JP2009269062A - Binder composition for casting mold making, sand composition for casting mold making, and manufacturing method of casting mold - Google Patents

Binder composition for casting mold making, sand composition for casting mold making, and manufacturing method of casting mold Download PDF

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JP2009269062A
JP2009269062A JP2008122679A JP2008122679A JP2009269062A JP 2009269062 A JP2009269062 A JP 2009269062A JP 2008122679 A JP2008122679 A JP 2008122679A JP 2008122679 A JP2008122679 A JP 2008122679A JP 2009269062 A JP2009269062 A JP 2009269062A
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binder composition
mass
mold
mold making
casting mold
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Yasuhiro Nagai
康弘 永井
Masaji Yoshimura
正司 吉村
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Gun Ei Chemical Industry Co Ltd
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Gun Ei Chemical Industry Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder composition for casting mold making which is high in curing speed and is satisfactory in curing in the inside (deep part) of a casting mold, more preferably to provide the binder composition for casting mold making which is eliminated of a flash point so as not to correspond to the Fire Defence Law Class 4 Third Petroleum, is high in curing speed and is satisfactory in curing in the inside (deep part) of the casting mold, and further to provide a sand composition for casting mold making using the binder composition for casting mold making and a method for manufacturing a casting mold using the sand composition for casting mold making. <P>SOLUTION: The binder composition for casting mold making is a binder composition for casting mold making containing an acid curable material and a solvent, in which the acid curable material contains furfuryl alcohol, and the solvent contains a chlorine-based organic solvent. In addition, the content of the solvent in the binder composition for casting mold making is preferably ≥15 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、鋳型造型用粘結剤組成物、鋳型造型用砂組成物および鋳型の製造方法に関する。   The present invention relates to a binder composition for mold making, a sand composition for mold making, and a method for producing a mold.

従来より、鋳造用鋳型の一つとして自硬性鋳型が知られている。この自硬性鋳型は、ケイ砂等の耐火性粒状材料に、酸硬化性物質を主成分とした粘結剤とキシレンスルホン酸やリン酸等の硬化剤とを添加、混練した後、得られた混練砂を型に充填し、粘結剤を酸硬化性物質の重縮合によって硬化させる方法で製造されている。   Conventionally, a self-hardening mold is known as one of casting molds. This self-hardening mold was obtained after adding and kneading a binder mainly composed of an acid curable substance and a curing agent such as xylene sulfonic acid or phosphoric acid to a refractory granular material such as silica sand. It is manufactured by a method in which kneaded sand is filled into a mold and the binder is cured by polycondensation of an acid curable substance.

このような自硬性鋳型の粘結剤に用いる酸硬化性物質は、一般的にフルフリルアルコールを主原料とする。
ところが、フルフリルアルコールは引火点が低く、消防法第4類第三石油類に該当しており、フルフリルアルコールを用いた引火点の低い粘結剤は著しく保管数量が制限されている。そこで、フルフリルアルコールに水を添加することで引火点がなく、消防法第4類第三石油類に該当しないものとした粘結剤が広く流通している。
しかしながら、この引火点がない粘結剤は水を多く含んでいるため、硬化速度が遅く、かつ鋳型内部(深部)の硬化が不良となり易い。従って、型から鋳型を取り出すのに時間がかかり、鋳型製造に時間がかかるという問題がある。
The acid curable substance used for the binder of such a self-hardening mold generally contains furfuryl alcohol as a main raw material.
However, furfuryl alcohol has a low flash point and falls under the category 4 of the Fire Services Act, Class 3 Petroleum. Binders with a low flash point using furfuryl alcohol are remarkably limited in storage quantity. Therefore, binders that do not fall under the Fire Service Act Type 4 and Type 3 Petroleum are widely distributed by adding water to furfuryl alcohol so that there is no flash point.
However, since the binder having no flash point contains a large amount of water, the curing rate is slow, and the inside of the mold (deep part) tends to be poor. Therefore, it takes time to take out the mold from the mold, and there is a problem that it takes time to manufacture the mold.

そこで硬化速度を向上させる方法として、硬化剤として酸濃度の比較的高い硫酸を使用する方法、或いは使用する硬化剤量を多くする方法が挙げられるが、十分な鋳型強度を発現させることは難しく、型から鋳型を取り出す時間を短くすることが著しく困難であった。
更に、このように硬化剤として硫酸を多量に用いると、鋳型を構成する砂が硫黄を多く含むものであるため、注湯時に亜硫酸ガスを大量発生させて作業環境を悪化させる、若しくは砂中の残留硫黄を増加させて砂特性を悪化させる等の問題が生じた。
Therefore, as a method for improving the curing rate, a method of using sulfuric acid having a relatively high acid concentration as a curing agent, or a method of increasing the amount of the curing agent to be used is mentioned, but it is difficult to express sufficient mold strength, It was extremely difficult to shorten the time for removing the mold from the mold.
Further, when a large amount of sulfuric acid is used as a curing agent in this way, the sand constituting the mold contains a large amount of sulfur, so a large amount of sulfurous acid gas is generated during pouring to deteriorate the working environment, or residual sulfur in the sand. This causes problems such as increasing sand and deteriorating sand characteristics.

また、硬化速度を向上させる方法としては、耐火性粒状材料に塩化カルシウム等のアルカリ土類金属の塩化物を添加し、硬化の過程で生成する縮合水を塩化物に吸収させて硬化反応を円滑にするとともに、より硬化促進効果の高い塩酸を生成させる方法(例えば、特許文献1参照。)も挙げられる。
特開昭48−56520号公報
As a method for improving the curing rate, an alkaline earth metal chloride such as calcium chloride is added to the refractory granular material, and the condensed water generated in the curing process is absorbed by the chloride to facilitate the curing reaction. And a method of generating hydrochloric acid having a higher curing acceleration effect (see, for example, Patent Document 1).
JP-A-48-56520

しかしながら、特許文献1に記載の方法では、塩化カルシウム等のアルカリ土類の塩化物は粉末状で用いるため、吸湿し易く、一定以上の量を添加することが困難であり、実用化に向かないという問題がある。   However, in the method described in Patent Document 1, since alkaline earth chloride such as calcium chloride is used in a powder form, it is easy to absorb moisture, and it is difficult to add a certain amount or more, which is not suitable for practical use. There is a problem.

本発明は、上記事情を鑑みてなされたもので、硬化速度が速く、かつ鋳型内部(深部)でも硬化が良好な、鋳型造型用粘結剤組成物を提供することを目的とし、より好ましくは、引火点をなくして消防法第4類第三石油類に該当しないものとした、硬化速度が速く、かつ鋳型内部(深部)でも硬化が良好である、鋳型造型用粘結剤組成物を提供することを目的とする。
更に、本発明は該鋳型造型用粘結剤組成物を用いた鋳型造型用砂組成物と、該鋳型造型用砂組成物を用いた鋳型の製造方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and has an object to provide a binder for mold making, which has a high curing rate and good curing even in the mold (deep part), and more preferably. Provides a binder composition for mold making that eliminates the flash point and does not fall under the category of the third class petroleum products of the Fire Service Act, has a fast curing speed and good curing even inside the mold (deep part) The purpose is to do.
Another object of the present invention is to provide a mold-making sand composition using the mold-forming binder composition and a method for producing a mold using the mold-making sand composition.

本発明の鋳型造型用粘結剤組成物は、酸硬化性物質と溶媒とを含有する鋳型造型用粘結剤組成物であり、前記酸硬化性物質がフルフリルアルコールを含有し、前記溶媒が塩素系有機溶剤を含有することを特徴とする。   The binder composition for mold making of the present invention is a binder composition for mold making containing an acid curable substance and a solvent, wherein the acid curable substance contains furfuryl alcohol, and the solvent contains It contains a chlorinated organic solvent.

本発明の鋳型造型用粘結剤組成物において、前記塩素系有機溶剤が、四塩化炭素、クロロホルム、テトラクロロエチレン、トリクロロエチレン、及び塩化メチレンからなる群より選ばれる1種又は2種以上であると好ましい。
本発明の鋳型造型用粘結剤組成物において、前記溶媒が塩素系有機溶剤のみからなると好ましい。
本発明の鋳型造型用粘結剤組成物において、前記溶媒が塩素系有機溶剤と水のみからなると好ましい。
本発明の鋳型造型用粘結剤組成物において、前記溶媒の含有率が15質量%以上であると好ましい。
本発明の鋳型造型用粘結剤組成物は、前記塩素系有機溶剤を1質量%以上含有すると好ましい。
本発明の鋳型造型用粘結剤組成物において、前記溶媒の含有率が50質量%以下であると好ましい。
本発明の鋳型造型用粘結剤組成物は、前記酸硬化性物質として、フルフリルアルコール、フェノール類及び尿素よりなる群から選ばれる1種又は2種以上と、アルデヒド類とを、縮合又は共縮合させた酸硬化性樹脂を1種又は2種以上含有すると好ましい。
In the binder composition for mold making of the present invention, the chlorinated organic solvent is preferably one or more selected from the group consisting of carbon tetrachloride, chloroform, tetrachloroethylene, trichloroethylene, and methylene chloride.
In the binder composition for mold making according to the present invention, it is preferable that the solvent comprises only a chlorinated organic solvent.
In the binder composition for mold making according to the present invention, it is preferable that the solvent comprises only a chlorinated organic solvent and water.
In the binder composition for mold making of the present invention, the content of the solvent is preferably 15% by mass or more.
The binder composition for mold making of the present invention preferably contains 1% by mass or more of the chlorinated organic solvent.
In the binder composition for mold making of the present invention, the content of the solvent is preferably 50% by mass or less.
The binder composition for mold making according to the present invention comprises, as the acid curable substance, one or more selected from the group consisting of furfuryl alcohol, phenols and urea, and an aldehyde. It is preferable to contain one or two or more condensed acid curable resins.

本発明の鋳型造型用砂組成物は、前記鋳型造型用粘結剤組成物と耐火性粒状材料と硬化剤とを含有することを特徴とする。
また、本発明の鋳型の製造方法は、前記鋳型造型用砂組成物を鋳型造型用の型に充填して、前記鋳型造型用粘結剤組成物を硬化させることを特徴とする。
The sand mold molding composition of the present invention is characterized by containing the above binder molding molding composition, a refractory granular material, and a curing agent.
The mold manufacturing method of the present invention is characterized in that the mold making sand composition is filled into a mold making mold and the mold making binder composition is cured.

本発明によれば、硬化速度が速く、かつ鋳型内部(深部)でも硬化が良好である鋳型造型用粘結剤組成物が提供でき、より好ましい対応によれば、引火点をなくして消防法第4類第三石油類に該当しないものとした、硬化速度が速く、かつ鋳型内部(深部)でも硬化が良好である、鋳型造型用粘結剤組成物を提供することができる。
このような鋳型造型用粘結剤組成物を含有している、本発明の鋳型造型用砂組成物を用いて鋳型を製造すると鋳型の製造時間を短縮できる。
また、本発明の鋳型造型用粘結剤組成物を用いた鋳型の製造方法によれば、時間をかけずに十分な鋳型強度を有した鋳型を得ることが可能となる。
According to the present invention, it is possible to provide a mold-forming binder composition having a high curing rate and good curing even in the interior (deep part) of the mold. There can be provided a binder composition for mold making, which does not correspond to Group 4 third petroleums, has a high curing rate and good curing even in the mold (deep part).
When a mold is produced using the mold-forming sand composition of the present invention containing such a mold-forming binder composition, the production time of the mold can be shortened.
Further, according to the method for producing a mold using the binder composition for mold making of the present invention, it is possible to obtain a mold having sufficient mold strength without taking time.

以下、本発明を詳細に説明する。
[鋳型造型用粘結剤組成物]
本発明の鋳型造型用粘結剤組成物(以下「粘結剤組成物」という。)は、鋳型を製造する際の粘結剤として使用されるものであり、酸硬化性物質と溶媒とを含有することを特徴とする。
Hereinafter, the present invention will be described in detail.
[Binder composition for mold making]
The binder composition for mold making of the present invention (hereinafter referred to as “binder composition”) is used as a binder in the production of a mold, and comprises an acid curable substance and a solvent. It is characterized by containing.

(酸硬化性物質)
本発明における酸硬化性物質とは、酸により重縮合して硬化する物質であり、フルフリルアルコールを含有するものである。
酸硬化性物質は、フルフリルアルコール以外に、従来公知の酸硬化性樹脂を含有することができる。
酸硬化性樹脂として例えば、フルフリルアルコール、フェノール類及び尿素よりなる群から選ばれる1種、又は2種以上と、アルデヒド類とを、縮合又は共縮合させた樹脂を挙げることができる。
これらの酸硬化性樹脂は1種を用いても、2種以上を併用しても良い。
(Acid curable substance)
The acid curable substance in the present invention is a substance that is cured by polycondensation with an acid and contains furfuryl alcohol.
The acid curable substance may contain a conventionally known acid curable resin in addition to furfuryl alcohol.
Examples of the acid curable resin include a resin obtained by condensation or cocondensation of one or two or more aldehydes selected from the group consisting of furfuryl alcohol, phenols, and urea.
These acid curable resins may be used alone or in combination of two or more.

各縮合物を製造する際に使用されるアルデヒド類としては、ホルムアルデヒド、グリオキザール、フルフラール等が挙げられる。これらは2種以上を組み合わせて使用してもよい。ただし、縮合物の種類によっては、アルデヒド類としてグリオキザールやフルフラールを単独で使用した際には、酸硬化が進行しない場合もある。そのような場合には、アルデヒド類として少なくともホルムアルデヒドを使用すればよい。   Examples of aldehydes used in producing each condensate include formaldehyde, glyoxal, and furfural. You may use these in combination of 2 or more type. However, depending on the type of condensate, when glyoxal or furfural is used alone as an aldehyde, acid curing may not proceed. In such a case, at least formaldehyde may be used as the aldehyde.

フェノール類としては、フェノール、クレゾール、レゾルシノール、ビスフェノールA、ビスフェノールC、ビスフェノールE、ビスフェノールF、ビスフェノールZなどが挙げられる。これらは2種以上を組み合わせて使用してもよい。   Examples of phenols include phenol, cresol, resorcinol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, and bisphenol Z. You may use these in combination of 2 or more type.

フルフリルアルコールとアルデヒド類の縮合物を製造する場合には、フルフリルアルコール1モルに対して、アルデヒド類を0.1〜1モル使用することが好ましい。アルデヒド類の使用量が0.1モル以上であれば、重合度の低い縮合物となるため、可使時間設定が容易となり、1モル以下であれば、重合度の高い縮合物となるため、鋳型強度発現が良好となる。
また、フェノール類とアルデヒド類の縮合物を製造する場合には、フェノール類1モルに対して、アルデヒド類を1〜3モル使用することが好ましい。アルデヒド類の使用量が1モル以上であれば、重合度の低い縮合物となるため、可使時間設定が容易となり、3モル以下であれば、重合度の高い縮合物となるため、鋳型強度発現が良好となる。
また、尿素とアルデヒド類の縮合物など、窒素原子を含む縮合物を製造する場合には、得られた縮合物中の窒素原子量が粘結剤組成物を100質量%とした際に、0.1〜6質量%の範囲となるように尿素の使用量を決定することが好ましい。より好ましくは0.1〜4.5質量%である。窒素原子量が0.1質量%以上であれば、鋳型の初期強度が向上し、6質量%以下であれば、鋳型の最終強度が向上する。
When manufacturing the condensate of furfuryl alcohol and aldehydes, it is preferable to use 0.1-1 mol of aldehydes with respect to 1 mol of furfuryl alcohol. If the amount of aldehyde used is 0.1 mol or more, it becomes a condensate with a low degree of polymerization, so that the pot life can be easily set, and if it is 1 mol or less, it becomes a condensate with a high degree of polymerization. The mold strength is improved.
Moreover, when manufacturing the condensate of phenols and aldehydes, it is preferable to use 1-3 mol of aldehydes with respect to 1 mol of phenols. If the amount of aldehyde used is 1 mol or more, it becomes a condensate with a low degree of polymerization, so that it is easy to set the pot life, and if it is 3 mol or less, it becomes a condensate with a high degree of polymerization. Good expression.
In the case of producing a condensate containing a nitrogen atom, such as a condensate of urea and aldehydes, when the amount of nitrogen atoms in the obtained condensate is 100% by mass of the binder composition, the concentration is 0. It is preferable to determine the amount of urea used so as to be in the range of 1 to 6% by mass. More preferably, it is 0.1-4.5 mass%. If the amount of nitrogen atoms is 0.1% by mass or more, the initial strength of the template is improved, and if it is 6% by mass or less, the final strength of the template is improved.

(溶媒)
溶媒としては少なくとも不燃性の塩素系有機溶剤を用いる。
塩素系有機溶剤とは、塩素を含む有機化合物のことである。
塩素系有機溶剤としては、四塩化炭素、クロロホルム、テトラクロロエチレン、トリクロロエチレン及び塩化メチレンが挙げられ、好ましくは、テトラクロロエチレン、トリクロロエチレン及び四塩化炭素が用いられ、中でも自消効果の高い四塩化炭素を用いると好ましい。
また、塩素系有機溶剤の他に溶媒として水を併用してもよい。
水以外に併用可能な溶媒として、メタノール、エタノール、イソプロピルアルコール等の1価アルコール;エチレングリコール、プロピレングリコール等の2価アルコール等が挙げられる。これらは、鋳型造型用粘結剤組成物の粘性を下げる場合や、耐火性粒状材料との界面張力を下げる場合などに用いることができる。
(solvent)
As the solvent, at least a nonflammable chlorinated organic solvent is used.
A chlorinated organic solvent is an organic compound containing chlorine.
Examples of the chlorinated organic solvent include carbon tetrachloride, chloroform, tetrachloroethylene, trichlorethylene, and methylene chloride, preferably tetrachloroethylene, trichloroethylene, and carbon tetrachloride are used, and carbon tetrachloride having a high self-extinguishing effect is particularly preferable. .
In addition to the chlorinated organic solvent, water may be used in combination.
Examples of solvents that can be used in addition to water include monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; dihydric alcohols such as ethylene glycol and propylene glycol. These can be used when the viscosity of the binder composition for mold making is lowered, or when the interfacial tension with the refractory granular material is lowered.

このような塩素系有機溶剤を本発明の鋳型造型用粘結剤組成物に含有させると、硬化速度が向上し、鋳型内部(深部)の硬化を良好なものとすることができる。
本発明で用いる塩素系有機溶剤は、硫酸水溶液等の硬化剤と混合すると、塩素が遊離し塩酸が生成される傾向にある。この塩酸は、酸硬化性物質を硬化せしめる硬化剤としての役割を果たすことができ、硬化速度が向上すると推察される。
When such a chlorinated organic solvent is contained in the binder composition for mold making of the present invention, the curing rate is improved, and the inside of the mold (deep part) can be cured well.
When the chlorinated organic solvent used in the present invention is mixed with a curing agent such as an aqueous sulfuric acid solution, chlorine is liberated and hydrochloric acid tends to be generated. This hydrochloric acid can play a role as a curing agent for curing the acid curable substance, and it is assumed that the curing rate is improved.

本発明の粘結剤組成物に占める塩素系有機溶剤の割合は、1質量%以上であることが好ましく、5質量%以上であることが更に好ましく、15質量%以上であることが特に好ましい。
本発明の粘結剤組成物に占める塩素系有機溶剤の割合が1質量%以上であれば、硬化速度が良好となる傾向にある。
The proportion of the chlorinated organic solvent in the binder composition of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 15% by mass or more.
If the ratio of the chlorinated organic solvent in the binder composition of the present invention is 1% by mass or more, the curing rate tends to be good.

本発明の粘結剤組成物に占める溶媒の割合は、50質量%以下であることが好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましく、25質量%以下であることが特に好ましい。
溶媒の割合が50質量%以下であれば、硬化速度を低下させることがなく、鋳型内部(深部)の硬化が良好になる傾向にある。
The proportion of the solvent in the binder composition of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and 25% by mass. It is particularly preferred that
If the ratio of the solvent is 50% by mass or less, the curing rate does not decrease and the curing inside the mold (deep part) tends to be good.

更に、本発明で用いる塩素系有機溶剤は不燃性であり、この不燃性の性質を有する成分をフルフリルアルコールに添加することで、フルフリルアルコールの引火点が無くすことができると推察される。
溶媒として、塩素系有機溶剤のみ又は塩素系有機溶剤と水の混合物のみを用いる場合、本発明の粘結剤組成物に占める溶媒の割合が15質量%以上であるとフルフリルアルコールの引火点をなくす事が可能となり好ましい。
Furthermore, the chlorinated organic solvent used in the present invention is nonflammable, and it is presumed that the flash point of furfuryl alcohol can be eliminated by adding a component having this nonflammable property to furfuryl alcohol.
When only a chlorinated organic solvent or a mixture of a chlorinated organic solvent and water is used as the solvent, the flash point of furfuryl alcohol is 15% by mass or more of the solvent in the binder composition of the present invention. This is preferable because it can be eliminated.

(その他の成分)
また、粘結剤組成物中には、得られる鋳型の強度を向上させる目的で、N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン等のシランカップリング剤を添加してもよい。
更に、粘結剤組成物中には、造型注湯時に発生するホルムアルデヒドを低減させる目的で、尿素、レゾルシノール、ピロガロール等を含有させてもよい。
(Other ingredients)
In the binder composition, a silane coupling agent such as N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane may be added for the purpose of improving the strength of the obtained template.
Further, the binder composition may contain urea, resorcinol, pyrogallol and the like for the purpose of reducing formaldehyde generated during casting pouring.

本発明の粘結剤組成物において、シランカップリング剤は0.01〜3質量%含有させることが可能であり、0.1〜1質量%含有させることがより好ましい。シランカップリング剤を0.01質量%以上含有させると、鋳型の強度を上げることができ、3質量%以下であれば、大幅なコスト上昇を抑えることができる。   In the binder composition of the present invention, the silane coupling agent can be contained in an amount of 0.01 to 3% by mass, and more preferably 0.1 to 1% by mass. If the silane coupling agent is contained in an amount of 0.01% by mass or more, the strength of the mold can be increased, and if it is 3% by mass or less, a significant cost increase can be suppressed.

本発明の粘結剤組成物は、未硬化の状態にある酸硬化性物質と、溶媒と、必要に応じて添加されるその他の成分とを混合することで製造できる。
また、未硬化の酸硬化性物質を製造する過程で、塩素系有機溶剤や水分を添加することで、結果的にこれらの成分を含有する粘結剤組成物を得てもよい。
The binder composition of the present invention can be produced by mixing an acid curable substance in an uncured state, a solvent, and other components added as necessary.
Moreover, you may obtain the binder composition containing these components as a result by adding a chlorinated organic solvent and a water | moisture content in the process of manufacturing an uncured acid-curable substance.

[鋳型造型用砂組成物]
上記粘結剤組成物とこの粘結剤組成物を硬化させる硬化剤とを耐火性粒状材料に加え、これらを攪拌機などで混練することによって、鋳型造型用砂組成物(以下、「砂組成物」という。)を得ることができる。
[Sand composition for mold making]
The above-mentioned binder composition and a curing agent for curing the binder composition are added to a refractory granular material, and these are kneaded with a stirrer or the like to obtain a sand composition for molding (hereinafter referred to as “sand composition”). Can be obtained.)

耐火性粒状材料としては、ケイ砂、クロマイト砂、ジルコン砂、オリビン砂、アルミナ砂、ムライト砂、合成ムライト砂等の従来公知のものを使用でき、また、使用済みの耐火性材料を回収したものや再生処理をしたものなども使用できる。   As the refractory granular material, conventionally known materials such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, synthetic mullite sand can be used, and used refractory material is recovered. You can also use or reprocessed ones.

硬化剤としては、キシレンスルホン酸などのスルホン酸系化合物、リン酸系化合物、硫酸など、従来公知のものを1種又は2種以上使用できる。   As the curing agent, one or more conventionally known compounds such as sulfonic acid compounds such as xylene sulfonic acid, phosphoric acid compounds, and sulfuric acid can be used.

本発明の砂組成物における耐火性粒状材料と粘結剤組成物と硬化剤との比率は適宜設定できるが、耐火性粒状材料100質量部に対し、粘結剤組成物が0.5〜1.5質量部で、硬化剤が0.075〜0.9質量部の範囲が好ましい。このような混合比率であると、十分な強度の鋳型が得られやすい。   The ratio of the refractory granular material, the binder composition and the curing agent in the sand composition of the present invention can be appropriately set, but the binder composition is 0.5 to 1 with respect to 100 parts by mass of the refractory granular material. 0.5 mass part and the range of 0.075-0.9 mass part of hardening | curing agents are preferable. With such a mixing ratio, it is easy to obtain a mold having sufficient strength.

[鋳型製造方法]
本発明の砂組成物から鋳型を製造する方法としては、自硬性鋳型造型法を採用することができる。すなわち、本発明の砂組成物を鋳型造型用の所定の型に充填すると、砂組成物中の粘結剤組成物が硬化剤の作用により硬化する。その結果、鋳型を得ることができる。
[Mold manufacturing method]
As a method for producing a mold from the sand composition of the present invention, a self-hardening mold making method can be employed. That is, when the sand composition of the present invention is filled in a predetermined mold for mold making, the binder composition in the sand composition is cured by the action of the curing agent. As a result, a template can be obtained.

以上説明したように、本発明では、フルフリルアルコールに塩素系有機溶剤を含有させたことにより、硬化速度が速く、かつ鋳型深部(内部)の硬化を良好にすることが可能な粘結剤組成物を得ることができた。
従って、該粘結剤組成物を用いた本発明の砂組成物においては、硬化速度を高めるために硬化剤を多量に使用する必要はなく、硬化剤をむしろ少なく抑えることができる。
従来、硬化剤として、スルホン酸系化合物や硫酸を使用した際には、得られた鋳型への注湯時において、鋳型を構成している硬化物が熱分解し、亜硫酸ガスが発生することが知られているが、このように硬化剤量を抑えることができれば、亜硫酸ガス発生量も大幅に低減できる。亜硫酸ガス発生量を低減すると、より良好な作業環境が得られると同時に、亜硫酸ガス中の硫黄に起因する鋳物球状化阻害の発生率も低下させることができる。
更に、本発明の砂組成物は、硬化速度が向上した本発明の粘結剤組成物を用いているため、鋳型内部(深部)の硬化不良を低減した鋳型を、より早く製造することもできる。
また、本発明の砂組成物を用いた鋳型製造方法によれば、鋳型内部(深部)の硬化不良が低減しながらも、短時間で、充分な鋳型強度を有した鋳型を得ることが可能である。
また、本発明の粘結剤組成物は消防法第4類第三石油類に該当するフルフリルアルコールを含有している。しかしながら本発明では、溶媒(塩素系有機溶剤のみ又は塩素系有機溶剤と水の混合物のみ)を15質量%以上含有することにより、引火点がなく、消防法第4類第三石油類に該当しない粘結剤組成物を得ることが可能となる。このように引火点のない粘結剤組成物は、フルフリルアルコールを含有しながらも、保管数量が限定されない。
As described above, in the present invention, a binder composition capable of increasing the curing speed and improving the curing of the deep part (inside) of the mold by adding a chlorinated organic solvent to furfuryl alcohol. I was able to get things.
Therefore, in the sand composition of the present invention using the binder composition, it is not necessary to use a large amount of the curing agent in order to increase the curing rate, and the curing agent can be suppressed to a small amount.
Conventionally, when a sulfonic acid compound or sulfuric acid is used as a curing agent, a cured product constituting the mold is thermally decomposed and sulfurous acid gas is generated when pouring into the obtained mold. As is known, if the amount of the curing agent can be suppressed in this way, the amount of sulfurous acid gas generated can be greatly reduced. When the amount of sulfurous acid gas generated is reduced, a better working environment can be obtained, and at the same time, the rate of inhibition of casting spheroidization due to sulfur in the sulfurous acid gas can be reduced.
Furthermore, since the sand composition of the present invention uses the binder composition of the present invention having an improved curing rate, it is possible to produce a mold with reduced curing failure inside the mold (deep part) earlier. .
In addition, according to the mold manufacturing method using the sand composition of the present invention, it is possible to obtain a mold having sufficient mold strength in a short time while reducing poor curing inside the mold (deep part). is there.
Moreover, the binder composition of this invention contains the furfuryl alcohol applicable to Fire Service Act 4th class 3rd petroleum. However, in the present invention, by containing 15% by mass or more of the solvent (only the chlorinated organic solvent or the mixture of the chlorinated organic solvent and water), there is no flash point, and it does not fall under the Fire Service Law Class 4 Third Petroleum. It becomes possible to obtain a binder composition. As described above, the binder composition having no flash point contains furfuryl alcohol, but the storage quantity is not limited.

以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。   Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[実施例1〜9]
フルフリルアルコールに、四塩化炭素或いは四塩化炭素と水からなる溶媒と、シランカップリング剤であるN−β(アミノエチル)γ−アミノプロピルメチルジメトキシシランとを添加、混合し、各成分を表1に示す混合率で含有する粘結剤組成物を調製した。
[Examples 1 to 9]
A solvent comprising carbon tetrachloride or carbon tetrachloride and water and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane as a silane coupling agent are added to and mixed with furfuryl alcohol, and each component is represented. A binder composition containing the mixing ratio shown in 1 was prepared.

次に、フリーマントル6号砂(ケイ砂、三菱商事建材製)100質量部に対して、上記粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有、テイカトックス120、テイカ(株)製)0.4質量部とを添加し、品川式万能攪拌機(MIXER、(株)品川工業所製)で混練して、砂組成物を得た。   Next, with respect to 100 parts by mass of Fremantle No. 6 sand (silica sand, manufactured by Mitsubishi Corporation Building Materials), 1 part by mass of the above binder composition and a curing agent (containing 65% by mass of xylene sulfonic acid, Teikatox 120, 0.4 parts by mass (Taika Co., Ltd.) was added and kneaded with a Shinagawa universal stirrer (MIXER, Shinagawa Kogyo Co., Ltd.) to obtain a sand composition.

[比較例1〜7]
フルフリルアルコール単独、又はフルフリルアルコールに水を添加したものに、シランカップリング剤であるN−β(アミノエチル)γ−アミノプロピルメチルジメトキシシランを添加、混合し、各成分を表1に示す混合率で含有する粘結剤組成物を調製した。
[Comparative Examples 1-7]
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, which is a silane coupling agent, is added to and mixed with furfuryl alcohol alone or with water added to furfuryl alcohol, and each component is shown in Table 1. A binder composition containing the mixture was prepared.

次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。   Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.

実施例1〜9及び比較例1〜7で得られた各粘結剤組成物及び砂組成物について、以下の引火点試験及び鋳型強度試験を行った。結果を表1に示す。   The following flash point tests and mold strength tests were performed on the binder compositions and sand compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 7. The results are shown in Table 1.

(引火点試験)
各実施例及び比較例において得られた粘結剤組成物を、クリーブランド開放式により引火点70〜120℃について測定した。
(Flash point test)
The binder composition obtained in each Example and Comparative Example was measured for a flash point of 70 to 120 ° C. by the Cleveland open type.

(鋳型強度試験)
各実施例及び比較例にて得られた砂組成物の一部を、直ちに温度25℃、湿度40%の条件下、内径50mm、高さ50mmの型が形成されたテストピース作製用木型に充填して硬化させ、更に鋳型の内部(深部)を想定して、外気影響を受けにくくするため、テストピース作製用木型に蓋をした。
そして、1時間経過後と3時間経過後に硬化後のテストピースを取り出し、その鋳型強度(圧縮強度)を、JIS Z 2601の鋳物砂の試験方法に準じ、卓上抗圧力試験機(高千穂機械(株)製)を用いて測定した。
(Mold strength test)
A part of the sand composition obtained in each of the examples and comparative examples was immediately formed into a test piece production wooden mold in which a mold having an inner diameter of 50 mm and a height of 50 mm was formed under the conditions of a temperature of 25 ° C. and a humidity of 40%. In order to make it hard to be affected by outside air, assuming that the inside (deep part) of the mold was filled, the wooden piece for test piece preparation was covered.
Then, after 1 hour and 3 hours have passed, the cured test pieces are taken out, and the mold strength (compressive strength) is determined according to the testing method for foundry sand of JIS Z 2601 (table pressure test machine (Takachiho Machine Co., Ltd.). )).

Figure 2009269062
Figure 2009269062

表1に示されるように、フルフリルアルコールと不燃性液体である四塩化炭素とを含有させた実施例1〜9の粘結剤組成物と、フルフリルアルコールを単独で用いた比較例1の粘結剤組成物及びフルフリルアルコールと不燃性液体である水とを含有させた比較例2〜7の粘結剤組成物とを比較すると、フルフリルアルコールと四塩化炭素とを含有させた実施例1〜9の粘結剤組成物の方が、硬化速度が速く、かつ鋳型強度に優れている。
詳しくは、四塩化炭素を5質量%含有させた実施例1と、フルフリルアルコールを単独で用いた比較例1を比較すると、四塩化炭素を含有させた実施例1の方が、初期及び硬化時間3時間の段階における鋳型強度が優れていた。
また、四塩化炭素のみを含有させた実施例1〜6と、水のみを含有させた比較例2〜7とを比較すると、四塩化炭素のみを含有させた実施例1〜6については、初期の鋳型強度が高まり、硬化時間3時間の段階では、より鋳型内部(深部)の硬化が良好であるといえる鋳型強度が得られた。一方、不燃性液体として水のみを含有させた比較例2〜7については、初期の鋳型強度が全く得られず、硬化時間3時間の段階でも、鋳型強度を得にくかった。
また、四塩化炭素と水の混合溶媒を20質量%含有させた実施例7〜9と、水のみを20質量%含有させた比較例4とを比較すると、四塩化炭素と水の混合溶媒20質量%を含有させた実施例5〜7については、初期の鋳型強度が高まり、硬化時間3時間の段階では、より鋳型内部(深部)の硬化が良好であるといえる鋳型強度が得られた。一方、比較例4では、初期の鋳型強度が全く得られず、硬化時間3時間の段階でも、鋳型強度を得にくかった。
更に、表1に示されるように、不燃性液体として、四塩化炭素又は四塩化炭素と水の混合溶媒を用いている実施例においては、これら不燃性液体を15質量%以上含有させた場合(実施例2〜9)引火点をなくすことが可能であった。
As shown in Table 1, the binder composition of Examples 1 to 9 containing furfuryl alcohol and carbon tetrachloride which is an incombustible liquid, and Comparative Example 1 using furfuryl alcohol alone. Compared with the binder composition and the binder composition of Comparative Examples 2 to 7 containing water which is a non-flammable liquid and furfuryl alcohol, the practice was to contain furfuryl alcohol and carbon tetrachloride. The binder compositions of Examples 1 to 9 have a faster curing rate and superior mold strength.
Specifically, when Example 1 containing 5% by mass of carbon tetrachloride and Comparative Example 1 using furfuryl alcohol alone are compared, Example 1 containing carbon tetrachloride is more initial and cured. The mold strength at the stage of 3 hours was excellent.
Further, when Examples 1 to 6 containing only carbon tetrachloride and Comparative Examples 2 to 7 containing only water were compared, Examples 1 to 6 containing only carbon tetrachloride were The mold strength was increased, and at the stage where the curing time was 3 hours, a mold strength that could be said to be better cured inside the mold (deep part) was obtained. On the other hand, in Comparative Examples 2 to 7 containing only water as the nonflammable liquid, the initial mold strength was not obtained at all, and it was difficult to obtain the mold strength even at the stage of curing time of 3 hours.
Further, when Examples 7 to 9 containing 20% by mass of a mixed solvent of carbon tetrachloride and water are compared with Comparative Example 4 containing 20% by mass of water alone, a mixed solvent of carbon tetrachloride and water 20 With respect to Examples 5 to 7 containing mass%, the initial mold strength was increased, and a mold strength that could be said to be better cured inside the mold (deep part) was obtained when the curing time was 3 hours. On the other hand, in Comparative Example 4, the initial mold strength was not obtained at all, and it was difficult to obtain the mold strength even when the curing time was 3 hours.
Furthermore, as shown in Table 1, in Examples using carbon tetrachloride or a mixed solvent of carbon tetrachloride and water as the incombustible liquid, when these incombustible liquids are contained in an amount of 15% by mass or more ( Examples 2 to 9) It was possible to eliminate the flash point.

[実施例10〜13]
フルフリルアルコールに、溶媒として、クロロホルム、テトラクロロエチレン、トリクロロエチレン、塩化メチレンのいずれかを20質量%と、シランカップリング剤であるN−β(アミノエチル)γ−アミノプロピルメチルジメトキシシランとを添加、混合し、各成分を表2に示す混合率で含有する粘結剤組成物を調製した。
[Examples 10 to 13]
Add and mix 20% by mass of chloroform, tetrachloroethylene, trichloroethylene, or methylene chloride with N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane as a silane coupling agent to furfuryl alcohol. Then, a binder composition containing each component at a mixing ratio shown in Table 2 was prepared.

次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。
実施例10〜13で得られた各粘結剤組成物及び砂組成物について、前述の引火点試験及び鋳型強度試験を行った。結果を表2に示す。
Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.
About each binder composition and sand composition obtained in Examples 10-13, the above-mentioned flash point test and mold strength test were done. The results are shown in Table 2.

Figure 2009269062
Figure 2009269062

表2に示されるように、実施例10〜13で得られた粘結剤組成物は、不燃性液体として各塩素系有機溶剤を20質量%含有しており、引火点のないものであった。
また、不燃性液体として各塩素系有機溶剤のみを20質量%用いた実施例10〜13と、不燃性液体として水のみを20質量%用いた比較例4とを比較すると、各塩素系有機溶剤のみを20質量%用いた実施例8〜11については、初期の鋳型強度が高まり、硬化時間3時間の段階では、より鋳型内部(深部)の硬化が良好であるといえる鋳型強度が得られた。
As shown in Table 2, the binder compositions obtained in Examples 10 to 13 contained 20% by mass of each chlorinated organic solvent as a non-flammable liquid and had no flash point. .
Further, when comparing Examples 10 to 13 using only 20% by mass of each chlorinated organic solvent as the incombustible liquid and Comparative Example 4 using only 20% by mass of water as the incombustible liquid, each chlorinated organic solvent was compared. In Examples 8 to 11 in which only 20% by mass was used, the initial mold strength was increased, and a mold strength that could be said to be better cured inside the mold (deep part) was obtained when the curing time was 3 hours. .

[実施例14]
酸硬化性物質、四塩化炭素、水及びシランカップリング剤を表3に示す混合率で含有する粘結剤組成物を調製した。
具体的には、まず、フルフリルアルコール246.0質量部と、50質量%ホルムアルデヒド水溶液50.0質量部と、10質量%塩酸1.0質量部とを、温度計、冷却器及び攪拌機を備えた4つ口フラスコ中に入れて100℃で3時間反応させ、フルフリルアルコールとホルムアルデヒドの縮合物及び遊離フルフリルアルコール91.3質量%と、水8.7質量%からなる混合物を得た。
ついで、この混合物93質量部に対して、水1.9質量%と、四塩化炭素5質量部と、シランカップリング剤0.1質量部とを加えて、各成分を表3に示す混合率で含有する粘結剤組成物を調製した。
[Example 14]
A binder composition containing an acid curable substance, carbon tetrachloride, water, and a silane coupling agent at a mixing ratio shown in Table 3 was prepared.
Specifically, first, 246.0 parts by mass of furfuryl alcohol, 50.0 parts by mass of a 50% by mass aqueous formaldehyde solution, and 1.0 part by mass of 10% by mass hydrochloric acid are provided with a thermometer, a cooler, and a stirrer. Then, the mixture was placed in a four-necked flask and reacted at 100 ° C. for 3 hours to obtain a mixture comprising a furfuryl alcohol-formaldehyde condensate and 91.3% by mass of free furfuryl alcohol and 8.7% by mass of water.
Subsequently, with respect to 93 parts by mass of this mixture, 1.9% by mass of water, 5 parts by mass of carbon tetrachloride, and 0.1 parts by mass of a silane coupling agent were added, and the mixing ratios shown in Table 3 for the respective components. The binder composition contained in was prepared.

次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。   Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.

[実施例15]
酸硬化性物質、四塩化炭素、水及びシランカップリング剤を表3に示す混合率で含有する粘結剤組成物を調製した。
具体的には、まず、フェノール500.0質量部と、50質量%ホルムアルデヒド水溶液44.2質量部と、48質量%水酸化カリウム水溶液26.9質量部とを、温度計、冷却器及び攪拌機を備えた4つ口フラスコ中に入れて70℃で2時間反応させ、その後、65質量%パラトルエンスルホン酸水溶液55.5質量部を加えて中和し、フェノールとホルムアルデヒドの縮合物72.9質量%と、水27.1質量%からなる混合物を得た。
ついで、この混合物18.5質量部に対して、フルフリルアルコール71.4質量部と、水5質量部と、四塩化炭素5質量部と、シランカップリング剤0.1質量部とを加えて、各成分を表3に示す混合率で含有する粘結剤組成物を調製した。
[Example 15]
A binder composition containing an acid curable substance, carbon tetrachloride, water, and a silane coupling agent at a mixing ratio shown in Table 3 was prepared.
Specifically, first, 500.0 parts by mass of phenol, 44.2 parts by mass of 50% by mass aqueous formaldehyde solution, and 26.9 parts by mass of 48% by mass aqueous potassium hydroxide solution were added with a thermometer, a cooler, and a stirrer. The mixture was placed in a four-necked flask and allowed to react at 70 ° C. for 2 hours, and then neutralized by adding 55.5 parts by mass of a 65% by mass paratoluenesulfonic acid aqueous solution, and 72.9 masses of a phenol / formaldehyde condensate. % And 27.1% by weight of water were obtained.
Next, 71.4 parts by mass of furfuryl alcohol, 5 parts by mass of water, 5 parts by mass of carbon tetrachloride, and 0.1 parts by mass of a silane coupling agent were added to 18.5 parts by mass of this mixture. A binder composition containing each component at a mixing ratio shown in Table 3 was prepared.

次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。   Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.

[実施例16]
酸硬化性物質、四塩化炭素、水及びシランカップリング剤を表3に示す混合率で含有する粘結剤組成物を調製した。
具体的には、まず、フルフリルアルコール182.5質量部と、尿素66.0質量部と、50質量%ホルムアルデヒド水溶液169.14質量部と、15質量%水酸化ナトリウム水溶液2.0質量部とを、温度計、冷却器及び攪拌機を備えた4つ口フラスコ中に入れて80℃で1時間反応させ、更に、10質量%塩酸3.5質量部を添加して、80℃で1時間反応させた。その後、15質量%水酸化ナトリウム水溶液0.8質量部と、尿素40.0質量部とを添加して、80℃で30分間反応させ、フルフリルアルコールと尿素とホルムアルデヒドの縮合物及び遊離フルフリルアルコール80.6質量%と、水19.4質量%からなる混合物を得た。
ついで、この混合物18.0質量部に対して、フルフリルアルコール70.4質量部と、水6.5質量部と、四塩化炭素5.0質量部と、シランカップリング剤0.1質量部とを加えて、各成分を表3に示す混合率で含有する粘結剤組成物を調製した。
[Example 16]
A binder composition containing an acid curable substance, carbon tetrachloride, water, and a silane coupling agent at a mixing ratio shown in Table 3 was prepared.
Specifically, first, 182.5 parts by mass of furfuryl alcohol, 66.0 parts by mass of urea, 169.14 parts by mass of a 50% by mass aqueous formaldehyde solution, and 2.0 parts by mass of a 15% by mass sodium hydroxide aqueous solution, In a four-necked flask equipped with a thermometer, a cooler, and a stirrer, reacted at 80 ° C. for 1 hour, further added 3.5 mass parts of 10 mass% hydrochloric acid, and reacted at 80 ° C. for 1 hour. I let you. Thereafter, 0.8 parts by mass of a 15% by mass aqueous sodium hydroxide solution and 40.0 parts by mass of urea were added and reacted at 80 ° C. for 30 minutes to give a condensate of furfuryl alcohol, urea and formaldehyde, and free furfuryl. A mixture composed of 80.6% by mass of alcohol and 19.4% by mass of water was obtained.
Next, 70.4 parts by mass of furfuryl alcohol, 6.5 parts by mass of water, 5.0 parts by mass of carbon tetrachloride, and 0.1 parts by mass of a silane coupling agent are added to 18.0 parts by mass of this mixture. And a binder composition containing each component at a mixing ratio shown in Table 3 was prepared.

次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。   Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.

[比較例8]
四塩化炭素を添加せず、その代わりに水の配合量を増加させた以外は実施例14と同様にして、表3に示す粘結剤組成物を調製した。
次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65質量%含有)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。
[Comparative Example 8]
A binder composition shown in Table 3 was prepared in the same manner as in Example 14 except that carbon tetrachloride was not added and the amount of water was increased instead.
Next, 1 part by mass of a binder composition and 0.4 part by mass of a curing agent (containing 65% by mass of xylene sulfonic acid) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand). A sand composition was obtained by kneading with a Shinagawa universal agitator.

[比較例9]
四塩化炭素を添加せず、その代わりに水の配合量を増加させた以外は実施例15と同様にして、表3に示す粘結剤組成物を調製した。
次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65%)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。
[Comparative Example 9]
Binder compositions shown in Table 3 were prepared in the same manner as in Example 15 except that carbon tetrachloride was not added and the amount of water was increased instead.
Next, 1 part by mass of the binder composition and 0.4 part by mass of the curing agent (xylene sulfonic acid 65%) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand), and the Shinagawa type A sand composition was obtained by kneading with a universal stirrer.

[比較例10]
四塩化炭素を添加せず、その代わりに水の配合量を増加させた以外は実施例16と同様にして、表3に示す粘結剤組成物を調製した。
次に、フリーマントル6号砂(ケイ砂)100質量部に対して、粘結剤組成物1質量部と、硬化剤(キシレンスルホン酸65%)0.4質量部とを添加し、品川式万能攪拌機で混練して、砂組成物を得た。
[Comparative Example 10]
A binder composition shown in Table 3 was prepared in the same manner as in Example 16 except that carbon tetrachloride was not added and the amount of water was increased instead.
Next, 1 part by mass of the binder composition and 0.4 part by mass of the curing agent (xylene sulfonic acid 65%) are added to 100 parts by mass of Freemantle No. 6 sand (silica sand), and the Shinagawa type A sand composition was obtained by kneading with a universal stirrer.

実施例14〜16及び比較例8〜10で得られた各粘結剤組成物及び砂組成物について、前述の引火点試験及び鋳型強度試験を行った。結果を表3に示す。   About each binder composition and sand composition obtained in Examples 14-16 and Comparative Examples 8-10, the above-mentioned flash point test and mold strength test were done. The results are shown in Table 3.

Figure 2009269062
Figure 2009269062

表3に示されるように、不燃性液体として四塩化炭素と水との混合溶媒を用いた実施例14〜16では、初期の鋳型強度が高まり、硬化時間3時間の段階では、より鋳型内部(深部)の硬化が良好であるといえる鋳型強度が得られた。対して、不燃性液体として水のみを用いた比較例8〜10では、初期の鋳型強度が得にくく、硬化時間3時間の段階ではある程度の鋳型強度が得られているが、実施例14〜16のような鋳型強度は得られなかった。
また、実施例14〜16で得られた粘結剤組成物は、不燃性液体として、四塩化炭素と水との混合溶媒を15質量%含有しており、引火点のないものであった。
As shown in Table 3, in Examples 14 to 16 using a mixed solvent of carbon tetrachloride and water as the non-flammable liquid, the initial mold strength was increased, and in the stage where the curing time was 3 hours, the inside of the mold ( A mold strength that can be said to be excellent in curing of the deep part was obtained. On the other hand, in Comparative Examples 8 to 10 using only water as the incombustible liquid, it is difficult to obtain the initial mold strength, and a certain mold strength is obtained at the stage of the curing time of 3 hours. A mold strength such as was not obtained.
Moreover, the binder composition obtained in Examples 14 to 16 contained 15% by mass of a mixed solvent of carbon tetrachloride and water as an incombustible liquid, and had no flash point.

Claims (10)

酸硬化性物質と溶媒とを含有する鋳型造型用粘結剤組成物であり、
前記酸硬化性物質がフルフリルアルコールを含有し、前記溶媒が塩素系有機溶剤を含有する鋳型造型用粘結剤組成物。
A binder composition for mold making containing an acid curable substance and a solvent,
The binder composition for mold making, wherein the acid curable substance contains furfuryl alcohol and the solvent contains a chlorinated organic solvent.
前記塩素系有機溶剤が、四塩化炭素、クロロホルム、テトラクロロエチレン、トリクロロエチレン、及び塩化メチレンからなる群より選ばれる1種又は2種以上である請求項1に記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to claim 1, wherein the chlorinated organic solvent is one or more selected from the group consisting of carbon tetrachloride, chloroform, tetrachloroethylene, trichloroethylene, and methylene chloride. 前記溶媒が塩素系有機溶剤のみからなる、請求項1又は2記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to claim 1 or 2, wherein the solvent comprises only a chlorinated organic solvent. 前記溶媒が塩素系有機溶剤と水のみからなる、請求項請求項1又は2に記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to claim 1 or 2, wherein the solvent comprises only a chlorinated organic solvent and water. 前記溶媒の含有率が15質量%以上である請求項3又は4に記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to claim 3 or 4, wherein the content of the solvent is 15% by mass or more. 前記塩素系有機溶剤を1質量%以上含有する請求項1乃至5のいずれかに記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to any one of claims 1 to 5, comprising 1% by mass or more of the chlorinated organic solvent. 前記溶媒の含有率が50質量%以下である請求項1乃至6のいずれかに記載の鋳型造型用粘結剤組成物。   The binder composition for mold making according to any one of claims 1 to 6, wherein the content of the solvent is 50% by mass or less. 前記酸硬化性物質として、フルフリルアルコール、フェノール類及び尿素よりなる群から選ばれる1種又は2種以上と、アルデヒド類とを、縮合又は共縮合させた酸硬化性樹脂を1種又は2種以上含有する請求項1乃至7のいずれかに記載の鋳型造型用粘結剤組成物。   As the acid curable substance, one or two acid curable resins obtained by condensation or co-condensation of one or more selected from the group consisting of furfuryl alcohol, phenols and urea and aldehydes are used. The binder composition for mold making according to any one of claims 1 to 7, which is contained above. 請求項1乃至8いずれかに記載の鋳型造型用粘結剤組成物と耐火性粒状材料と硬化剤とを含有する、鋳型造型用砂組成物。   A sand composition for mold making, comprising the binder composition for mold making according to any one of claims 1 to 8, a refractory granular material, and a curing agent. 請求項9に記載の鋳型造型用砂組成物を鋳型造型用の型に充填して、前記鋳型造型用粘結剤組成物を硬化させる鋳型の製造方法。   A method for producing a mold, comprising: filling a mold for mold making according to claim 9 into a mold for mold making, and curing the binder composition for mold making.
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JP2011125926A (en) * 2009-12-21 2011-06-30 Kao Corp Binder composition for mold molding
JP2011140034A (en) * 2010-01-06 2011-07-21 Gun Ei Chem Ind Co Ltd Method for producing sand composition for molding casting mold, and method for producing casting mold
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JP2007326122A (en) * 2006-06-07 2007-12-20 Gun Ei Chem Ind Co Ltd Binder composition for molding mold, its manufacturing method, sand composition for molding mold, and method for manufacturing mold
JP2008023529A (en) * 2006-07-18 2008-02-07 Kao Corp Furan resin composition for making casting mold

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JP2007326122A (en) * 2006-06-07 2007-12-20 Gun Ei Chem Ind Co Ltd Binder composition for molding mold, its manufacturing method, sand composition for molding mold, and method for manufacturing mold
JP2008023529A (en) * 2006-07-18 2008-02-07 Kao Corp Furan resin composition for making casting mold

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JP2011125926A (en) * 2009-12-21 2011-06-30 Kao Corp Binder composition for mold molding
US8822568B2 (en) 2009-12-25 2014-09-02 Kao Corporation Binder composition for self-curing mold formation
JP2011140034A (en) * 2010-01-06 2011-07-21 Gun Ei Chem Ind Co Ltd Method for producing sand composition for molding casting mold, and method for producing casting mold
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