WO2007026498A1 - 溶融金属出湯口用閉塞材 - Google Patents

溶融金属出湯口用閉塞材 Download PDF

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Publication number
WO2007026498A1
WO2007026498A1 PCT/JP2006/315293 JP2006315293W WO2007026498A1 WO 2007026498 A1 WO2007026498 A1 WO 2007026498A1 JP 2006315293 W JP2006315293 W JP 2006315293W WO 2007026498 A1 WO2007026498 A1 WO 2007026498A1
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Prior art keywords
mass
molten metal
binder
solvent
molecular weight
Prior art date
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PCT/JP2006/315293
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English (en)
French (fr)
Inventor
Yukitoshi Kubota
Tatsuya Kageyama
Masatsugu Kitamura
Daisuke Tanaka
Original Assignee
Shinagawa Refractories Co., Ltd.
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Publication date
Application filed by Shinagawa Refractories Co., Ltd. filed Critical Shinagawa Refractories Co., Ltd.
Priority to AU2006286076A priority Critical patent/AU2006286076A1/en
Publication of WO2007026498A1 publication Critical patent/WO2007026498A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/12—Opening or sealing the tap holes
    • C21B7/125—Refractory plugging mass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/14—Closures
    • B22D41/44—Consumable closure means, i.e. closure means being used only once
    • B22D41/46—Refractory plugging masses
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63496—Bituminous materials, e.g. tar, pitch
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/42—Constructional features of converters
    • C21C5/46—Details or accessories
    • C21C5/4653—Tapholes; Opening or plugging thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/15—Tapping equipment; Equipment for removing or retaining slag
    • F27D3/1509—Tapping equipment
    • F27D3/1536—Devices for plugging tap holes, e.g. plugs stoppers
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/3427—Silicates other than clay, e.g. water glass
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    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
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Definitions

  • the present invention relates to a plugging material for a molten metal tap.
  • a plugging material for plugging a molten metal tap for example, an organic binder such as tar or phenol resin is combined with a refractory raw material containing clay and a sintering aid such as metal.
  • a composition was used.
  • the general characteristics required for a molten metal outlet plugging material are as follows: (1) Good filling with a press-fitting machine; (2) High bond strength at high temperatures and excellent hot metal resistance (3) Good hole opening workability; (4) Black smoke generation and dust generation are small from the viewpoint of environmental conservation.
  • Patent Document 1 discloses that a refractory raw material having a particle size of 1 mm or more is 25 to 45 wt% (mass%), and a refractory raw material having a particle size of 0.075 mm or less is 25 to 40 wt%.
  • Patent Document 2 the amount of residual phenol is reduced to 1 wt% (mass%) or less.
  • a blast furnace plugging material characterized by containing a novolak type phenolic resin (A) having a number average molecular weight of 00 to 1000 by GPC (Claim 1); and further containing a refractory aggregate (B) A blast furnace closing material (Claim 3) is disclosed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11 349383 Patent Claim
  • Patent Document 2 Japanese Patent Laid-Open No. 2004-299961 Patent Claim
  • the resole type phenolic resin itself is thermosetting and is not suitable for long-term storage.
  • the change with time is large, and those that have passed the number of days after manufacture are more likely to be poorly filled when plugged. Therefore, the use of resole-type phenol resin is preferred, except in special cases where fast strength properties after filling are required.
  • One of the effects of the binder on the performance of the plugging material is the amount of volatile components, and it is desirable to reduce the amount of volatile components as much as possible.
  • the amount of volatile components is large, the porosity after volatilization increases, leading to a decrease in strength and a decrease in corrosion resistance.
  • an object of the present invention is to provide a highly durable molten metal outlet plugging material using a phenolic resin capable of reducing the amount of solvent addition as compared with the prior art.
  • the present inventors use a novolac type phenol resin having a number average molecular weight of less than 00 by GPC, which can reduce the amount of solvent addition.
  • the carbon bond is strengthened without using a curing agent such as hexamine, high durability can be obtained, and the conventional occlusive material using phenol resin is also slow to cure by heating.
  • a curing agent such as hexamine
  • high durability can be obtained
  • the conventional occlusive material using phenol resin is also slow to cure by heating.
  • the present inventors have found that it is possible to provide a plug for a molten metal outlet that can form a strong hot structure, and have completed the present invention.
  • the plugging material for the molten metal tap according to the present invention has a Nopolac type phenolic resin having a number average molecular weight of less than 00 by GPC of more than 70% by mass and 90% by mass or less, and a solvent of 10% by mass or more. It is composed of a binder composed of less than mass% and having a viscosity of 1 to 3 Pa ′ seconds at 60 ° C. and a refractory aggregate.
  • the plugging material for a molten metal tap according to the present invention is characterized in that the solvent is ethylene glycol.
  • the plugging material for the molten metal tap according to the present invention is characterized in that the amount of the binder is within the range of 10 to 20% by mass with respect to the refractory aggregate.
  • the plugging material for the molten metal tap according to the present invention uses a novolak type phenolic resin having a number average molecular weight force of less than 00 by GPC in order to reduce the blending amount of the solvent in the binder to less than 30% by mass.
  • a resin component By using it as a resin component, it is possible to reduce the tissue collapse due to gasification of volatile components, improve the corrosion resistance and wear resistance, and extend the output time. Play.
  • the plugging material for the molten metal tap according to the present invention comprises a novolak type phenolic resin having a number average molecular weight force of less than 00 by GPC of the phenolic resin used as a binder, more than 70% by mass and 90% by mass or less. It is characterized in that it is composed of at least 30% and less than 30% by weight and has a viscosity at 60 ° C in the range of 3 to 3 Pa's.
  • the viscosity at 60 ° C of the binder is greater than 3 Pa, sec, it will be difficult to obtain a uniform kneaded product during kneading, and the plugging material for the molten metal outlet will be mudgun in an actual furnace. When filling, the extrusion resistance becomes too large, which is not preferable.
  • the viscosity of the binder at 60 ° C is specified when the operating temperature is 60 to 80 ° C when used in the blast furnace exit hole, and the filling workability can be secured at 60 ° C. This is because the filling operation is possible even at 60 ° C or higher. Therefore, when adjusting the viscosity at 60 ° C to 1 to 3 Pa 'seconds, in order to reduce the amount of solvent added, it is necessary to reduce the number average molecular weight by GPC of the novolac-type phenol resin, less than 400 Preferably, it is in the range of 200 to 350, most preferably 250 to 320.
  • examples of the solvent that can be used for the plug for the molten metal outlet of the present invention include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and furfuryl alcohol; ethylene glycol, polyether glycol, and the like.
  • examples include glycols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as methoxybutanol.
  • ethylene glycol is preferable.
  • the mixing ratio of the novolak type phenolic resin and the solvent is more than 70% by mass and less than 90% by mass, preferably 70 to 85% by mass, more preferably 70 to 80% by mass, and 10% by mass or more of the solvent.
  • the amount of binder having the above-described structure is 10 to 20% by mass, preferably 15 to 19% by mass with respect to the refractory aggregate. It is within the range.
  • the blending amount of the binder exceeds 20% by mass, the volatile matter increases, so that the porosity increases after heating the plug for the molten metal outlet, and the durability deteriorates. If the blending amount is less than 10% by mass, sufficient slipperiness cannot be obtained.
  • refractory aggregates include general refractory raw materials such as alumina raw materials, silica raw materials, silicon carbide raw materials, silicon nitride raw materials, carbon raw materials, clay raw materials, mullite, spinel, zircoure, zircon, magnesia, various Metals can be used.
  • the raw material was blended at the blending ratio shown in Table 1 below, and kneaded at 60 ° C for 30 minutes with a mixer equipped with a heat retaining device to obtain the plug material for the molten metal outlet of the present invention product and the comparative product. It was.
  • noinders A to E used in the present invention product and the comparative product are as follows: Binder A: Number average molecular weight 300 by GPC, solvent (ethylene glycol) content 2
  • Binder B GPC number average molecular weight 350, solvent (ethylene glycol) content 2
  • Binder C Number average molecular weight 350 by GPC, solvent (ethylene glycol) content 3
  • the test piece was molded to 40 x 40 x 160 mm at a molding pressure of 5 MPa and reduced and fired at 1000 ° C for 3 hours.
  • pig iron and blast furnace slag were used as erosion agents.
  • the erosion dimension was measured, and the erosion dimension when the erosion dimension of the specimen obtained in Comparative Product 1 was taken as 100 was taken as the erosion index. The smaller the erosion index, the better the corrosion resistance.
  • the rapid heating test evaluates the presence or absence of cracks during rapid heating.
  • a test piece molded to 6 Omm ⁇ X 200 mm at a molding pressure of 5 MPa is immersed in hot metal at 1550 ° C for 3 minutes, then visually. This is an evaluation of the occurrence of cracks.
  • a circle indicates that there are few cracks, and a circle indicates that there are many cracks.
  • the product 1 of the present invention is a plugging material for molten metal outlets to which the binder A is added
  • the product 2 of the present invention is a plugging material for molten metal taps to which the binder B is added.
  • the products 1 and 2 of the present invention both have a compressive strength exceeding 30 MPa and have sufficient strength characteristics. In addition, it is a plug for molten metal outlets that has sufficient durability even in an actual furnace with few cracks in the rapid heating test.
  • Comparative Product 1 is a molten metal outlet plugging material to which the above-mentioned binder C having a solvent content of 35% by mass is added, and has a higher compressive strength than the present product. For the rapid heating test! Many cracks occurred.
  • Comparative product 2 is a molten metal outlet plugging material added with the above-mentioned binder D, which has a GPC number average molecular weight of 500 and a solvent content of 50% by mass, and has a lower compressive strength than comparative product 1. Many cracks occurred in the rapid heating test.
  • Comparative product 3 is a plug for molten metal outlets that has the number average molecular weight measured by GPC of 500 and the above-mentioned solder 1E added with a solvent content of 30% by mass, and has a compressive strength higher than that of comparative product 2. Many cracks occurred in the rapid heating test.

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Abstract

　本発明の溶融金属出湯口用閉塞材は、ゲル・パーミエイション・クロマトグラフィー（以下、「ＧＰＣ」と記載する）による数平均分子量が４００未満のノボラック型フェノール樹脂７０質量％超え９０質量％以下と、溶剤１０質量％以上３０質量％未満から構成され、６０°Cにおける粘度が１～３Ｐａ・秒であるバインダーと、耐火骨材から構成されることを特徴とする。

Description

明 細 書
溶融金属出湯口用閉塞材
技術分野
[0001] 本発明は、溶融金属出湯口用閉塞材に関する。
背景技術
[0002] 従来、溶融金属の出湯口を閉塞するための閉塞材としては、例えば、粘土を含む 耐火原料と金属等の焼結助剤にタール、フエノール榭脂などの有機バインダーを配 合してなる組成物が使用されて 、た。溶融金属出湯口用閉塞材に要求される一般 的な特性としては、（1)圧入機による充填性が良好なこと；（2)高温下での結合強度 が大きぐ耐溶銑滓性に優れていること；（3)開孔作業性が良いこと；（4)環境保全の 面から黒煙の発生や発塵が少ないこと等である。しかしながら、タール系の閉塞材は
、充填後の硬化が緩慢であるため、充分な初期強度を確保することが難しぐかつバ インダ一の揮発も緩慢であるため出湯開始時の発煙 ·発塵が多ぐ安定した出湯ある いは環境保全の点で満足できるものではない。また、フエノール榭脂などの榭脂バイ ンダーを用いた閉塞材にお 、ても、熱可塑性榭脂のみを用いた場合はタール系閉 塞材と同様の特性となり、充分なものではなかった。
[0003] また、例えば、特許文献 1には、粒径が lmm以上である耐火原料を 25〜45重量 % (質量％)、粒径が 0. 075mm以下である耐火原料を 25〜40重量％ (質量％)含 有した耐火原料配合物に、レゾール型フエノール榭脂 (R)とノボラック型フエノール榭 脂（N)と軟化点が 250〜400°Cのコールタールピッチ（C)と力 なり、重量（質量）比 で RZ (R+N) =0. 15〜0. 40、 C/ (R+N + C) =0. 1〜0. 3のノ インダーを 10 〜20重量％ (質量％)の割合で含有させたことを特徴とする出湯口閉塞材が開示さ れている。
[0004] また、特許文献 2には、残留フエノール量を 1重量％ (質量％)以下まで低減した、
GPCによる数平均分子量力 00〜 1000のノボラック型フ ノール榭脂（A)を含有す ることを特徴とする高炉用閉塞材 (請求項 1)；更に、耐火性骨材 (B)を含有した高炉 用閉塞材 (請求項 3)が開示されて 、る。 [0005] 特許文献 1：特開平 11 349383号公報 特許請求の範囲
特許文献 2：特開 2004— 299961号公報 特許請求の範囲
発明の開示
発明が解決しょうとする課題
[0006] し力しながら、特許文献 1に記載されているような出湯口閉塞材においては、レゾー ル型フ ノール榭脂は、それ自体が熱硬化性であるため、長期保存には不向きであ り、出湯口閉塞材に使用する場合、経時変化が大きいため、製造後日数が経過した ものは閉塞時に充填不良を生じ易くなる。従って、充填後の早強特性が必要である 特別な場合を除き、レゾール型フエノール榭脂の使用は好ましくな 、。
[0007] また、閉塞材の性能に与えるバインダーの影響の 1つに揮発成分量があり、揮発成 分量を極力削減することが望ましい。揮発成分量が多いと、揮発後の気孔率が高まり 、強度低下及び耐食性の低下を招く。そのためには溶剤量を低減させる必要があり、 ゲル ·パーミエイシヨン ·クロマトグラフィー（以下、「GPC」と記載する）による数平均分 子量の低いノボラック型フエノール榭脂を使用することが溶剤量低減には有効である 。これは、 GPCによる数平均分子量が高いと、粘性が高まり、閉塞材として必要な充 填性を確保するためには、粘性を調整するために多量の溶剤が必要となる。この溶 剤は。閉塞材使用時には揮発成分としてガス化するものであり、閉塞材の特性を低 下させるために極力削減することが好ま 、。特許文献 2に記載されて 、るような GP Cによる数平均分子量力 00〜 1000のノボラック型フエノール榭脂では、 30質量％ を超えるような多量の溶剤の添カ卩が必要となり、好ましくない。
[0008] 従って、本発明の目的は、従来よりも溶剤添加量を低減することが可能なフエノー ル榭脂を使用した高耐用の溶融金属出湯口用閉塞材を提供することにある。
課題を解決するための手段
[0009] 本発明者らは、上記課題を解決すべく、鋭意検討を重ねた結果、溶剤添加量を低 減することができる GPCによる数平均分子量力 00未満のノボラック型フエノール榭 脂を使用することにより、へキサミンなどの硬化剤を使用しなくてもカーボンボンドが 強化され、高耐用を得ることができ、かつ従来のフエノール榭脂を使用した閉塞材ょ りも加熱による硬化が遅いことにより、急加熱時に亀裂の発生を抑制させることができ 、強固な熱間組織を形成されることができる溶融金属出湯口用閉塞材を提供するこ とができることを見出し、本発明を完成するに至った。
[0010] 即ち、本発明の溶融金属出湯口用閉塞材は、 GPCによる数平均分子量力 00未 満のノポラック型フ ノール榭脂 70質量％超え 90質量％以下と、溶剤 10質量％以 上 30質量％未満から構成され、 60°Cにおける粘度が l〜3Pa'秒であるバインダー と、耐火骨材から構成されることを特徴とする。
[0011] また、本発明の溶融金属出湯口用閉塞材は、溶剤がエチレングリコールであること を特徴とする。
[0012] 更に、本発明の溶融金属出湯口用閉塞材は、バインダーの配合量力 耐火骨材に 対して外掛で 10〜20質量％の範囲内であることを特徴とする。
発明の効果
[0013] 本発明の溶融金属出湯口用閉塞材は、バインダー中の溶剤の配合量を 30質量％ 未満に低減するために、 GPCによる数平均分子量力 00未満のノボラック型フエノー ル榭脂をバインダーの榭脂成分として使用することにより、揮発成分のガス化による 組織崩壊を少なくすることができ、耐食性、耐摩耗性を向上させることができ、出銑時 間を延長することができるという効果を奏する。また、急加熱時の亀裂の発生を抑制 することができ、亀裂への溶銑、スラグの差し込みによる横穴の発生を抑制でき、開 孔作業の負担を大幅に軽減することができるという効果を奏する。
発明を実施するための最良の形態
[0014] 本発明の溶融金属出湯口用閉塞材は、バインダーとして使用されるフエノール榭 脂の GPCによる数平均分子量力 00未満であるノボラック型フエノール榭脂 70質量 %超え 90質量％以下と溶剤 10質量％以上 30質量％未満より構成され、 60°Cにお ける粘度力^〜 3Pa'秒の範囲内にあるものを使用するところに特徴を有する。このよ うなバインダーを使用することにより、良好な混練性及び充填作業性を溶融金属出湯 口用閉塞材に付与することができる。
[0015] ノボラック型フエノール榭脂の GPCによる数平均分子量力 00以上となると、溶融 金属出湯口用閉塞材の充填性の確保あるいは製造時の分散性を確保するための粘 度を調整するため溶剤を多量に使用する必要がある。そのため、著しく強度が低下し 、溶融金属出湯口用閉塞材としての耐食性、耐摩耗性が低下するために好ましくな い。また、バインダーの 60°Cにおける粘度が lPa'秒より小さいと、溶融金属出湯口 用閉塞材中の耐火骨材を保持するための接着力が弱まり、また、溶融金属出湯口用 閉塞材自体の可塑性が低下するために好ましくない。一方、バインダーの 60°Cにお ける粘度が 3Pa，秒より大きい場合には、混練時に均一な混練物を得ることが困難と なり、また、実炉で溶融金属出湯口用閉塞材をマッドガンで充填する際に押出抵抗 が大きくなり過ぎるために好ましくない。
[0016] バインダーの 60°Cにおける粘度を規定するのは、高炉出銑孔にて使用する際の使 用温度が 60〜80°Cであり、 60°Cで充填作業性が確保可能な場合は、 60°C以上の 条件においても充填作業は可能であることによる。よって、 60°Cでの粘度を l〜3Pa' 秒に調整するに際し、溶剤添加量を低減させるためには、ノボラック型フエノール榭 脂の GPCによる数平均分子量を小さくすることが必要となり、 400未満とすることが望 ましく、好ましくは 200〜350、最も好ましくは 250〜320の範囲内である。 GPCによ る数平均分子量力 00以上であると、 60°Cにおける粘度を 3Pa'秒以下にするため には、 30質量％を超える溶剤添加量が必要となり、溶剤添加量の増加により溶融金 属出湯口用閉塞材の耐用性が低下するために好ましくな！/、。
[0017] また、本発明の溶融金属出湯口用閉塞材に使用可能な溶剤としては、例えばエタ ノール、イソプロピルアルコール、ブチルアルコール、フルフリルアルコール等のアル コール類；エチレングリコール、ポリエーテルグリコール等のグリコール類；酢酸ェチ ル等のエステル類；アセトン、メチルェチルケトン等のケトン類;メトシキブタノール等 のエーテル類などを挙げることができ、中でも、エチレングリコールが好ましい。なお、 ノボラック型フエノール榭脂と溶剤の混合割合は、ノボラック型フエノール榭脂 70質量 %超え 90質量％未満、好ましくは 70〜85質量％、更に好ましくは 70〜80質量％、 溶剤 10質量％以上 30質量％未満、好ましくは 15質量％以上 30質量％未満、更に 好ましくは 20質量％以上 30質量％未満の範囲内である。なお、溶剤の添加量が 30 質量％以上となると、急加熱時の亀裂の発生が顕著となり、溶融金属出湯口用閉塞 材の耐用性が低下することがあるために好ましくなぐまた、該添加量が 10質量％未 満では、バインダーの 60°Cにおける粘度を l〜3Pa'秒の範囲内とすることができな いために好ましくない。
[0018] なお、レゾール型フエノール榭脂は、加熱による硬化が著しぐ待機中にマッドガン 中で溶融金属出湯口用閉塞材が硬化することがあるために併用することは好ましくな い。
[0019] 本発明の溶融金属出湯口用閉塞材は、上述のような構成を有するバインダーの配 合量は、耐火骨材に対して外掛で 10〜20質量％、好ましくは 15〜19質量％の範 囲内である。ここで、バインダーの配合量が 20質量％を超えると、揮発分が増加する ため溶融金属出湯口用閉塞材を加熱後、気孔率が大きくなり、耐用性が劣化するた め好ましくなぐまた、バインダーの配合量が 10質量％未満であると、充分なすべり 性を得ることができないため好ましくない。なお、耐火骨材としては、例えば、アルミナ 原料、シリカ原料、炭化珪素原料、窒化珪素原料、カーボン原料、粘土原料等の一 般的な耐火原料や、ムライト、スピネル、ジルコユア、ジルコン、マグネシア、各種金 属等を使用することができる。
実施例
[0020] 以下に実施例及び比較例を挙げて本発明の溶融金属出湯口用閉塞材を更に説 明する。
実施例
以下の表 1に記載する配合割合にて、原料を配合し、保温装置付きミキサーにて 6 0°Cで 30分間混練することにより本発明品及び比較品の溶融金属出湯口用閉塞材 を得た。
なお、本発明品及び比較品に使用したノ インダー A〜Eは、以下の通り： バインダー A: GPCによる数平均分子量 300、溶剤（エチレングリコール）配合量 2
3質量0 /0、 60°Cにおける粘度 = 2. 5Pa'秒
バインダー B： GPCによる数平均分子量 350、溶剤（エチレングリコール）配合量 2
5質量％、 60°Cにおける粘度 = 2Pa'秒
バインダー C： GPCによる数平均分子量 350、溶剤（エチレングリコール）配合量 3
5質量％、 60°Cにおける粘度 = lPa'秒
バインダー D: GPCによる数平均分子量 500、溶剤（エチレングリコール）配合量 5 0質量％、 60°Cにおける粘度 = lPa'秒
バインダー E： GPCによる数平均分子量 500、溶剤（エチレングリコール）配合量 3 0質量％、 60°Cにおける粘度 = 12Pa'秒
[0021] [表 1]
表 1
Figure imgf000007_0001
[0022] 表 1中、圧縮強さ及び見掛気孔率は、成形圧 5MPaで 40 X 40 X 160mmに成形し 、 1350°Cで 3時間還元焼成した試験片につ 、て測定したものである。
耐食性試験は、成形圧 5MPaで 40 X 40 X 160mmに成形し、 1000°Cで 3時間還 元焼成したものを試験片とし、高周波誘導炉により、銑鉄と高炉スラグを侵食剤として 使用し、 1550°Cで 5時間試験を行った後、侵食寸法を測定し、比較品 1で得られた 試験片の侵食寸法を 100とした時の侵食寸法を溶損指数としたものである。なお、溶 損指数が小さい程、耐食性が良いことを示す。
急加熱試験は、急加熱時の亀裂の有無を評価するものであり、成形圧 5MPaで、 6 Omm φ X 200mmに成形した試験片を 1550°Cの溶銑中に 3分間浸漬した後、目視 により亀裂の発生状況を評価したものである。〇印は、亀裂が少ないを、 X印は、亀 裂が多いをそれぞれ示す。 本発明品 1は、上記バインダー Aを添加した溶融金属出湯口用閉塞材で、本発明 品 2は、上記バインダー Bを添加した溶融金属出湯口用閉塞材である。本発明品 1及 び 2は、いずれも圧縮強さが 30MPaを超えており、充分な強度特性を有している。ま た、急加熱試験における亀裂の発生も少なぐ実炉においても充分な耐用性を有す る溶融金属出湯口用閉塞材である。
これに対して、比較品 1は、溶剤配合量が 35質量％の上記バインダー Cを添加した 溶融金属出湯口用閉塞材であり、本発明品と比較して見掛気孔率が高ぐ圧縮強さ は低ぐ急加熱試験にお！、て亀裂が多数発生した。
比較品 2は、 GPCによる数平均分子量が 500で、溶剤配合量が 50質量％の上記 バインダー Dを添加した溶融金属出湯口用閉塞材であり、比較品 1よりも更に圧縮強 さが低ぐ急加熱試験において亀裂が多数発生した。
比較品 3は、 GPCによる数平均分子量が 500で、溶剤配合量が 30質量％の上記 ノ^ンダ一 Eを添加した溶融金属出湯口用閉塞材であり、比較品 2よりも更に圧縮強 さが低ぐ急加熱試験において亀裂が多数発生した。

Claims

請求の範囲
[1] ゲル ·パーミエイシヨン ·クロマトグラフィーによる数平均分子量力 00未満のノボラッ ク型フ ノール榭脂 70質量％超え 90質量％以下と、溶剤 10質量％以上 30質量％ 未満から構成され、 60°Cにおける粘度が l〜3Pa'秒であるバインダーと、耐火骨材 から構成されることを特徴とする溶融金属出湯口用閉塞材。
[2] 溶剤は、エチレングリコールである、請求項 1記載の溶融金属出湯口用閉塞材。
[3] ノ インダ一の配合量は、耐火骨材に対して外掛で 10〜20質量％の範囲内である
、請求項 1または 2記載の溶融金属出湯口用閉塞材。
PCT/JP2006/315293 2005-08-29 2006-08-02 溶融金属出湯口用閉塞材 WO2007026498A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51140909A (en) * 1975-05-30 1976-12-04 Nippon Steel Corp Mud for blast furnace
JPS51140908A (en) * 1975-05-30 1976-12-04 Nippon Steel Corp Mud for blast furnace
JPH03271168A (ja) * 1990-03-19 1991-12-03 Shinagawa Refract Co Ltd 不定形耐火物
JPH04280878A (ja) * 1991-03-07 1992-10-06 Shinagawa Rozai Kk 高炉出銑口用マッド材
JPH08169766A (ja) * 1994-12-15 1996-07-02 Nippon Steel Corp 耐火物用原料、耐火物用バインダー及び耐火物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51140909A (en) * 1975-05-30 1976-12-04 Nippon Steel Corp Mud for blast furnace
JPS51140908A (en) * 1975-05-30 1976-12-04 Nippon Steel Corp Mud for blast furnace
JPH03271168A (ja) * 1990-03-19 1991-12-03 Shinagawa Refract Co Ltd 不定形耐火物
JPH04280878A (ja) * 1991-03-07 1992-10-06 Shinagawa Rozai Kk 高炉出銑口用マッド材
JPH08169766A (ja) * 1994-12-15 1996-07-02 Nippon Steel Corp 耐火物用原料、耐火物用バインダー及び耐火物の製造方法

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