a short time at room temperature and can develop sufficient strength.
代 理 人teenager Reason Man
Claims (5)
ら選ばれる少なくとも一種の金属塩化物（Ａ）、耐火性
骨材（Ｂ）並びにレゾール型フェノール樹脂（Ｃ）から
なる耐火物。1. A refractory comprising at least one metal chloride (A) selected from ferric chloride, aluminum chloride, and stannous chloride, a refractory aggregate (B), and a resol type phenolic resin (C).
である請求項１記載の耐火物。2. The refractory according to claim 1, wherein the refractory aggregate (B) is an acidic or neutral refractory aggregate.
１記載の耐火物。3. The refractory according to claim 1, wherein the refractory aggregate (B) is a basic resistant aggregate.
ル樹脂１００重量部に対して２〜１２０重量部である請
求項２記載の耐火物。4. The refractory according to claim 2, wherein the amount of the metal chloride (A) used is 2 to 120 parts by weight based on 100 parts by weight of the resol type phenolic resin.
ル樹脂１００重量部に対して３〜６０重量部である請求
項３記載の耐火物。5. The refractory according to claim 3, wherein the amount of the metal chloride (A) used is 3 to 60 parts by weight based on 100 parts by weight of the resol type phenolic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1166534A JPH0333056A (en) | 1989-06-30 | 1989-06-30 | Refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1166534A JPH0333056A (en) | 1989-06-30 | 1989-06-30 | Refractories |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0333056A true JPH0333056A (en) | 1991-02-13 |
Family
ID=15833076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1166534A Pending JPH0333056A (en) | 1989-06-30 | 1989-06-30 | Refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0333056A (en) |
-
1989
- 1989-06-30 JP JP1166534A patent/JPH0333056A/en active Pending
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