JP2005186097A - Binder composition for making mold and composition for making mold, and method for making mold for casting - Google Patents
Binder composition for making mold and composition for making mold, and method for making mold for casting Download PDFInfo
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本発明は鋳造用の鋳型を製造するのに、加熱を必要としない常温硬化法に関するものである。更に詳しくは、水溶性フェノール樹脂を有機エステルにより硬化させる、有機エステル硬化型フェノール樹脂を用いた鋳型製造用粘結剤組成物、鋳型製造用組成物、および鋳造用鋳型製造方法に関するものである。 The present invention relates to a room temperature curing method that does not require heating to produce a casting mold. More specifically, the present invention relates to a binder composition for mold production using an organic ester curable phenol resin, a composition for mold production, and a casting mold production method, wherein a water-soluble phenol resin is cured with an organic ester.
鋳造用鋳型を製造する方法として、水溶性フェノール樹脂を含む粘結剤溶液を使用し、液状の有機エステル化合物で硬化させる自硬性型鋳型製造法とガス状又はエアロゾル状物質で常温硬化させるガス硬化型鋳型製造法は公知である。（例えば、特許文献１参照。）
この粘結剤組成物を用いた鋳型製造法は、粘結剤組成物中に硫黄元素を含まないので、酸硬化性樹脂を用いた鋳型製造法に比べて浸硫による影響が少ないという特徴を有する反面、特に鋳型製造時及び鋳造時にホルムアルデヒド臭気が発生するので、作業環境が悪いという問題がある。
As a method for producing a casting mold, a self-hardening mold manufacturing method using a binder solution containing a water-soluble phenol resin and curing with a liquid organic ester compound, and gas curing using a gaseous or aerosol-like material at room temperature. Mold production methods are known. (For example, refer to Patent Document 1.)
The mold manufacturing method using this binder composition does not contain elemental sulfur in the binder composition, and therefore has a feature that it is less affected by sulfurization than the mold manufacturing method using an acid curable resin. On the other hand, there is a problem that the working environment is bad because formaldehyde odor is generated particularly during mold production and casting.
この問題の解決法として、水溶性フェノール樹脂にホルムアルデヒド捕捉剤として有機窒素化合物を添加する方法が知られている。（特許文献２参照。）しかし、水溶性フェノール樹脂に有機窒素化合物、例えば、尿素を添加すると、尿素はフェノール樹脂と縮合反応をする（非特許文献１参照。）ので、水溶性フェノール樹脂が変質、増粘するため貯蔵、鋳型造型にとって好ましくない。 As a solution to this problem, a method of adding an organic nitrogen compound as a formaldehyde scavenger to a water-soluble phenol resin is known. However, when an organic nitrogen compound such as urea is added to the water-soluble phenol resin, urea undergoes a condensation reaction with the phenol resin (see Non-Patent Document 1), so that the water-soluble phenol resin is altered. Because of thickening, it is not preferable for storage and mold making.
本発明は、水溶性フェノール樹脂を粘結剤とし、これを有機エステルで硬化させる鋳型製造用粘結剤組成物を用いた鋳型製造法において、鋳型製造時及び鋳造時にホルムアルデヒド臭気の発生を抑制し、しかも貯蔵時に水溶性フェノール樹脂を変質、増粘させることのないホルムアルデヒド捕捉剤を含有する鋳型製造用粘結剤組成物を提供することを目的としている。 The present invention suppresses the generation of formaldehyde odor during mold production and casting in a mold production method using a binder composition for mold production in which a water-soluble phenol resin is used as a binder and cured with an organic ester. And it aims at providing the binder composition for mold manufacture containing the formaldehyde scavenger which does not denature and thicken water-soluble phenol resin at the time of storage.
本発明者らは、前記課題である、有機エステル硬化型フェノール樹脂を用いた鋳型製造用粘結剤組成物、鋳型製造用組成物、および鋳造用鋳型製造法において、鋳型製造時及び鋳造時にホルムアルデヒド臭気が発生し、作業環境が悪いという課題の解決法を鋭意検討した結果、有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液を硬化剤として用いて、硬化剤にエチレン尿素を添加、溶解することにより、ホルムアルデヒド臭気の発生を顕著に抑制できることを見い出し、本発明を完成するに至った。 In the binder production composition for mold production using the organic ester curable phenolic resin, the composition for mold production, and the casting mold production method, which are the above-mentioned problems, the present inventors provide formaldehyde during mold production and casting. As a result of diligent research on a solution to the problem that the odor is generated and the working environment is bad, an organic ester mixed solution obtained by mixing one organic ester or a mixture of two or more organic esters is used as a curing agent, and ethylene is used as the curing agent. It has been found that generation of formaldehyde odor can be remarkably suppressed by adding and dissolving urea, and the present invention has been completed.
すなわち、本発明は、下記（１）に示した自硬性型鋳型製造用粘結剤組成物、および下記（２）と（３）に示した自硬性型鋳型製造用組成物である。
（１）有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有し、該有機エステルまたは有機エステル混合液のエチレン尿素溶液をA成分とし、B成分として水溶性フェノール樹脂からなる自硬性型鋳型製造用粘結剤組成物。
（２）有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有し、該有機エステルまたは有機エステル混合液のエチレン尿素溶液をA成分とし、B成分として水溶性フェノール樹脂、及びC成分として耐火性骨材からなる自硬性型鋳型製造用組成物。
（３）エチレン尿素を０．１〜２０重量％、好ましくは１〜１０重量％溶解したA成分を０．０５〜５重量部、好ましくは０．１〜２重量部、B成分である水溶性フェノール樹脂が０．１〜５重量部、好ましくは０．５〜３重量部、及びＣ成分である耐火性骨材１００重量部を含有する自硬性型鋳型製造用組成物。
That is, this invention is the binder composition for self-hardening type | mold mold manufacture shown to following (1), and the composition for self-hardening type | mold mold manufacturing shown to following (2) and (3).
(1) One kind of organic ester or an organic ester mixed liquid in which two or more kinds of organic esters are mixed, wherein the organic ester or the organic ester mixed liquid has an ethylene urea solubility of 0.1% by weight or more, A binder composition for producing a self-hardening mold, comprising an organic ester or an ethylene urea solution of an organic ester mixed solution as an A component and a B component as a water-soluble phenol resin.
(2) One kind of organic ester or an organic ester mixed liquid in which two or more kinds of organic esters are mixed, wherein the organic ester or organic ester mixed liquid has an ethylene urea solubility of 0.1% by weight or more, A composition for producing a self-hardening mold, comprising an ethylene ester solution of an organic ester or an organic ester mixed solution as a component A, a water-soluble phenol resin as a component B, and a refractory aggregate as a component C.
(3) 0.1 to 20% by weight, preferably 1 to 10% by weight of ethylene urea dissolved in component A, 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, water component B A composition for producing a self-hardening mold containing 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight of a phenol resin, and 100 parts by weight of a refractory aggregate which is a C component.
また本発明は、有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有し、該有機エステルまたは有機エステル混合液のエチレン尿素溶液であるA成分と、C成分である耐火性骨材を混合し、この混合物にB成分である水溶性フェノール樹脂を添加、混合して自硬性型鋳型製造用組成物を調整後、この自硬性型鋳型製造用組成物を鋳型製造用型枠内に収納して成形し硬化させる、鋳造用鋳型製造方法である。 Further, the present invention is an organic ester mixed liquid obtained by mixing one kind of organic ester alone or two or more kinds of organic esters, and the organic ester or organic ester mixed liquid has an ethylene urea solubility of 0.1% by weight or more. , A component which is ethylene urea solution of the organic ester or organic ester mixed solution and refractory aggregate which is C component are mixed, and water-soluble phenolic resin which is B component is added to this mixture and mixed to be self-hardening This is a casting mold manufacturing method in which, after the mold mold manufacturing composition is prepared, the self-hardening mold manufacturing composition is housed in a mold manufacturing mold, molded and cured.
硬化剤にエチレン尿素を添加、溶解することにより、ホルムアルデヒド臭気の発生を顕著に抑制し、作業環境の向上を可能にした。これは、エチレン尿素が硬化剤に溶解しているので、粒状耐火性骨材、水溶性フェノール樹脂と充分に均一に混合できるためである。また、硬化剤にエチレン尿素を添加、溶解したことにより、従来用いられてきた鋳造用鋳型製造法に、ホルムアルデヒド捕捉剤を添加する新たな作業、工程の増加、装置の増設も必要としない。すなわち、粒状耐火性骨材と硬化剤を混合後、水溶性フェノール樹脂を添加、混合することで鋳造用鋳型を製造できる。更に、水溶性フェノール樹脂に有機窒素化合物を添加する方法のように水溶性フェノール樹脂の変質、増粘のようなことも生じないので、貯蔵、鋳型造型にとって好ましくないことも起こらない。 By adding and dissolving ethylene urea in the curing agent, the generation of formaldehyde odor was remarkably suppressed and the working environment was improved. This is because ethylene urea is dissolved in the curing agent, so that it can be sufficiently uniformly mixed with the granular refractory aggregate and the water-soluble phenol resin. In addition, since ethylene urea is added to and dissolved in the curing agent, a new operation for adding a formaldehyde scavenger, an increase in the number of processes, and an additional apparatus are not required in the conventional casting mold manufacturing method. That is, a casting mold can be manufactured by adding and mixing a water-soluble phenol resin after mixing a granular refractory aggregate and a curing agent. Further, since there is no alteration or thickening of the water-soluble phenolic resin as in the method of adding an organic nitrogen compound to the water-soluble phenolic resin, it is not undesirable for storage and mold making.
従来の自硬性型鋳型製造法は、粒状耐火性骨材と硬化剤である有機エステルを混合後、水溶性フェノール樹脂を添加、混合する。この方法は、粒状耐火性骨材、硬化剤、及び水溶性フェノール樹脂の３成分より成っている。
ホルムアルデヒド臭気の発生を抑制するために、例えば、粒状耐火性骨材と有機窒素化合物あるいは有機窒素化合物溶液を予め混合しておき、その後、硬化剤、水溶性フェノール樹脂を混合する方法も考えられるが、この方法では、粒状耐火性骨材、有機窒素化合物あるいは有機窒素化合物溶液、硬化剤、及び水溶性フェノール樹脂の４成分になるので、従来の鋳造用鋳型製造法に比べて工程、作業量が増加し、場合によっては、製造装置の改良、増設が必要になり好ましくない。
In a conventional self-hardening mold manufacturing method, a granular refractory aggregate and an organic ester as a curing agent are mixed, and then a water-soluble phenol resin is added and mixed. This method consists of three components: a granular refractory aggregate, a curing agent, and a water-soluble phenolic resin.
In order to suppress the generation of formaldehyde odor, for example, a method in which granular refractory aggregate and an organic nitrogen compound or an organic nitrogen compound solution are mixed in advance and then a curing agent and a water-soluble phenol resin are mixed is also considered. In this method, since it becomes four components of granular refractory aggregate, organic nitrogen compound or organic nitrogen compound solution, curing agent, and water-soluble phenol resin, the process and work volume are compared with the conventional casting mold manufacturing method. In some cases, the manufacturing apparatus needs to be improved or expanded, which is not preferable.
以上説明したとおり、水溶性フェノール樹脂を粘結剤とし、これを有機エステルで硬化させる鋳型製造用粘結剤組成物を用いた鋳型製造法において、硬化剤にエチレン尿素を添加、溶解することにより、ホルムアルデヒド臭気の発生を顕著に抑制し、作業環境の向上を可能にした。これは、エチレン尿素が硬化剤に溶解しているので、粒状耐火性骨材、水溶性フェノール樹脂と充分に均一に混合できるからである。また、前記した、有機窒素化合物を水溶性フェノール樹脂に添加する場合のように、水溶性フェノール樹脂が変質、増粘するようなことも起こらない。更に、硬化剤にエチレン尿素を添加、溶解することにより、従来の鋳造用鋳型製造法に新たな作業、工程の増加、装置の増設なしにホルムアルデヒド臭気の発生を顕著に抑制し、作業環境の向上を可能にした。 As described above, in a mold production method using a binder composition for mold production in which a water-soluble phenol resin is used as a binder and cured with an organic ester, ethylene urea is added to and dissolved in the curing agent. In addition, the generation of formaldehyde odor was remarkably suppressed and the working environment was improved. This is because ethylene urea is dissolved in the curing agent, so that it can be sufficiently uniformly mixed with the granular refractory aggregate and the water-soluble phenol resin. Further, unlike the case where the organic nitrogen compound is added to the water-soluble phenol resin as described above, the water-soluble phenol resin is not altered or thickened. In addition, ethylene urea is added to and dissolved in the curing agent to significantly reduce the generation of formaldehyde odors and improve the work environment without adding new operations, increasing the number of processes, or adding equipment to the conventional casting mold manufacturing method. Made possible.
本発明で用いられる水溶性フェノール樹脂は、有機エステルで硬化可能な樹脂であり、例えばフェノール、クレゾール、レゾルシン、３，５−キシレノール、ビスフェノールＡ、その他の置換フェノールを含めたフェノール類を大量のアルカリ性物質の水溶液の中でホルムアルデヒド単独あるいはアセトアルデヒド、フルフリルアルデヒド及びアルデヒドの混合物等のアルデヒドとの併用による反応によって得られるフェノール樹脂が上げられるが、ホルムアルデヒド単独が好ましい。これらの水溶性フェノール樹脂の製造の際に用いられる適当なアルカリ性触媒は、アルカリ金属の水酸化物である水酸化ナトリウム、水酸化カリウム、水酸化リチウム及びこれらの混合物であるが、水酸化カリウムが最も好ましい。水溶性フェノール樹脂は、粉末状で鋳物砂又はその再生砂に添加しても良い。 The water-soluble phenol resin used in the present invention is a resin curable with an organic ester. For example, phenols including phenol, cresol, resorcin, 3,5-xylenol, bisphenol A, and other substituted phenols have a large amount of alkaline. In the aqueous solution of the substance, a phenol resin obtained by reaction with formaldehyde alone or in combination with an aldehyde such as a mixture of acetaldehyde, furfurylaldehyde and aldehyde can be raised, but formaldehyde alone is preferred. Suitable alkaline catalysts used in the production of these water-soluble phenolic resins are sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof, which are alkali metal hydroxides. Most preferred. The water-soluble phenol resin may be added to the foundry sand or its recycled sand in a powder form.
更に、水溶性フェノール樹脂には、粒状耐火性骨材を樹脂で被覆した時の鋳型製造用型枠への充填性、鋳型と鋳物との離型性等を向上するために各種の添加剤を添加する場合がある。 In addition, various additives are added to the water-soluble phenolic resin in order to improve the filling property of the mold for mold production when the granular refractory aggregate is coated with the resin, and the mold releasability between the mold and the casting. May be added.
樹脂被覆骨材の充填性を向上させる効果のある添加剤としては、各種の界面活性剤が有効であり、ノニオン界面活性剤、カチオン界面活性剤、アニオン界面活性剤、両性界面活性剤等が使用できる。具体的に例示すると、ノニオン界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン−ポリオキシプロピレングリコール、ポリオキシエチレン−ポリオキシプロピレングリコールエチレンジアミン等のポリオキシエチレン型界面活性剤、エチレングリコールモノ脂肪酸エステル、グリセリンモノ脂肪酸エステル、ソルビタントリ脂肪酸エステル等の多価アルコール型界面活性剤、脂肪酸モノエタノールアミド、脂肪酸モノイソプロパノールアミド等のアルキロールアミド型界面活性剤があげられる。 Various additives are effective as additives that improve the filling properties of resin-coated aggregates. Nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc. are used. it can. Specifically, as the nonionic surfactant, polyoxyethylene type surfactants such as polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glycol ethylenediamine, ethylene glycol mono Examples thereof include polyhydric alcohol surfactants such as fatty acid esters, glycerin monofatty acid esters and sorbitan trifatty acid esters, and alkylolamide surfactants such as fatty acid monoethanolamides and fatty acid monoisopropanolamides.
アニオン界面活性剤の具体例としては、ステアリン酸の金属塩、ナフテン酸等の脂肪酸型界面活性剤、オレイル硫酸エステルの金属塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、脂肪族モノグリセリド脂肪族エステル塩、オリーブ油等の硫酸化油、脂肪族アルキル硫酸エステル塩、脂肪族アミド硫酸エステル塩等の硫酸エステル塩型界面活性剤、スルホン酸塩型界面活性剤、燐酸エステル塩型界面活性剤が使用できる。 Specific examples of the anionic surfactant include stearic acid metal salt, fatty acid type surfactant such as naphthenic acid, oleyl sulfate metal salt, polyoxyethylene alkyl ether sulfate ester, aliphatic monoglyceride aliphatic ester salt, Sulfated oils such as olive oil, sulfate ester type surfactants such as aliphatic alkyl sulfate ester salts and aliphatic amide sulfate ester salts, sulfonate type surfactants and phosphate ester type surfactants can be used.
カチオン界面活性剤の具体例としては、アルキルピリジニウム塩、アルキルキノリニウム硫酸塩、アシルアミノエチルピリジニウム塩等の第４級アンモニウム塩、脂肪族トリエタノールアミン、脂肪族トリエタノールアミン蟻酸塩、ポリオキシエチレン脂肪酸トリエタノールアミン、脂肪酸ジブチルアミノエタノール、ｐ−イソオクチルフェノキシエトキシエチルベンジルアンモニウム塩等のエステル結合アミン及びエーテル結合を有する第４級アンモニウム塩型が、アルキルイミダゾリン、１−ヒドロキシエチル−２−アルキルイミダゾリン、１−アセチルアミノエチル−２−アルキルイミダゾリン及びこれらの４級塩等の複素環アミン型界面活性剤が使用できる。 Specific examples of the cationic surfactant include quaternary ammonium salts such as alkylpyridinium salts, alkylquinolinium sulfates, acylaminoethylpyridinium salts, aliphatic triethanolamines, aliphatic triethanolamine formates, polyoxy Quaternary ammonium salt types having ester bond amine and ether bond such as ethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, p-isooctylphenoxyethoxyethylbenzylammonium salt are alkylimidazolines, 1-hydroxyethyl-2-alkyl Heterocyclic amine type surfactants such as imidazoline, 1-acetylaminoethyl-2-alkylimidazoline and quaternary salts thereof can be used.
また、両性界面活性剤としては、Ｎ−アルキルトリグリシン、ジメチルアルキルベタイン、アルキルベタイン、アルキルジアミノエチルグリシン塩酸塩、ジアルキルジエチレントリアミノ酢酸の塩酸塩、Ｎ−アルキルタウリン塩等が使用できる。その他、フッ素系界面活性剤、シリコン系界面活性剤も使用でき、界面活性剤としては特に限定はされない。 As the amphoteric surfactant, N-alkyltriglycine, dimethylalkylbetaine, alkylbetaine, alkyldiaminoethylglycine hydrochloride, hydrochloride of dialkyldiethylenetriaminoacetic acid, N-alkyltaurine salt and the like can be used. In addition, a fluorine-based surfactant and a silicon-based surfactant can also be used, and the surfactant is not particularly limited.
また、本発明の鋳型製造用粘結剤組成物に、耐火性骨材と粘結剤の接着力改善剤として、シランカップリング剤を添加することができる。シランカップリング剤として具体的な例をあげると、γ−アミノプロピルトリエトキシシラン、γ−２−アミノエチル−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン等が挙げられる。 Moreover, a silane coupling agent can be added to the binder composition for producing a mold of the present invention as an adhesive strength improver between a refractory aggregate and a binder. Specific examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-2-aminoethyl-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like.
本発明で用いられる硬化剤としては、有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有する有機エステルまたは有機エステル混合液が使用できる。例えば、γ−ブチロラクトン、トリアセチン、エチレングリコールジアセテート、コハク酸ジメチル、グルタル酸ジメチル、アジピン酸ジメチルなどの二塩基酸エステル、またはこれらの混合物が挙げられる。 The curing agent used in the present invention is an organic ester mixed liquid obtained by mixing one kind of organic ester alone or two or more kinds of organic esters, and the organic ester or organic ester mixed liquid has an ethylene urea solubility of 0.1 wt. % Organic esters or organic ester mixtures can be used. Examples thereof include dibasic acid esters such as γ-butyrolactone, triacetin, ethylene glycol diacetate, dimethyl succinate, dimethyl glutarate, and dimethyl adipate, or mixtures thereof.
本発明において使用される粒状耐火性骨材としては、硅砂、フリマントル硅砂、クロム鉄鉱砂、ジルコン砂、かんらん石砂等の従来から鋳型鋳造用に使用されている耐火性の粒状砂のほか、微粉状の砂、粘土質の砂、再生砂等も使用することができる。また砂以外のものとしてはムライト砂、アルミナ砂、中空アルミナビーズ、シラスバルーン、ガラスビーズ等も使用できるが、通常は平均粒径５０〜２０００マイクロメートル（μｍ）程度の砂が好ましい。 The granular refractory aggregate used in the present invention includes refractory granular sand conventionally used for mold casting, such as dredged sand, Fremantle dredged sand, chromite sand, zircon sand, olivine sand and the like. Fine powdery sand, clayey sand, reclaimed sand and the like can also be used. In addition to sand, mullite sand, alumina sand, hollow alumina beads, shirasu balloons, glass beads and the like can be used, but sand having an average particle size of about 50 to 2000 micrometers (μm) is usually preferred.
本発明の鋳型製造用粘結剤組成物を用いて鋳型を自硬性型鋳型製造法によって製造するには、耐火性骨材１００重量部に、有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有し、該有機エステルまたは有機エステル混合液にエチレン尿素を０．１〜２０重量％、好ましくは１〜１０重量％溶解した溶液を０．０５〜５重量部、好ましくは０．１〜２重量部、及び水溶性フェノール樹脂を０．１〜５重量部、好ましくは０．５〜３重量部含有する自硬性型鋳型製造用組成物を周知の方法で混練し鋳型製造用組成物を得て、従来の自硬性型鋳型製造プロセスをそのまま利用して鋳型を製造することができる。 In order to produce a mold by the self-hardening mold production method using the binder composition for mold production of the present invention, one kind of organic ester or two or more kinds of organic esters are added to 100 parts by weight of refractory aggregate. A mixed organic ester mixed solution, wherein the organic ester or organic ester mixed solution has an ethylene urea solubility of 0.1 wt% or more, and 0.1 to 20 ethylene urea is added to the organic ester or organic ester mixed solution. 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, and 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight of a water-soluble phenol resin. A composition for producing a self-hardening mold containing 5 to 3 parts by weight is kneaded by a known method to obtain a composition for producing a mold, and a mold can be produced by using a conventional self-hardening mold production process as it is. Can .
例えば、自硬性型鋳型製造法では、水溶性フェノール樹脂溶液、エチレン尿素が溶解した硬化剤、粒状耐火性骨材を好ましくは−１０〜５０℃の範囲で、ミキサーにより各成分が均一に混合するように十分に混練することによって粘結剤被覆粒状耐火性骨材の調製を行うことができる。混練に際しては、エチレン尿素が溶解した硬化剤と粒状耐火性骨材を均一に混合した後、この混合物に主剤である水溶性フェノール樹脂を添加して均一に混合するのが好ましい。調製した所望量の粘結剤被覆粒状耐火性骨材を鋳型製造用型枠内に導入し硬化させる。鋳型を型枠から取り出す際、鋳型の損傷を防止するためには、硬化させるのに十分な時間経過してから鋳型を型枠から取り出すのが好ましい。 For example, in the self-hardening mold manufacturing method, a water-soluble phenol resin solution, a curing agent in which ethylene urea is dissolved, and granular refractory aggregate are preferably mixed in a range of −10 to 50 ° C. with a mixer so that each component is uniformly mixed. Thus, the binder-coated granular refractory aggregate can be prepared by sufficiently kneading. At the time of kneading, it is preferable to uniformly mix the curing agent in which ethylene urea is dissolved and the granular refractory aggregate, and then add the water-soluble phenol resin as the main agent to the mixture and mix them uniformly. The prepared desired amount of binder-coated granular refractory aggregate is introduced into a mold manufacturing mold and cured. When removing the mold from the mold, in order to prevent damage to the mold, it is preferable to remove the mold from the mold after a sufficient time has elapsed for curing.
また、本発明において、鋳型をガス硬化性型鋳型製造法によって製造するには、まず耐火性骨材１００重量部に、水溶性フェノール樹脂０．１〜５重量部、好ましくは０．５〜３重量部を含有させた混練砂を手込め、もしくは加圧空気でのブローイングにより鋳型製造用型枠中に充填し、次いでガス状もしくはエアロゾル状の有機エステル１種類単独または２種類以上の有機エステルを混合した有機エステル混合液であって、該有機エステルまたは有機エステル混合液がエチレン尿素溶解度として０．１重量％以上を有し、該有機エステルまたは有機エステル混合液にエチレン尿素を０．１〜２０重量％、好ましくは１〜１０重量％溶解した溶液を０．０５〜５重量部、好ましくは０．５〜３重量部を吹きこんで硬化させることにより鋳型を製造する。 In the present invention, in order to produce a mold by a gas curable mold production method, first, 0.1 to 5 parts by weight of water-soluble phenol resin, preferably 0.5 to 3 parts are added to 100 parts by weight of refractory aggregate. The kneaded sand containing parts by weight is put into a mold for mold production by blowing or blowing with pressurized air, and then one or more organic esters in gaseous or aerosol form are used alone. A mixed organic ester mixed solution, wherein the organic ester or organic ester mixed solution has an ethylene urea solubility of 0.1 wt% or more, and 0.1 to 20 ethylene urea is added to the organic ester or organic ester mixed solution. A mold is obtained by blowing and curing 0.05 to 5 parts by weight, preferably 0.5 to 3 parts by weight of a dissolved solution of 1 to 10% by weight. To elephants.
硬化剤である有機エステルまたは有機エステル混合液へのエチレン尿素の溶解量が０．１重量％未満では、鋳型造型時に発生するホルムアルデヒド臭気の抑制効果が殆どなく、一方２０重量％を超えると鋳物の品質が劣る等の問題が発生しやすくなる。 If the amount of ethylene urea dissolved in the organic ester or organic ester mixed liquid as the curing agent is less than 0.1% by weight, there is almost no effect of suppressing formaldehyde odor generated during mold molding, while if it exceeds 20% by weight, Problems such as inferior quality are likely to occur.
以下、本発明を実施例により詳細に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example.
粒状耐火性骨材としてフリマントル珪砂、有機エステル硬化型フェノール自硬性バインダーとして水溶性フェノール樹脂水溶液である保土谷アシュランド（株）製 Ｃｈｅｍ Ｒｅｚ ６３０、硬化剤として有機エステルであるγ−ブチロラクトンを用いた。γ−ブチロラクトン、エチレン尿素は市販の試薬特級を使用した。 Fremantle silica sand as granular refractory aggregate, ChemRez 630 manufactured by Hodogaya Ashland Co., Ltd., which is a water-soluble phenolic resin aqueous solution as organic ester curable phenol self-hardening binder, and γ-butyrolactone, an organic ester, is used as a curing agent. It was. For γ-butyrolactone and ethylene urea, commercially available reagent grades were used.
室温２０℃で、フリマントル硅砂１００部と、エチレン尿素を５重量％溶解した硬化剤であるγ−ブチロラクトン ０．４部を品川式ミキサー（（株）ダルトン製 ５０M−ｒ型ミキサー）で６０秒混練後、主剤であるＣｈｅｍ Ｒｅｚ ６３０を２部加えて３０秒混練した。混合中、混合終了１０分後に発生するホルムアルデヒド臭気を官能的に評価した。その結果、混合中、混合終了１０分後もホルムアルデヒド臭気は殆どしなかった。 At room temperature of 20 ° C., 100 parts of Fremantle cinnabar and 0.4 parts of γ-butyrolactone, a curing agent in which 5% by weight of ethylene urea was dissolved, were used for 60 seconds with a Shinagawa mixer (50M-r type mixer manufactured by Dalton Co., Ltd.). After kneading, 2 parts of Chem Rez 630 as the main agent was added and kneaded for 30 seconds. During mixing, formaldehyde odor generated 10 minutes after the end of mixing was sensory evaluated. As a result, there was almost no formaldehyde odor during mixing, 10 minutes after completion of mixing.
［比較例１］
室温２０℃で、フリマントル硅砂１００部と、硬化剤であるγ−ブチロラクトン ０．４部を品川式ミキサー（（株）ダルトン製 ５０M−ｒ型ミキサー）で６０秒混練後、主剤であるＣｈｅｍ Ｒｅｚ ６３０を２部加えて３０秒混練した。混合中、混合終了１０分後に発生するホルムアルデヒド臭気を官能的に評価した。その結果、混合中、混合終了１０分後もホルムアルデヒド臭気が強く、目に刺激性が充分認められた。
[Comparative Example 1]
At room temperature of 20 ° C., 100 parts of Fremantle cinnabar and 0.4 part of γ-butyrolactone as a curing agent were kneaded with a Shinagawa mixer (50M-r mixer manufactured by Dalton Co., Ltd.) for 60 seconds, followed by Chem Rez as the main agent. Two parts of 630 were added and kneaded for 30 seconds. During mixing, the formaldehyde odor generated 10 minutes after the completion of mixing was sensory evaluated. As a result, during mixing, even after 10 minutes from the end of mixing, the formaldehyde odor was strong and irritation was sufficiently recognized in the eyes.
硬化剤であるγ−ブチロラクトンに有機窒素化合物であるエチレン尿素を溶解した実施例１と、γ−ブチロラクトンにエチレン尿素を溶解しなかった比較例１を比較することにより、γ−ブチロラクトンにエチレン尿素を溶解することにより、鋳型製造中、鋳型製造後もホルムアルデヒド臭気が殆どしないことがわかる。これは、硬化剤であるγ−ブチロラクトンにエチレン尿素を溶解することにより、鋳型製造時にホルムアルデヒド臭気の発生を防ぎ、作業環境を著しく向上できることを示す。 By comparing Example 1 in which ethylene urea as an organic nitrogen compound was dissolved in γ-butyrolactone as a curing agent and Comparative Example 1 in which ethylene urea was not dissolved in γ-butyrolactone, ethylene urea was dissolved in γ-butyrolactone. By dissolving, it can be seen that there is almost no formaldehyde odor during and after mold production. This indicates that by dissolving ethylene urea in γ-butyrolactone, which is a curing agent, the generation of formaldehyde odor can be prevented during mold production and the working environment can be significantly improved.
従来から知られている、水溶性フェノール樹脂を含む粘結剤溶液を使用し、液状の有機エステル化合物で硬化させる自硬性型鋳型製造法とガス状又はエアロゾル状物質で常温硬化させるガス硬化型鋳型製造法は、鋳型製造時及び鋳造時にホルムアルデヒド臭気が発生するので、作業環境が悪いという問題があった。
本発明は、硬化剤である有機エステル化合物にエチレン尿素を添加、溶解することにより、ホルムアルデヒド臭気の発生を顕著に抑制し、更に、硬化剤にエチレン尿素を添加、溶解することにより、従来の鋳造用鋳型製造法に新たな工程、作業量の増加なしに、ホルムアルデヒド臭気の発生を顕著に抑制し、作業環境の向上を可能にした。
Conventionally known self-hardening mold manufacturing method using a binder solution containing a water-soluble phenol resin and curing with a liquid organic ester compound, and a gas curing mold that cures at room temperature with a gaseous or aerosol-like substance The manufacturing method has a problem that the working environment is poor because a formaldehyde odor is generated during mold manufacturing and casting.
The present invention remarkably suppresses the generation of formaldehyde odor by adding and dissolving ethylene urea to the organic ester compound that is a curing agent, and further adding and dissolving ethylene urea to the curing agent, thereby converting the conventional casting. New process for manufacturing molds for industrial use, and without increasing the amount of work, the generation of formaldehyde odor was remarkably suppressed and the working environment was improved.
Claims (7)
An organic ester mixed liquid obtained by mixing one kind of organic ester or two or more kinds of organic esters, wherein the organic ester or organic ester mixed liquid has an ethylene urea solubility of 0.1% by weight or more, and the organic ester or Composition for manufacturing self-hardening mold by mixing A component which is ethylene urea solution of organic ester mixture and refractory aggregate which is C component, and adding and mixing water-soluble phenol resin which is B component to this mixture A casting mold manufacturing method in which a composition for manufacturing a self-hardening mold is stored in a mold manufacturing mold, molded and cured after the product is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013298A (en) * | 2007-07-05 | 2009-01-22 | Showa Highpolymer Co Ltd | Process for producing water soluble resol resin |
| JP2015123479A (en) * | 2013-12-26 | 2015-07-06 | 花王株式会社 | Manufacturing method for self-curing mold, molding binder kit, and molding composition |
| JP2019063842A (en) * | 2017-10-04 | 2019-04-25 | 花王株式会社 | Aggregate composition for mold |
| JP7341610B2 (en) | 2019-10-30 | 2023-09-11 | 花王株式会社 | Hardener composition for mold making |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013298A (en) * | 2007-07-05 | 2009-01-22 | Showa Highpolymer Co Ltd | Process for producing water soluble resol resin |
| JP2015123479A (en) * | 2013-12-26 | 2015-07-06 | 花王株式会社 | Manufacturing method for self-curing mold, molding binder kit, and molding composition |
| JP2019063842A (en) * | 2017-10-04 | 2019-04-25 | 花王株式会社 | Aggregate composition for mold |
| JP7341610B2 (en) | 2019-10-30 | 2023-09-11 | 花王株式会社 | Hardener composition for mold making |
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