JPH05262958A - Phenolic resin composition for refractory - Google Patents
Phenolic resin composition for refractoryInfo
- Publication number
- JPH05262958A JPH05262958A JP4064681A JP6468192A JPH05262958A JP H05262958 A JPH05262958 A JP H05262958A JP 4064681 A JP4064681 A JP 4064681A JP 6468192 A JP6468192 A JP 6468192A JP H05262958 A JPH05262958 A JP H05262958A
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- resin composition
- parts
- refractories
- refractory
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、不焼成煉瓦、焼成煉瓦
をはじめとする各種耐火物の結合剤として使用される耐
火物用フェノ−ル樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin composition for refractories used as a binder for various refractory materials such as unfired bricks and fired bricks.
【０００２】[0002]
【従来の技術】近年、不焼成煉瓦、焼成煉瓦をはじめと
する各種耐火物の結合剤として、低公害で取扱い易く乾
燥強度及び焼成強度等各種特性に優れたフェノ−ル樹脂
が多用されている。耐火物用の結合剤として用いられる
フェノ−ル樹脂としては、ノボラック型又は／及びレゾ
−ル型の液状又は／及び粉末の樹脂が、単独または併用
のかたちで使用されている。代表的な例を挙げると、ノ
ボラック型フェノ−ル樹脂をあらかじめエチレングリコ
−ル等の溶剤に溶解した液状樹脂が単独又はヘキサメチ
レンテトラミンとの併用で使用されたり、水溶媒又はエ
チレングリコ−ル等の溶剤を含有した液状レゾ−ル樹脂
が単独で使用されたり、ノボラック型又はレゾ−ル型の
粉末フェノ−ル樹脂がメタノ−ル、エチレングリコ−ル
等の湿潤剤又は液状の各種フェノ−ル樹脂との併用で使
用されている。2. Description of the Related Art In recent years, phenolic resins, which are low in pollution and easy to handle and excellent in various properties such as dry strength and baking strength, have been widely used as a binder for various refractory materials such as unfired bricks and baked bricks. .. As the phenol resin used as the binder for the refractory, a novolac type and / or a resole type liquid or / and powder resin is used alone or in combination. As a typical example, a liquid resin prepared by previously dissolving a novolac type phenol resin in a solvent such as ethylene glycol is used alone or in combination with hexamethylenetetramine, or is used as an aqueous solvent or ethylene glycol. The liquid resole resin containing the above solvent is used alone, or the novolak or resole type powder phenol resin is a wetting agent such as methanol or ethylene glycol, or various liquid phenols. Used in combination with resin.
【０００３】以上のように、さまざまなタイプのフェノ
−ル樹脂が各種耐火物用の結合剤として使用されている
が、これら通常のフェノ−ル樹脂の欠点として、高温域
での耐酸化性に乏しいことがあげられる。特に、フェノ
−ル樹脂を結合剤として用いている耐火物は、高温で酸
化され易い黒鉛を骨材として含有するものが大部分であ
り、耐酸化性向上が大きな課題となっている。耐酸化性
改良の手段として、例えば、不焼成マグネシアカ−ボン
煉瓦等の耐火物については、金属シリコン、金属アルミ
のような金属粉を添加するという方法が採られている。
金属粉の添加によって、800-1000℃以上の温度域での耐
酸化性は向上するが、フェノ−ル樹脂の熱分解温度域で
ある400-700℃では、前記の金属粉が溶融しないため酸
化防止効果がほとんどない。また、耐酸化性向上のため
にホウ素酸化物を骨材と結合剤との混練時に添加する方
法が考えられるが、ホウ素酸化物の分散が十分でないた
め多量に添加しないと効果が乏しく、多量に添加した場
合、耐火度の低下等耐火物としての諸特性を損なう恐れ
がある。As described above, various types of phenolic resins have been used as binders for various refractory materials, but one of the drawbacks of these ordinary phenolic resins is that they are resistant to oxidation at high temperatures. Something is scarce. In particular, most of the refractory materials using a phenol resin as a binder contain graphite, which is easily oxidized at high temperature, as an aggregate, and improvement of oxidation resistance is a major issue. As a means for improving the oxidation resistance, for example, for refractory materials such as unburned magnesia carbon bricks, a method of adding metal powder such as metallic silicon or metallic aluminum has been adopted.
The addition of metal powder improves the oxidation resistance in the temperature range of 800-1000 ° C or higher, but at 400-700 ° C, which is the thermal decomposition temperature range of phenolic resin, the above-mentioned metal powder does not melt and thus is oxidized. There is almost no preventive effect. Further, in order to improve the oxidation resistance, a method of adding boron oxide at the time of kneading the aggregate and the binder can be considered, but the effect is poor unless a large amount is added because the dispersion of the boron oxide is insufficient, If it is added, there is a possibility that various properties as a refractory such as a decrease in fire resistance may be impaired.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明者は、
フェノ−ル樹脂自体の耐酸化性を向上させる方法につい
て鋭意検討した結果、本発明を完成するに至ったもので
ある。Therefore, the inventor of the present invention
As a result of extensive studies on a method of improving the oxidation resistance of the phenolic resin itself, the present invention has been completed.
【０００５】[0005]
【課題を解決するための手段】本発明は、フェノ−ル類
とホルムアルデヒド類との付加縮合反応終了後ホウ素酸
化物を配合してなることを特徴とする高温域での耐酸化
性に優れた耐火物用フェノ−ル樹脂組成物に関するもの
である。本発明の耐火物用フェノ−ル樹脂組成物を製造
するために使用するフェノ−ル類には、フェノ−ル、ク
レゾ−ル、キシレノ−ル、エチルフェノ−ル、プロピル
フェノ−ル、カテコ−ル、レゾルシン、ハイドロキノ
ン、ビスフェノ−ルＡ、その他各種アルキルフェノ−ル
などがあり、さらに、これらのフェノ−ル類を製造する
際の副生物も含まれ、これらを単独または２種類以上組
合わせて使用する。一方、アルデヒド類としては、ホル
ムアルデヒド、パラホルムアルデヒド、ベンズアルデヒ
ド等を使用する。ホウ素酸化物としては、ホウ酸、無水
ホウ酸、酸化ホウ素、メタホウ酸等を使用するが、中で
も、ホウ酸（Ｈ3ＢＯ3）がフェノ−ル樹脂との相溶性の
点などから特に好ましい。また、ホウ酸を用いた場合の
ホウ酸の添加量については、フェノ−ル類１００重量部
に対して５〜３０重量部が好ましい。ホウ酸の添加量が
５重量部以下の場合、耐酸化性向上効果が十分ではこと
があり、一方、３０重量部以上の場合、フェノ−ル樹脂
との相溶性が乏しく分離現象を起すことがある。The present invention is excellent in oxidation resistance in a high temperature range characterized by containing a boron oxide after completion of addition condensation reaction of phenols and formaldehydes. The present invention relates to a phenol resin composition for refractories. The phenols used for producing the phenol resin composition for refractory of the present invention include phenol, cresol, xylenol, ethylphenol, propylphenol and catechol. , Resorcin, hydroquinone, bisphenol A, and various other alkylphenols, and by-products in the production of these phenols are also included. These can be used alone or in combination of two or more. To do. On the other hand, formaldehyde, paraformaldehyde, benzaldehyde, etc. are used as aldehydes. The boron oxide, boric acid, boric anhydride, boron oxide, and using the metaboric acid. Of these, boric acid (H 3 BO 3) is phenol - particularly preferable from such viewpoint of compatibility with the Le resin. When boric acid is used, the amount of boric acid added is preferably 5 to 30 parts by weight with respect to 100 parts by weight of phenols. When the addition amount of boric acid is 5 parts by weight or less, the effect of improving the oxidation resistance may be sufficient, while when it is 30 parts by weight or more, the compatibility with the phenol resin is poor and a separation phenomenon may occur. is there.
【０００６】フェノ−ル類とアルデヒド類とを付加縮合
反応する際の触媒としては、樹脂のタイプに応じて、蓚
酸、塩酸、硫酸等の酸類、酢酸亜鉛等の金属塩類、水酸
化ナトリウム、水酸化カリウム、水酸化バリウム、水酸
化カルシウム等のアルカリ類、アンモニア、トリエチル
アミン等のアミン類を単独又は２種以上の併用で使用す
る。液状フェノ−ル樹脂を製造する場合では、溶剤とし
てメタノ−ル、エタノ−ル等のアルコ−ル類、エチレン
グリコ−ル、ジエチレングリコ−ル、プロピレングリコ
−ル、ジプロピレングリコ−ル等のグリコ−ル類の他、
エ−テル類、エステル類、エ−テルテステル類、ケトン
類等各種のものを単独又は２種以上の併用で使用できる
が、ホウ酸との相溶性の面から、水酸基（−ＯＨ）を持
ったアルコ−ル類、グリコ−ル類等が主体であることが
好ましい。本発明の耐火物用フェノ−ル樹脂組成物を製
造する際、ホウ素酸化物は、フェノ−ル類とホルムアル
デヒド類の付加縮合反応の後に添加する。ホウ素酸化物
の添加時期が付加縮合反応以前の場合、ホウ素酸化物が
フェノ−ル類とホルムアルデヒド類との付加縮合反応に
関与して、設計どおりの樹脂が得られないため好ましく
ない。また、粉末樹脂の製造において、粉砕時等にホウ
素酸化物をドライミックスすることは、均一分散性の面
からみて好ましくない。As the catalyst for the addition condensation reaction of phenols and aldehydes, acids such as oxalic acid, hydrochloric acid and sulfuric acid, metal salts such as zinc acetate, sodium hydroxide and water may be used depending on the type of resin. Alkalis such as potassium oxide, barium hydroxide and calcium hydroxide, and amines such as ammonia and triethylamine are used alone or in combination of two or more kinds. In the case of producing a liquid phenol resin, alcohols such as methanol and ethanol as solvents, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol are used as a solvent. Other than
Various substances such as ethers, esters, ether testers, and ketones can be used alone or in combination of two or more, but they have a hydroxyl group (-OH) from the viewpoint of compatibility with boric acid. Alcohols, glycols and the like are preferred. In producing the phenol resin composition for refractory of the present invention, the boron oxide is added after the addition condensation reaction of the phenols and the formaldehydes. When the addition time of the boron oxide is before the addition condensation reaction, the boron oxide participates in the addition condensation reaction between the phenols and the formaldehyde, and the resin as designed cannot be obtained, which is not preferable. Further, in the production of the powder resin, it is not preferable to dry mix the boron oxide at the time of pulverization or the like from the viewpoint of uniform dispersibility.
【０００７】[0007]
【実施例】以下本発明を実施例を用いて具体的に説明す
る。文中に記載されている「部」及び「％」は、すべて
「重量部」及び「重量％」である。 実施例１ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン７７６部及び１０
％水酸化ナトリウム水溶液５０部を仕込み、８５℃で２
時間反応させた。６０℃に冷却後ホウ酸１５０部を添加
し、次いで、６０〜８０ｍｍＨｇの減圧下で内温７５℃
となるまで脱水を行った。内温が７５℃になった時点で
常圧に戻して、エチレングリコ−ル７５０部及びメタノ
−ル１００部を添加混合し、耐火物用フェノ−ル樹脂組
成物を得た。この樹脂は常温で液状であり、２５℃にお
ける粘度は ０.４Pa・sであった。 実施例２ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン５８７部及び３５
％塩酸２部を仕込み、還流条件下で３時間反応させた。
６０℃に冷却後ホウ酸２００部を添加し、次いで、６０
〜８０ｍｍＨｇの減圧下で内温１４０℃となるまで脱水
を行った後取り出し、融点８０℃の固形ノボラック型フ
ェノ−ル樹脂を得た。この樹脂１０００部とヘキサメチ
レンテトラミン１００部とを混合粉砕して、耐火物用フ
ェノ−ル樹脂組成物を得た。この樹脂は常温で粉末であ
り、平均粒径３５μｍ、融点８６℃であった。 実施例３ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン５６０部及び蓚酸
１０部を仕込み、還流条件下で３時間反応させた。６０
℃に冷却後ホウ酸１００部を添加し、次いで、６０〜８
０ｍｍＨｇの減圧下で内温１３０℃となるまで脱水を行
った。内温が１３０℃になった時点で、常圧に戻してエ
チレングリコ−ル６５０部を添加混合し、耐火物用フェ
ノ−ル樹脂組成物を得た。この樹脂は常温で液状であ
り、２５℃における粘度は ７.０Pa・sであった。EXAMPLES The present invention will be specifically described below with reference to examples. All “parts” and “%” described in the text are “parts by weight” and “% by weight”. Example 1 A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 1000 parts of phenol, 776 parts of 37% formalin and 10 parts of 37% formalin.
50% aqueous sodium hydroxide solution was added and the mixture was heated at 85 ° C for 2 hours.
Reacted for hours. After cooling to 60 ° C., 150 parts of boric acid was added, and then the internal temperature was 75 ° C. under reduced pressure of 60 to 80 mmHg.
It was dehydrated until. When the internal temperature reached 75 ° C, the pressure was returned to normal pressure, and 750 parts of ethylene glycol and 100 parts of methanol were added and mixed to obtain a phenol resin composition for refractory. This resin was liquid at room temperature and had a viscosity of 0.4 Pa · s at 25 ° C. Example 2 In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 1000 parts of phenol, 587 parts and 587 parts of 37% formalin were added.
% 2% hydrochloric acid was charged, and the mixture was reacted under reflux conditions for 3 hours.
After cooling to 60 ° C., 200 parts of boric acid was added, then 60
It was dehydrated under reduced pressure of -80 mmHg until the internal temperature reached 140 ° C and then taken out to obtain a solid novolac type phenol resin having a melting point of 80 ° C. 1000 parts of this resin and 100 parts of hexamethylenetetramine were mixed and pulverized to obtain a phenol resin composition for refractory. This resin was a powder at room temperature and had an average particle size of 35 μm and a melting point of 86 ° C. Example 3 A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 1000 parts of phenol, 560 parts of 37% formalin and 10 parts of oxalic acid, and reacted under reflux conditions for 3 hours. 60
After cooling to ℃, 100 parts of boric acid was added, and then 60 to 8
It was dehydrated under reduced pressure of 0 mmHg until the internal temperature reached 130 ° C. When the internal temperature reached 130 ° C, the pressure was returned to normal pressure and 650 parts of ethylene glycol was added and mixed to obtain a phenol resin composition for refractory. This resin was liquid at room temperature and had a viscosity at 25 ° C. of 7.0 Pa · s.
【０００８】比較例１ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン１０３４部及び１
０％水酸化ナトリウム水溶液１００部を仕込み、８５℃
で３時間反応させた。６０℃に冷却後酢酸１５部を添加
し、次いで、６０〜８０ｍｍＨｇの減圧下で内温７５℃
となるまで脱水を行った。内温が７５℃になった時点で
常圧に戻して、エチレングリコ−ル７００部を添加混合
し、液状フェノ−ル樹脂を得た。この樹脂の２５℃にお
ける粘度は ０.５Pa・sであった。 比較例２ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン７３３部及び３５
％塩酸２部を仕込み、還流条件下で３時間反応させた。
次いで、６０〜８０ｍｍＨｇの減圧下で内温１４０℃と
なるまで脱水を行った後取り出し、融点８０℃の固形ノ
ボラック型フェノ−ル樹脂を得た。この樹脂１０００部
とヘキサメチレンテトラミン１００部とを混合粉砕し
て、粉末フェノ−ル樹脂を得た。この樹脂は常温で粉末
であり、平均粒径３３μｍ、融点８７℃であった。 比較例３ 撹拌機、還流冷却器及び温度計付きの反応装置に、フェ
ノ−ル１０００部、３７％ホルマリン６０４部及び蓚酸
１０部を仕込み、還流条件下で３時間反応させた。次い
で、６０〜８０ｍｍＨｇの減圧下で内温１３０℃となる
まで脱水を行った。内温が１３０℃になった時点で常圧
に戻して、エチレングリコ−ル６５０部を添加混合し液
状フェノ−ル樹脂を得た。この樹脂の２５℃における粘
度は ７.５Pa・sであった。Comparative Example 1 A reactor equipped with a stirrer, a reflux condenser and a thermometer was equipped with 1000 parts of phenol, 1034 parts of 37% formalin and 1 part.
Charge 100 parts of 0% sodium hydroxide aqueous solution, 85 ℃
And reacted for 3 hours. After cooling to 60 ° C, 15 parts of acetic acid was added, and then the internal temperature was 75 ° C under a reduced pressure of 60 to 80 mmHg.
It was dehydrated until. When the internal temperature reached 75 ° C, the pressure was returned to normal pressure, 700 parts of ethylene glycol was added and mixed, and a liquid phenol resin was obtained. The viscosity of this resin at 25 ° C. was 0.5 Pa · s. Comparative Example 2 In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 1000 parts of phenol, 733 parts of 37% formalin and 35 parts of 37% formalin were added.
% 2% hydrochloric acid was charged, and the mixture was reacted under reflux conditions for 3 hours.
Then, it was dehydrated under reduced pressure of 60 to 80 mmHg until the internal temperature reached 140 ° C., and then taken out to obtain a solid novolac type phenol resin having a melting point of 80 ° C. 1000 parts of this resin and 100 parts of hexamethylenetetramine were mixed and pulverized to obtain a powder phenol resin. This resin was a powder at room temperature and had an average particle size of 33 μm and a melting point of 87 ° C. Comparative Example 3 A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 1000 parts of phenol, 604 parts of 37% formalin and 10 parts of oxalic acid, and reacted under reflux conditions for 3 hours. Next, dehydration was performed under a reduced pressure of 60 to 80 mmHg until the internal temperature reached 130 ° C. When the internal temperature reached 130 ° C, the pressure was returned to normal pressure, and 650 parts of ethylene glycol was added and mixed to obtain a liquid phenol resin. The viscosity of this resin at 25 ° C. was 7.5 Pa · s.
【０００９】〈熱天秤による比較〉図１に実施例１に記
載した本発明の耐火物用フェノール樹脂組成物と比較例
１に示した通常の液状フェノ−ル樹脂の空気中での熱天
秤の比較デ−タを、また、図２に実施例２に記載した本
発明の耐火物用フェノ−ル樹脂組成物と比較例２に示し
た通常の粉末フェノ−ル樹脂の空気中での熱天秤の比較
デ−タを示した。 （測定条件） ・測定機器：理学電機製 示差熱天秤 ・雰囲気 ：空気中 ・昇温速度：５℃／分 これらのデ−タから明らかなように、通常のフェノ−ル
樹脂に比較して、本発明の耐火物用フェノ−ル樹脂組成
物は、熱分解温度が高温側にシフトし、課題であった４
００〜７００℃での耐酸化性に優れている。<Comparison by Thermal Balance> FIG. 1 shows a thermobalance in air of the phenol resin composition for a refractory of the present invention described in Example 1 and the ordinary liquid phenol resin shown in Comparative Example 1. Comparative data, and a thermobalance in air of the phenolic resin composition for a refractory of the present invention described in Example 2 in FIG. 2 and the ordinary powdered phenolic resin shown in Comparative Example 2. The comparison data of (Measurement conditions) -Measurement equipment: Rigaku Denki's differential thermal balance-Atmosphere: In air-Rate of temperature rise: 5 ° C / min As is apparent from these data, compared to ordinary phenol resin, The phenol resin composition for refractories of the present invention has a problem that the thermal decomposition temperature shifts to the high temperature side.
Excellent resistance to oxidation at 00-700 ° C.
【００１０】〈実用試験〉実験用万能混練機にマグネシ
アクリンカー粗粒（１〜３ｍｍ）１８００部、マグネシ
アクリンカ−微粉(０.３ｍｍ以下）６００部、りん状黒
鉛６００部、実施例３に記載した耐火物用フェノール樹
脂組成物又は比較例３に記載した液状フェノ−ル樹脂１
２０部、ヘキサメチレンテトラミン１２部を入れ、２５
℃で６０分間混練した。次いで、混練物１２０ｇを１５
×２５×１００ｍｍの金型にとり、９.８×１０7Ｐａの
圧力をかけて成形し、得られた試験片を１７０℃で１２
時間乾燥した。さらに、この試験片について空気中で５
００℃、３時間加熱処理を行った。そして、１７０℃乾
燥後及び５００℃加熱処理後それぞれの試験片につい
て、かさ比重、気孔率、曲げ強度を測定した。結果を表
１に示す。<Practical test> 1800 parts of magnesia clinker coarse particles (1 to 3 mm), 600 parts of magnesia clinker-fine powder (0.3 mm or less), 600 parts of phosphorous graphite, and 600 parts of phosphorous graphite were described in a practical universal kneader. Phenolic resin composition for refractory or liquid phenol resin 1 described in Comparative Example 3
Add 20 parts and 12 parts of hexamethylenetetramine, and add 25
The mixture was kneaded at 60 ° C. for 60 minutes. Next, add 120 g of the kneaded material to 15
It is placed in a mold of × 25 × 100 mm and molded under a pressure of 9.8 × 10 7 Pa, and the obtained test piece is heated at 170 ° C. for 12 hours.
Dried for hours. Furthermore, about this test piece, 5
Heat treatment was performed at 00 ° C. for 3 hours. Then, the bulk specific gravity, the porosity, and the bending strength of each test piece after drying at 170 ° C. and after heat treatment at 500 ° C. were measured. The results are shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】表１から明らかなように、比較例３で示さ
れる通常のフェノ−ル樹脂に比較して、実施例３で示さ
れる本発明の耐火物用フェノ−ル樹脂組成物は、特に５
００℃加熱処理後の曲げ強度が大きく、この温度域で酸
化劣化が起こりにくいことがわかる。As is clear from Table 1, in comparison with the ordinary phenolic resin shown in Comparative Example 3, the phenolic resin composition for refractory of the present invention shown in Example 3 has particularly 5 parts.
It can be seen that the bending strength after the heat treatment at 00 ° C. is large, and oxidative deterioration is unlikely to occur in this temperature range.
【００１３】[0013]
【発明の効果】本発明の耐火物用フェノ−ル樹脂組成物
を各種耐火物の結合剤として用いた場合、従来の耐火物
用フェノ−ル樹脂結合剤の欠点であった高温域での耐酸
化性が改良され、耐用性に優れた耐火物を製造すること
ができる。When the phenol resin composition for refractories of the present invention is used as a binder for various refractory materials, the acid resistance in the high temperature range, which has been a drawback of conventional phenol resin binders for refractory materials, is high. It is possible to manufacture a refractory having improved chemical resistance and excellent durability.
【図１】熱天秤による加熱減量の比較デ−タ。FIG. 1 is a comparison data of the weight loss on heating by a thermobalance.
【図２】熱天秤による加熱減量の比較デ−タ。FIG. 2 is a comparison data of weight loss on heating using a thermobalance.
Claims (1)
付加縮合反応終了後ホウ素酸化物を配合してなることを
特徴とする耐火物用フェノ−ル樹脂組成物。1. A refractory phenol resin composition comprising a boron oxide after the addition condensation reaction of phenols and formaldehyde has been completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06468192A JP3518610B2 (en) | 1992-03-23 | 1992-03-23 | Phenolic resin composition for refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06468192A JP3518610B2 (en) | 1992-03-23 | 1992-03-23 | Phenolic resin composition for refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05262958A true JPH05262958A (en) | 1993-10-12 |
| JP3518610B2 JP3518610B2 (en) | 2004-04-12 |
Family
ID=13265151
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06468192A Expired - Lifetime JP3518610B2 (en) | 1992-03-23 | 1992-03-23 | Phenolic resin composition for refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3518610B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010047524A (en) * | 1999-11-22 | 2001-06-15 | 송성원 | An Oxidation resistant resin composition |
| JP2007246594A (en) * | 2006-03-14 | 2007-09-27 | Dainippon Ink & Chem Inc | Resin composition having naphthalene skeleton |
| US7569267B2 (en) | 2003-10-22 | 2009-08-04 | Kureha Corporation | Laminate and production process thereof |
| US7608339B2 (en) | 2003-10-22 | 2009-10-27 | Kureha Corporation | Multilayer film |
| JP2010031079A (en) * | 2008-07-25 | 2010-02-12 | Dic Corp | Manufacturing method of boric acid-modified phenolic resin |
| CN108950873A (en) * | 2018-07-27 | 2018-12-07 | 中原工学院 | A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position phenyl-borate modified heat convertible phenolic aldehyde base |
| JP2019094396A (en) * | 2017-11-21 | 2019-06-20 | 住友ベークライト株式会社 | Phenol resin composition and refractory |
| CN118005413A (en) * | 2024-04-08 | 2024-05-10 | 江苏欧泰新材料有限公司 | High-strength anti-corrosion stemming and preparation method thereof |
-
1992
- 1992-03-23 JP JP06468192A patent/JP3518610B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010047524A (en) * | 1999-11-22 | 2001-06-15 | 송성원 | An Oxidation resistant resin composition |
| US7569267B2 (en) | 2003-10-22 | 2009-08-04 | Kureha Corporation | Laminate and production process thereof |
| US7608339B2 (en) | 2003-10-22 | 2009-10-27 | Kureha Corporation | Multilayer film |
| JP2007246594A (en) * | 2006-03-14 | 2007-09-27 | Dainippon Ink & Chem Inc | Resin composition having naphthalene skeleton |
| JP2010031079A (en) * | 2008-07-25 | 2010-02-12 | Dic Corp | Manufacturing method of boric acid-modified phenolic resin |
| JP2019094396A (en) * | 2017-11-21 | 2019-06-20 | 住友ベークライト株式会社 | Phenol resin composition and refractory |
| CN108950873A (en) * | 2018-07-27 | 2018-12-07 | 中原工学院 | A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position phenyl-borate modified heat convertible phenolic aldehyde base |
| CN108950873B (en) * | 2018-07-27 | 2020-03-10 | 中原工学院 | Preparation method of high-ortho-position phenyl borate modified thermosetting phenolic-based hollow nano gradient activated carbon fiber membrane |
| CN118005413A (en) * | 2024-04-08 | 2024-05-10 | 江苏欧泰新材料有限公司 | High-strength anti-corrosion stemming and preparation method thereof |
| CN118005413B (en) * | 2024-04-08 | 2024-06-04 | 江苏欧泰新材料有限公司 | High-strength anti-corrosion stemming and preparation method thereof |
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|---|---|
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