JP2014208364A - Self-curing mold molding composition, method of manufacturing the same, and method of manufacturing mold - Google Patents

Self-curing mold molding composition, method of manufacturing the same, and method of manufacturing mold Download PDF

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JP2014208364A
JP2014208364A JP2013132902A JP2013132902A JP2014208364A JP 2014208364 A JP2014208364 A JP 2014208364A JP 2013132902 A JP2013132902 A JP 2013132902A JP 2013132902 A JP2013132902 A JP 2013132902A JP 2014208364 A JP2014208364 A JP 2014208364A
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mold
component
mass
parts
self
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JP6132681B2 (en
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康弘 永井
Yasuhiro Nagai
康弘 永井
祐樹 羽鳥
Yuki Hatori
祐樹 羽鳥
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Gun Ei Chemical Industry Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a self-curing mold molding composition, a method of manufacturing the same, and a method of manufacturing a mold, capable of providing a mold in which sufficient strength is kept until molding, collapsibility after molding is excellent, and working environment during molding or decomposition is good.SOLUTION: A self-curing mold molding composition is prepared by mixing fire resistant granular material, at least one kind selected from a group consisting of sulfuric acid and sulfonic acid or the like, organic ester, and water glass. In a method of manufacturing the self-curing mold molding composition, the fire resistant granular material, at least one kind selected from a group consisting of sulfuric acid and sulfonic acid or the like, and organic ester are mixed together to prepare a mixture, and then, the mixture is mixed with the water glass. In a method of manufacturing a mold, the self-curing mold molding composition is packed into a mold for manufacturing a mold, and carbon dioxide is allowed to ventilate as required to cure the self-curing mold molding composition.

Description

本発明は、自硬性鋳型造型用組成物とその製造方法、及び鋳型の製造方法に関する。   The present invention relates to a composition for molding a self-hardening mold, a method for producing the same, and a method for producing a mold.

鋳物を製造するには鋳型が必要である。鋳型には普通鋳型と特殊鋳型とがあり、普通鋳型には生型と乾燥型がある。一方、特殊鋳型には熱硬化鋳型、自硬性鋳型、ガス硬化鋳型がある。例えば、鋳物を大量生産する場合にはベントナイト系の生型が、中子用には熱硬化鋳型のシェルモールドが一般的に採用されている。また、多品種少量生産用には自硬性鋳型やガス硬化鋳型が主に適用されている。
また、鋳型には鋳物の形状に対応した大小様々な形状のものが求められる。熱硬化鋳型は小型の鋳型には好適であるが、大型の鋳型には不向きであった。一方、自硬性鋳型やガス硬化鋳型は、小型の鋳型にも大型の鋳型にも好適である。
A mold is required to produce a casting. There are two types of molds: normal molds and special molds. Normal molds include green molds and dry molds. On the other hand, the special mold includes a thermosetting mold, a self-hardening mold, and a gas curing mold. For example, bentonite green molds are generally used for mass production of castings, and thermosetting mold shell molds are generally used for cores. In addition, self-hardening molds and gas-curing molds are mainly applied for high-mix low-volume production.
The mold is required to have various shapes corresponding to the shape of the casting. Thermosetting molds are suitable for small molds but unsuitable for large molds. On the other hand, the self-hardening mold and the gas curing mold are suitable for both a small mold and a large mold.

鋳型の材料には珪砂などの耐火性粒状材料が用いられるが、耐火性粒状材料だけでは乾燥すると崩れやすいため粘結剤を加えて崩れにくくしている。
普通鋳型にはベントナイトなどの粘土が粘結剤として用いられる。一方、特殊鋳型にはフェノール樹脂、フラン樹脂、ウレタン樹脂などの有機系粘結剤や、水ガラスなどの無機系粘結剤が用いられる。例えば、耐火性粒状材料と、無機系粘結剤として水ガラスと、硬化剤として非晶質シリカとを含む熱硬化鋳型用の成形材料混合物が知られている(例えば、特許文献1参照)。
A fire-resistant granular material such as silica sand is used as the material of the mold, but since the refractory granular material alone tends to collapse when dried, a caking agent is added to make it difficult to collapse.
Clay such as bentonite is used as a binder for ordinary molds. On the other hand, organic binders such as phenol resin, furan resin and urethane resin, and inorganic binders such as water glass are used for the special mold. For example, a molding material mixture for a thermosetting mold containing a refractory granular material, water glass as an inorganic binder, and amorphous silica as a curing agent is known (see, for example, Patent Document 1).

各種方法により製造した鋳型には、鉄、銅、アルミニウム等の金属を高温で溶かした液体が注湯され、鋳物が得られる。鋳物は、鋳型を解体して取り出される。また、解体した鋳型から耐火性粒状材料を再生し、鋳型の製造に再利用するのが一般的である。
有機系粘結剤を用いた鋳型は、解体時の崩壊性に優れる。しかし、注湯時に有機系粘結剤が熱分解してガス(熱分解ガス)が発生しやすく、作業環境が悪化しやすい。
In a mold manufactured by various methods, a liquid in which a metal such as iron, copper, or aluminum is melted at a high temperature is poured to obtain a casting. The casting is taken out by dismantling the mold. Further, it is common to regenerate the refractory granular material from the dismantled mold and reuse it for the production of the mold.
Molds using organic binders are excellent in disintegration during dismantling. However, the organic binder is thermally decomposed during pouring, and gas (pyrolysis gas) is likely to be generated, so that the working environment is likely to deteriorate.

一方、無機系粘結剤を用いた鋳型は、無機系粘結剤が熱分解しにくいため注湯時に熱分解ガスが発生しにくいものの、注湯時の熱でガラス化しやすかった。ガラス化すると粘結力が強くなりすぎるため、鋳造後に鋳型を解体しにくくなり(例えば、非特許文献1参照)、解体時に粉塵が発生しやすい。また、耐火性粒状材料を再生するには耐火性粒状材料に付着した粘結剤を剥がす必要があるが、ガラス化していると粘結剤が剥がれにくいため、表面を破砕して耐火性粒状材料を再生しなければならない。鋳型の解体時や耐火性粒状材料の表面を破砕する際に発生する粉塵は、作業環境の悪化の原因となる。また、粉塵はゴミとして廃棄されるため、廃棄量が増える。   On the other hand, a mold using an inorganic binder was easily vitrified by the heat during pouring, although the inorganic binder was difficult to thermally decompose and pyrolysis gas was not easily generated during pouring. When vitrified, the caking force becomes too strong, so that it becomes difficult to dismantle the mold after casting (for example, see Non-Patent Document 1), and dust is likely to be generated during disassembly. In addition, to regenerate the refractory granular material, it is necessary to remove the binder adhering to the refractory granular material, but when vitrified, the binder is difficult to peel off. Have to play. The dust generated when the mold is disassembled or when the surface of the refractory granular material is crushed causes deterioration of the working environment. Moreover, since dust is discarded as garbage, the amount of disposal increases.

無機系粘結剤を用いた鋳型の崩壊性を改善する方法として、無機系粘結剤(水ガラス)と有機系粘結剤とを併用したり(例えば、特許文献2参照)、糖類や木粉等を添加したりして、粘結力を弱める方法が提案されている。   As a method for improving the disintegration property of a mold using an inorganic binder, an inorganic binder (water glass) and an organic binder are used in combination (for example, refer to Patent Document 2), sugars or wood. A method for reducing the caking force by adding powder or the like has been proposed.

特表2011−500330号公報Special table 2011-500330 gazette 特開昭64−22446号公報Japanese Unexamined Patent Publication No. 64-22446

「鋳型造型法」、第4版、社団法人日本鋳造技術協会、平成8年11月18日、第184−188頁"Mold making method", 4th edition, Japan Foundry Technology Association, November 18, 1996, pp. 184-188

しかしながら、特許文献2に記載のように水ガラスと有機系粘結剤とを併用したり、糖類や木粉等を添加したりして粘結力を弱める方法では、鋳型そのものの強度が低下してしまう。しかも、鋳造後の鋳型の崩壊性を充分に改善するには至っていない。   However, as described in Patent Document 2, the method of reducing the binding force by using water glass and an organic binder together, or adding saccharides, wood powder, or the like decreases the strength of the mold itself. End up. In addition, the mold disintegration after casting has not been improved sufficiently.

本発明は上記事情を鑑みてなされたもので、鋳造時までは充分な強度を維持しつつ、かつ鋳造後の崩壊性に優れ、鋳造時や解体時における作業環境が良好な鋳型を得ることが可能な自硬性鋳型造型用組成物とその製造方法、及び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 it is possible to obtain a mold that maintains a sufficient strength until casting, is excellent in disintegration after casting, and has a good working environment during casting and dismantling. It is an object of the present invention to provide a self-hardening mold making composition, a method for producing the same, and a method for producing the mold.

本発明は以下の態様を有する。
[1]耐火性粒状材料と、硫酸及びスルホン酸類からなる群から選択される1種以上と、有機エステルと、水ガラスとを混合した、自硬性鋳型造型用組成物。
[2]耐火性粒状材料100質量部に対して、水ガラスを1〜8質量部配合した、[1]に記載の自硬性鋳型造型用組成物。
[3]水ガラス100質量部に対して、硫酸及びスルホン酸類からなる群から選択される1種以上を無水物換算で0.75〜15質量部配合した、[1]または[2]に記載の自硬性鋳型造型用組成物。
[4]水ガラス100質量部に対して、有機エステルを10〜20質量部配合した、[1]〜[3]のいずれか一項に記載の自硬性鋳型造型用組成物。
[5]耐火性粒状材料と、硫酸及びスルホン酸類からなる群から選択される1種以上と、有機エステルとを混合して混合物を調製した後に、該混合物と水ガラスとを混合する、自硬性鋳型造型用組成物の製造方法。
[6][1]〜[4]のいずれか一項に記載の自硬性鋳型造型用組成物を鋳型製造用の型に充填し、前記自硬性鋳型造型用組成物を硬化させる、鋳型の製造方法。
[7][1]〜[4]のいずれか一項に記載の自硬性鋳型造型用組成物を鋳型製造用の型に充填し、炭酸ガスを通気させて前記自硬性鋳型造型用組成物を硬化させる、鋳型の製造方法。
The present invention has the following aspects.
[1] A self-hardening mold molding composition comprising a mixture of a refractory granular material, one or more selected from the group consisting of sulfuric acid and sulfonic acids, an organic ester, and water glass.
[2] The self-hardening mold making composition according to [1], wherein 1 to 8 parts by mass of water glass is blended with 100 parts by mass of the refractory granular material.
[3] As described in [1] or [2], one or more selected from the group consisting of sulfuric acid and sulfonic acids are blended in an amount of 0.75 to 15 parts by mass in terms of anhydride with respect to 100 parts by mass of water glass. A self-hardening mold molding composition.
[4] The self-hardening mold making composition according to any one of [1] to [3], in which 10 to 20 parts by mass of an organic ester is blended with 100 parts by mass of water glass.
[5] Self-hardening, in which a mixture is prepared by mixing a fire-resistant granular material, one or more selected from the group consisting of sulfuric acid and sulfonic acids, and an organic ester, and then mixing the mixture with water glass. A method for producing a mold making composition.
[6] Manufacture of a mold, in which a mold for mold production is filled with the self-hardening mold making composition according to any one of [1] to [4], and the self-hardening mold making composition is cured. Method.
[7] The self-hardening mold making composition according to any one of [1] to [4] is filled into a mold for producing a mold, and carbon dioxide gas is passed through the composition for self-hardening mold making. A mold manufacturing method for curing.

本発明によれば、鋳造時までは充分な強度を維持しつつ、かつ鋳造後の崩壊性に優れ、鋳造時や解体時における作業環境が良好な鋳型を得ることが可能な自硬性鋳型造型用組成物とその製造方法、及び鋳型の製造方法を提供できる。   According to the present invention, for self-hardening mold making, it is possible to obtain a mold that maintains sufficient strength until casting, has excellent disintegration after casting, and has a good working environment during casting and dismantling. A composition, a method for producing the composition, and a method for producing a mold can be provided.

「自硬性鋳型造型用組成物」
本発明の自硬性鋳型造型用組成物(以下、「鋳型用組成物」ともいう。)は、耐火性粒状材料(以下、「(A)成分」ともいう。)と、硫酸及びスルホン酸類からなる群から選択される1種以上(以下、「(B)成分」ともいう。)と、有機エステル(以下、「(C)成分」ともいう。)と、水ガラス(以下、「(D)成分」ともいう。)とを混合したものである。
なお、以下の明細書において、「鋳型」とは、本発明の自硬性鋳型造型用組成物を用いて造型してなるものである。また、「鋳型の強度」とは、鋳型を造型してから鋳造までの鋳型の強度のことである。また、「自硬性鋳型造型用組成物」とは、外部からの加熱や炭酸ガスの通気などを行わなくても常温で硬化する性質を有する組成物のことである。
"Self-hardening mold molding composition"
The self-hardening mold molding composition of the present invention (hereinafter also referred to as “molding composition”) comprises a refractory granular material (hereinafter also referred to as “component (A)”), sulfuric acid and sulfonic acids. One or more selected from the group (hereinafter also referred to as “component (B)”), an organic ester (hereinafter also referred to as “component (C)”), and water glass (hereinafter referred to as “component (D)”. Is also mixed.).
In the following specification, the “mold” is formed by using the self-hardening mold making composition of the present invention. “Mold strength” refers to the strength of the mold from casting to casting. The “self-hardening mold-forming composition” is a composition having a property of curing at room temperature without external heating or carbon dioxide aeration.

<(A)成分>
(A)成分は耐火性粒状材料である。
耐火性粒状材料としては、珪砂、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る。また、耐火性粒状材料として、使用済みの耐火性粒状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。
<(A) component>
The component (A) is a refractory granular material.
As the refractory granular material, conventionally known materials such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand can be used. Moreover, what collect | recovered used refractory granular material, the thing which carried out the regeneration process, etc. can be used as a refractory granular material.

<(B)成分>
(B)成分は、硫酸及びスルホン酸類からなる群から選択される1種以上である。(B)成分は(D)成分の硬化剤の役割を果たす。
スルホン酸類としては、キシレンスルホン酸、パラトルエンスルホン酸、ベンゼンスルホン酸、メタンスルホン酸などが挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。
(B)成分としては、硬化剤としての性能に優れ、しかもコストが安い点で、硫酸が好ましい。
<(B) component>
The component (B) is at least one selected from the group consisting of sulfuric acid and sulfonic acids. The component (B) serves as a curing agent for the component (D).
Examples of the sulfonic acids include xylene sulfonic acid, paratoluene sulfonic acid, benzene sulfonic acid, and methane sulfonic acid. These may be used alone or in combination of two or more.
(B) As a component, a sulfuric acid is preferable at the point which is excellent in the performance as a hardening | curing agent, and is cheap.

(D)成分100質量部に対して、無水物換算の(B)成分の配合量は0.75〜15質量部であることが好ましく、1.8〜9.4質量部であることがより好ましい。無水物換算の(B)成分の配合量が0.75質量部以上であれば、鋳造後の鋳型の崩壊性がより優れる。一方、無水物換算の(B)成分の配合量が15質量部以下であれば、鋳型の強度がより高まる。   (D) It is preferable that the compounding quantity of (B) component of an anhydride conversion is 0.75-15 mass parts with respect to 100 mass parts of component, and it is more preferable that it is 1.8-9.4 mass parts. preferable. If the blending amount of the component (B) in terms of anhydride is 0.75 part by mass or more, the mold disintegration after casting is more excellent. On the other hand, if the blending amount of component (B) in terms of anhydride is 15 parts by mass or less, the strength of the mold is further increased.

<(C)成分>
(C)成分は有機エステルである。(C)成分は(D)成分の硬化剤の役割を果たす。
有機エステルとしては、プロピレンカーボネート、γ−ブチロラクトン、エチレングリコールジアセテート、モノアセチン、ジアセチン、トリアセチンなどが挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。
<(C) component>
Component (C) is an organic ester. (C) component plays the role of the hardening | curing agent of (D) component.
Examples of the organic ester include propylene carbonate, γ-butyrolactone, ethylene glycol diacetate, monoacetin, diacetin, and triacetin. These may be used alone or in combination of two or more.

(D)成分100質量部に対して、(C)成分の配合量は10〜20質量部であることが好ましく、12〜17質量部であることがより好ましい。(C)成分の配合量が10質量部以上であれば、鋳型を造型する際に鋳型用組成物が充分に硬化する。ただし、(C)成分の配合量が多すぎると、鋳型の強度が低下する傾向にある。これは、過剰分の(C)成分が溶剤的に挙動するためであると考えられる。(C)成分の配合量が20質量部以下であれば、鋳型の強度を維持できる。   (D) It is preferable that the compounding quantity of (C) component is 10-20 mass parts with respect to 100 mass parts of component, and it is more preferable that it is 12-17 mass parts. When the amount of component (C) is 10 parts by mass or more, the mold composition is sufficiently cured when the mold is formed. However, if the amount of component (C) is too large, the strength of the mold tends to decrease. This is considered to be because the excess component (C) behaves like a solvent. (C) If the compounding quantity of a component is 20 mass parts or less, the intensity | strength of a casting_mold | template can be maintained.

また、無水物換算の(B)成分と、(C)成分との配合比((B)成分:(C)成分)は0.75:20〜15:10であることが好ましく、0.75:16〜15:14であることがより好ましい。(B)成分の比率が充分であれば、鋳造後の鋳型の崩壊性が良好となる。一方、(C)成分の比率が充分であれば、鋳型用組成物の硬化性および鋳型の強度が良好となる。   Moreover, it is preferable that the compounding ratio ((B) component: (C) component) of (B) component of an anhydride conversion and (C) component is 0.75: 20-15: 10, 0.75 : 16 to 15:14 is more preferable. If the ratio of the component (B) is sufficient, the mold disintegration after casting will be good. On the other hand, if the ratio of the component (C) is sufficient, the curability of the mold composition and the mold strength are good.

<(D)成分>
(D)成分は水ガラスである。(D)成分は無機系粘結剤の役割を果たす。
水ガラスとしては特に限定されず、非特許文献1等に開示されている従来公知のものを使用できる。例えば珪酸ナトリウム(具体的にはJIS K 1408:1966に記載されている1号、2号、3号やメタ珪酸ナトリウム(1種、2種))、珪酸カリウムや、これらの混合物を用いることができる。
<(D) component>
(D) A component is water glass. The component (D) serves as an inorganic binder.
It does not specifically limit as water glass, The conventionally well-known thing currently disclosed by the nonpatent literature 1 etc. can be used. For example, sodium silicate (specifically, No. 1, No. 2, No. 3, sodium metasilicate (1 type, 2 types) described in JIS K 1408: 1966), potassium silicate, or a mixture thereof may be used. it can.

また、水ガラスとしては、SiOとM(M=KOまたはNaO)のモル比(SiO/M)が1.6〜4.0である水ガラスを用いることが好ましく、モル比が2.1〜2.6である水ガラスを用いることがより好ましく、モル比が2.15〜2.5である水ガラスを用いることがさらに好ましい。モル比が小さくなると、鋳型用組成物の硬化速度が遅くなり、接着強度が高くなる傾向にある。逆に、モル比が大きくなると、鋳型用組成物の硬化速度が速くなり、接着強度が低くなる傾向にある。 As the water glass, it is preferable that SiO 2 and M (M = K 2 O or Na 2 O) molar ratio of (SiO 2 / M) is used water glass is 1.6 to 4.0, moles More preferably, water glass having a ratio of 2.1 to 2.6 is used, and water glass having a molar ratio of 2.15 to 2.5 is more preferably used. If the molar ratio is small, the curing rate of the mold composition tends to be slow and the adhesive strength tends to be high. Conversely, when the molar ratio increases, the curing rate of the mold composition tends to increase and the adhesive strength tends to decrease.

水ガラスの20℃におけるボーメ度は30〜60であることが好ましく、45〜55であることがより好ましい。水ガラスのボーメ度が小さくなると、粘性が下がり、鋳型用組成物の流動性が向上する一方で、接着強度が低下する傾向にある。逆に、水ガラスのボーメ度が大きくなると、粘性が上がり、鋳型用組成物の流動性が低下する一方で、接着強度が高まる傾向にある。   The Baume degree of water glass at 20 ° C. is preferably 30 to 60, and more preferably 45 to 55. When the Baume degree of the water glass is reduced, the viscosity is lowered and the fluidity of the mold composition is improved, while the adhesive strength tends to be lowered. On the other hand, when the baume degree of the water glass increases, the viscosity increases and the fluidity of the mold composition decreases, while the adhesive strength tends to increase.

(A)成分100質量部に対して、(D)成分の配合量は1〜8質量部であることが好ましく、3〜5質量部であることがより好ましく、3〜4質量部であることがさらに好ましい。(D)成分の配合量が1質量部以上であれば、鋳型を造型する際に鋳型用組成物が充分に硬化する。一方、(D)成分の配合量が8質量部以下であれば、注湯時にガラス化するのをより抑制でき、鋳造後の鋳型の崩壊性を良好に維持できる。また、より経済的なコストで鋳型を造型できる。   (A) It is preferable that the compounding quantity of (D) component is 1-8 mass parts with respect to 100 mass parts of component, It is more preferable that it is 3-5 mass parts, It is 3-4 mass parts Is more preferable. When the blending amount of component (D) is 1 part by mass or more, the mold composition is sufficiently cured when the mold is formed. On the other hand, if the blending amount of component (D) is 8 parts by mass or less, vitrification during pouring can be further suppressed, and the mold disintegration after casting can be maintained well. Further, the mold can be formed at a more economical cost.

また、無水物換算の(B)成分および(C)成分の配合量の合計と、(D)成分との配合比((B)成分+(C)成分:(D)成分)は10.75:8〜35:1であることが好ましく、10.75:4〜35:3であることがより好ましい。(B)成分+(C)成分の比率が充分であれば、充分に硬化した鋳型が得られる。ただし、(B)成分+(C)成分の比率が過剰であっても鋳型の強度は頭打ちとなるため、コストを高めるだけである。特に、(C)成分の比率が多いと、かえって鋳型の強度を低下させる傾向にある。   Also, the blending ratio ((B) component + (C) component: (D) component) of the sum of the blended amounts of the component (B) and the component (C) in terms of anhydride and the component (D) is 10.75. : It is preferable that it is 8-35: 1, and it is more preferable that it is 10.75: 4-35: 3. If the ratio of component (B) + component (C) is sufficient, a sufficiently cured mold can be obtained. However, even if the ratio of the component (B) + the component (C) is excessive, the strength of the mold reaches a peak, which only increases the cost. In particular, when the ratio of the component (C) is large, the strength of the mold tends to be lowered.

<自硬性鋳型造型用組成物の製造方法>
本発明の鋳型用組成物は、上述した(A)〜(D)成分を混合することで得られる。混合の順序は、(B)〜(D)成分のいずれかを最後に混合するのが好ましく、(D)成分を最後に混合する、すなわち(A)〜(C)成分を混合して混合物を調製した後に、該混合物と(D)成分とを混合するのが特に好ましい。
なお、(A)〜(D)成分のうち、(A)成分を最後に混合すると、すなわち(B)〜(D)成分を混合した後で(A)成分を混合すると、(A)成分を混合する前に硬化が開始してしまい、(A)成分が均一に混ざりにくくなる。
<Method for producing self-hardening mold making composition>
The mold composition of the present invention can be obtained by mixing the components (A) to (D) described above. The order of mixing is preferably that any of the components (B) to (D) is mixed last, and the component (D) is mixed last, that is, the components (A) to (C) are mixed to form a mixture. It is particularly preferable to mix the mixture and component (D) after preparation.
Of components (A) to (D), when component (A) is mixed last, that is, when components (B) to (D) are mixed and then component (A) is mixed, component (A) Curing starts before mixing, and the (A) component becomes difficult to mix uniformly.

(D)成分を最後に混合する場合、混合物と(D)成分との混合のタイミングは、鋳型を造型する直前が好ましい。一方、(A)〜(C)成分の混合の順序は特に制限されず、例えば以下の順序が挙げられる。
・(A)成分に(B)成分を添加し均一に混練した後、(C)成分を添加し全体が均一になるように混練して混合物を調製する。
・(A)成分に(C)成分を添加し均一に混練した後、(B)成分を添加し全体が均一になるように混練して混合物を調製する。
・(A)成分に(B)成分と(C)成分とを同時に添加し、全体が均一になるように混練して混合物を調製する。
・(B)成分と(C)成分とを混合した後で(A)成分を添加し全体が均一になるように混練して混合物を調製する。
When the component (D) is mixed last, the mixing timing of the mixture and the component (D) is preferably just before molding the mold. On the other hand, the order of mixing the components (A) to (C) is not particularly limited, and examples thereof include the following order.
-Component (B) is added to component (A) and uniformly kneaded, and then component (C) is added and kneaded so that the whole becomes uniform to prepare a mixture.
-Component (C) is added to component (A) and uniformly kneaded, and then component (B) is added and kneaded so that the whole becomes uniform to prepare a mixture.
-(B) component and (C) component are simultaneously added to (A) component, and it kneads so that the whole may become uniform, and prepares a mixture.
-After mixing (B) component and (C) component, (A) component is added and it kneads so that the whole may become uniform, and prepares a mixture.

なお、(B)成分または(C)成分を最後に混合する場合、(B)成分が最後でもよいし、(C)成分が最後でもよい。その理由は以下のように考えられる。
(B)成分または(C)成分を最後に混合する場合は、(D)成分が(A)成分および2種類の硬化剤((B)成分、(C)成分)の一方と混合している状態で、残りの硬化剤を混合することになる。(B)成分の方が(C)成分よりも(D)成分を硬化させる速度が速いため、(B)成分と(C)成分の混合順序が異なる程度の時間差は、(D)成分の硬化に影響しにくい。
In addition, when (B) component or (C) component is mixed last, (B) component may be the last and (C) component may be the last. The reason is considered as follows.
When the (B) component or the (C) component is mixed last, the (D) component is mixed with one of the (A) component and two kinds of curing agents ((B) component, (C) component). In the state, the remaining curing agent will be mixed. Since the component (B) is faster in curing the component (D) than the component (C), the time difference to the extent that the mixing order of the component (B) and the component (C) is different is the curing of the component (D). It is hard to affect.

<作用効果>
本発明によれば、自硬性鋳型造型用組成物において、粘結剤として無機系粘結剤である(D)成分(水ガラス)を用い、かつその硬化剤として(B)成分(硫酸及びスルホン酸類からなる群から選択される1種以上)と(C)成分(有機エステル)とを併用する。よって、本発明の自硬性鋳型造型用組成物は、鋳造時までは充分な強度を維持しつつ、かつ鋳造後の崩壊性に優れ、鋳造時や解体時における作業環境が良好な鋳型を得ることが可能である。かかる理由は以下のように考えられる。
<Effect>
According to the present invention, in the self-hardening mold molding composition, the component (D) (water glass), which is an inorganic binder, is used as the binder, and the component (B) (sulfuric acid and sulfone) is used as the curing agent. One or more selected from the group consisting of acids) and the component (C) (organic ester) are used in combination. Therefore, the composition for molding a self-hardening mold of the present invention can obtain a mold that maintains a sufficient strength until casting, has excellent disintegration after casting, and has a good working environment during casting and dismantling. Is possible. The reason for this is considered as follows.

鋳型用組成物に配合される(B)成分(硫酸及びスルホン酸類からなる群から選択される1種以上)は、(D)成分(水ガラス)を硬化させる速度が速く、可使時間が短い。また、(D)成分の硬化剤として(B)成分のみを用いると、鋳造時までの鋳型の強度の点では不利になるが、鋳造後の鋳型がガラス化しにくい。
一方、(C)成分(有機エステル)は、(D)成分を硬化させる速度が遅く、可使時間が長い。また、(D)成分の硬化剤として(C)成分のみを用いると、鋳造後の鋳型がガラス化するが、鋳造時までの鋳型の強度が高い。
The component (B) (one or more selected from the group consisting of sulfuric acid and sulfonic acids) blended in the mold composition has a high rate of curing the component (D) (water glass) and the pot life is short. . Further, if only the component (B) is used as the curing agent for the component (D), it is disadvantageous in terms of the strength of the mold until casting, but the cast mold is difficult to vitrify.
On the other hand, the component (C) (organic ester) is slow in curing the component (D) and has a long pot life. Further, when only the component (C) is used as the curing agent for the component (D), the cast mold is vitrified, but the mold strength up to the casting is high.

(C)成分のみで(D)成分を硬化させると、鋳造後の鋳型がガラス化するメカニズムは以下のように考えられる。
(D)成分が(C)成分と反応すると、(D)成分からNaやKが引き抜かれ、(C)成分との有機塩を形成する。この有機塩は注湯時の熱によって分解し、分解物であるNaやKが(A)成分(耐火性粒状材料)中のシリカと反応し、ガラス化する。
When the component (D) is cured only with the component (C), the mechanism by which the cast mold is vitrified is considered as follows.
When the component (D) reacts with the component (C), Na and K are extracted from the component (D) to form an organic salt with the component (C). This organic salt is decomposed by heat at the time of pouring, and decomposition products such as Na and K react with silica in the component (A) (refractory granular material) to vitrify.

(B)成分のみで(D)成分を硬化させると、鋳造後の鋳型がガラス化しにくいメカニズムは以下のように考えられる。
(B)成分が硫酸の場合、(D)成分からNaやKが引き抜かれ、硫酸との塩(NaSOやKSOなどの硫酸塩)を形成する。この硫酸塩は安定な物質であるため、注湯時の熱によって分解しにくい。よって、(A)成分中のシリカとの反応が抑制され、ガラス化が起こりにくい。
また、(B)成分がスルホン酸類の場合、(D)成分からNaやKが引き抜かれ、スルホン酸類との塩(例えば、キシレンスルホン酸ナトリウムやキシレンスルホン酸カリウムなどのスルホン酸塩)を形成する。このスルホン酸塩の−SONa以外の部分は注湯時の熱で分解するが、NaはSO によって補足されている。よって、(A)成分中のシリカとの反応が抑制され、ガラス化が起こりにくい。
When the component (D) is cured only with the component (B), the mechanism in which the cast mold is difficult to vitrify is considered as follows.
When the component (B) is sulfuric acid, Na or K is extracted from the component (D) to form a salt with sulfuric acid (a sulfate such as Na 2 SO 4 or K 2 SO 4 ). Since this sulfate is a stable substance, it is not easily decomposed by heat during pouring. Therefore, reaction with the silica in the component (A) is suppressed, and vitrification hardly occurs.
Further, when the component (B) is a sulfonic acid, Na or K is extracted from the component (D) to form a salt with the sulfonic acid (for example, a sulfonate such as sodium xylene sulfonate or potassium xylene sulfonate). . The portions other than -SO 3 Na sulfonate decomposes by heat at the time of pouring is, Na + is SO 3 - are supplemented by. Therefore, reaction with the silica in the component (A) is suppressed, and vitrification hardly occurs.

本発明では、(C)成分だけでなく(B)成分でも(D)成分を硬化させるので、注湯時のガラス化が抑制され、解体時の崩壊性に優れる。また、(B)成分だけでなく(C)成分でも(D)成分を硬化させるので、充分な可使時間を確保できるとともに、鋳造時までの鋳型の強度を高くすることができる。   In the present invention, not only the component (C) but also the component (B) is cured with the component (D), so vitrification during pouring is suppressed and the disintegration during disassembly is excellent. Further, since the component (D) is cured not only with the component (B) but also with the component (C), a sufficient pot life can be secured and the strength of the mold until casting can be increased.

鋳造時までの鋳型の強度と解体時の鋳型の崩壊性とのバランスは、(B)成分と(C)成分の配合量に依存する。(B)成分の配合量が多くなれば崩壊性が高くなる一方で、鋳型の強度が低下する。逆に、(C)成分の配合量が多くなれば鋳型の強度が高くなる一方で、崩壊性が低下する。
(D)成分全体の5〜8割程度を(B)成分で硬化させ、残りを(C)成分で硬化させれば、強度と崩壊性のバランスがより良好となる。(B)成分および(C)成分の配合量がそれぞれ上述した範囲内であれば、(D)成分の硬化の割合を制御しやすく、強度と崩壊性のバランスがより良好となる。
The balance between the strength of the mold until casting and the disintegration of the mold at the time of disassembly depends on the blending amounts of the component (B) and the component (C). When the blending amount of the component (B) is increased, the disintegration property is increased, while the strength of the mold is decreased. On the contrary, if the compounding amount of the component (C) is increased, the strength of the mold is increased while the disintegration property is lowered.
If about 50 to 80% of the total component (D) is cured with the component (B) and the rest is cured with the component (C), the balance between strength and disintegration becomes better. When the blending amounts of the component (B) and the component (C) are each within the above-described ranges, the curing ratio of the component (D) can be easily controlled, and the balance between strength and disintegration becomes better.

また、本発明の鋳型用組成物は、粘結剤として(D)成分(無機系粘着剤)を用いている。よって、本発明の鋳型用組成物を用いて鋳造された鋳型は、(D)成分が熱分解しにくいため注湯時に熱分解ガスが発生しにくい。また、(D)成分の硬化剤として(B)成分と(C)成分とを併用するので鋳造後の崩壊性に優れ、解体時に粉塵が発生しにくい。しかも、注湯時にガラス化しにくいので、表面を破砕して(A)成分を再生する場合でも(D)成分が容易に剥がれ、粉塵の発生を軽減できる。
よって、本発明であれば、鋳造時や解体時における作業環境の悪化を軽減できる。加えて、粉塵の廃棄量も削減できる。
Moreover, the composition for casting_mold | template of this invention uses (D) component (inorganic adhesive) as a binder. Therefore, the mold cast using the mold composition of the present invention is less likely to generate pyrolysis gas during pouring because the component (D) is difficult to pyrolyze. Moreover, since (B) component and (C) component are used together as a hardening | curing agent of (D) component, it is excellent in the disintegration property after casting, and it is hard to generate | occur | produce dust at the time of dismantling. And since it is hard to vitrify at the time of pouring, even when the surface is crushed and the component (A) is regenerated, the component (D) is easily peeled off and the generation of dust can be reduced.
Therefore, if it is this invention, the deterioration of the working environment at the time of casting or dismantling can be reduced. In addition, the amount of dust disposal can be reduced.

また、本発明の鋳型用組成物は自硬性鋳型造型用であるため、小型の鋳型にはもちろんのこと、大型の鋳型にも対応できる。   Further, since the mold composition of the present invention is used for molding a self-hardening mold, it can be applied not only to a small mold but also to a large mold.

「鋳型の製造方法」
<第一の実施形態>
本発明の第一の実施形態の鋳型の製造方法では、本発明の鋳型用組成物を用い、該組成物を鋳型製造用の型に充填し、鋳型用組成物を硬化させて鋳型を製造する。
第一の実施形態は、自硬性鋳型造型法を採用する方法である。すなわち、鋳型用組成物を鋳型造型用の所定の型に充填すると、鋳型用組成物が硬化剤((B)成分および(C)成分)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"
<First embodiment>
In the mold manufacturing method of the first embodiment of the present invention, a mold is manufactured by using the mold composition of the present invention, filling the mold into a mold for mold manufacturing, and curing the mold composition. .
The first embodiment is a method that employs a self-hardening mold making method. That is, when a predetermined mold for mold making is filled with the mold composition, the mold composition is cured by the action of the curing agents (component (B) and component (C)). As a result, a template can be obtained.

(作用効果)
本発明の第一の実施形態の鋳型の製造方法によれば、本発明の鋳型用組成物を用いるので、鋳造時までは充分な強度を維持しつつ、かつ鋳造後の崩壊性に優れ、鋳造時や解体時における作業環境が良好な鋳型が得られる。
(Function and effect)
According to the mold manufacturing method of the first embodiment of the present invention, the mold composition of the present invention is used, so that sufficient strength is maintained until casting, and excellent disintegration after casting is achieved. A mold with a good working environment at the time and during dismantling can be obtained.

<第二の実施形態>
本発明の第二の実施形態の鋳型の製造方法では、本発明の鋳型用組成物を用い、該組成物を鋳型製造用の型に充填し、炭酸ガス(以下、「(E)成分」ともいう。)を通気させて鋳型用組成物を硬化させて鋳型を製造する。
第二の実施形態は、自硬性鋳型造型法とガス硬化鋳型造型法とを併用する方法である。すなわち、鋳型用組成物を鋳型造型用の所定の型に充填し、(E)成分を通気させると、鋳型用組成物が硬化剤((B)成分、(C)成分および(E)成分)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。
<Second Embodiment>
In the mold production method of the second embodiment of the present invention, the mold composition of the present invention is used, the mold composition is filled into a mold for mold production, and carbon dioxide gas (hereinafter referred to as “component (E)”). The mold composition is cured to produce a mold.
In the second embodiment, a self-hardening mold making method and a gas hardening mold making method are used in combination. That is, when a predetermined mold for mold making is filled with the mold composition and the component (E) is vented, the mold composition becomes a curing agent (component (B), component (C) and component (E)). Cured by the action of As a result, a template can be obtained.

(E)成分の通気流量は1分間あたり5〜30Lであることが好ましく、10〜20Lであることがより好ましい。(E)成分の通気流量が5L/分以上であれば、鋳型を造型する際に鋳型用組成物が充分に硬化する。一方、(E)成分の通気流量が30L/分以下であれば、鋳型の強度を維持できる。
また、(E)成分を通気させる時間は、30〜180秒であることが好ましく、60〜180秒であることがより好ましい。通気時間が30秒以上であれば、鋳型用組成物が充分に硬化するが、180秒を超えても鋳型用組成物の硬化は頭打ちとなるため、コストを高めるだけである。
(E) It is preferable that the ventilation | gas flow rate of a component is 5-30L per minute, and it is more preferable that it is 10-20L. When the flow rate of the component (E) is 5 L / min or more, the mold composition is sufficiently cured when the mold is formed. On the other hand, if the flow rate of the component (E) is 30 L / min or less, the strength of the mold can be maintained.
Moreover, it is preferable that it is 30 to 180 second, and, as for the time which ventilates (E) component, it is more preferable that it is 60 to 180 second. If the aeration time is 30 seconds or more, the mold composition is sufficiently cured, but even if it exceeds 180 seconds, the curing of the mold composition reaches its peak, which only increases the cost.

(作用効果)
本発明の第二の実施形態の鋳型の製造方法によれば、本発明の鋳型用組成物を用いるので、鋳造時までは充分な強度を維持しつつ、かつ鋳造後の崩壊性に優れ、鋳造時や解体時における作業環境が良好な鋳型が得られる。
(Function and effect)
According to the mold manufacturing method of the second embodiment of the present invention, the mold composition of the present invention is used, so that sufficient strength is maintained until casting, and excellent disintegration after casting is achieved. A mold with a good working environment at the time and during dismantling can be obtained.

ところで、自硬性鋳型造型法は、鋳型の抜型までに時間がかかる傾向にある。一方、ガス硬化鋳型造型法は、(E)成分を通気すると瞬時に硬化反応が進行するため、(E)成分の通気後、短時間で鋳型の抜型が可能である。
しかし、ガス硬化鋳型造型法では、鋳型造型用の型の大きさに応じたガス通気装置を用いるため、量産性を重視した場合には大型の鋳型を製造するには不向きであった。そのため、大型の鋳型をガス硬化鋳型造型法で製造する際には、手作業により(E)成分を通気させることが多く、鋳型全体に(E)成分を均一に通気させるのは困難であった。その結果、硬化にムラが生じやすかった。
By the way, the self-hardening mold making method tends to take time until the mold is removed. On the other hand, in the gas curing mold making method, since the curing reaction proceeds instantaneously when the component (E) is vented, the mold can be removed in a short time after the component (E) is vented.
However, the gas-curing mold making method uses a gas venting device corresponding to the mold size for mold making, and therefore is not suitable for manufacturing a large mold when mass productivity is emphasized. Therefore, when manufacturing a large mold by the gas curing mold making method, the (E) component is often vented manually, and it is difficult to uniformly vent the (E) component throughout the mold. . As a result, unevenness in curing was likely to occur.

しかし、本発明の第二の実施形態の鋳型の製造方法であれば、本発明の鋳型組成物がもつ自硬性の性質に加えて、(E)成分の作用によっても鋳型組成物を硬化させることができる。そのため、まず(E)成分の作用によって鋳型の表面が瞬時に硬化するので、短時間で鋳型を抜型できる。また、手作業により(E)成分を通気させることによって通気にムラが生じても、鋳型組成物に含まれる硬化剤((B)成分および(C)成分)の作用によって均一に硬化できる。
このように、本発明の第二の実施形態の鋳型の製造方法であれば、自硬性鋳型造型法とガス硬化鋳型造型法とを併用して鋳型を製造する。よって、短時間で鋳型の抜型が可能でありながら、大型の鋳型を製造する場合でも、型の大きさに応じたガス通気装置を用いることなく均一に硬化できる。
However, in the mold manufacturing method according to the second embodiment of the present invention, in addition to the self-hardening property of the mold composition of the present invention, the mold composition is also cured by the action of component (E). Can do. Therefore, the mold surface is instantly cured by the action of the component (E), so that the mold can be removed in a short time. Moreover, even if the ventilation is uneven by manually ventilating the component (E), it can be uniformly cured by the action of the curing agents (component (B) and component (C)) contained in the mold composition.
Thus, if it is the manufacturing method of the casting_mold | template of 2nd embodiment of this invention, a casting_mold | template is manufactured using a self-hardening casting_mold | molding method and a gas-hardening casting_mold | molding method together. Therefore, the mold can be removed in a short time, and even when a large mold is manufactured, it can be uniformly cured without using a gas ventilation device corresponding to the size of the mold.

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。なお、各実施例及び比較例で得られた鋳型(テストピース)の物性の測定、および崩壊性の評価は以下の方法で行った。   Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, the measurement of the physical property of the casting_mold | template (test piece) obtained by each Example and the comparative example, and evaluation of disintegration were performed with the following method.

<テストピースの物性>
(圧縮強度の測定)
各実施例及び比較例で得られたテストピースの圧縮強度(鋳型強度)は、JIS Z 2601の鋳物砂の試験方法に準じて、卓上抗圧力試験機(高千穂機械(株)製)を用いることで測定した。
<Physical properties of test pieces>
(Measurement of compressive strength)
For the compressive strength (mold strength) of the test pieces obtained in each of the examples and comparative examples, use a desktop counter pressure tester (manufactured by Takachiho Kikai Co., Ltd.) according to the testing method for foundry sand of JIS Z 2601. Measured with

(嵩密度の測定)
各実施例及び比較例で得られたテストピースの嵩密度は、下記一般式(I)により求めた。質量測定に用いた電子天秤には、METTLER PM 4000(日本シイベルヘグナー(株)製)を用いた。
なお、嵩密度は木型に略同質量の混練砂(鋳型用組成物)が充填されたことを確認するために測定している。
テストピースの嵩密度(g/cm)=テストピースの質量(g)/木型内容積(cm)・・・(I)
(Measurement of bulk density)
The bulk density of the test pieces obtained in each Example and Comparative Example was determined by the following general formula (I). METLER PM 4000 (manufactured by Nippon Shibel Hegner Co., Ltd.) was used as an electronic balance used for mass measurement.
The bulk density is measured to confirm that the wooden mold is filled with approximately the same mass of kneaded sand (molding composition).
Bulk density (g / cm 3 ) of test piece = mass of test piece (g) / wooden volume (cm 3 ) (I)

<崩壊性の評価>
各実施例及び比較例で得られたテストピースを800℃の雰囲気下で15分間および30分間それぞれ加熱処理した。その後、室温(15℃)まで冷却し、加熱処理後のテストピースの物性(圧縮強度および嵩密度)を先の測定方法と同様にして測定した。加熱処理後のテストピースの圧縮強度は鋳型の崩壊性の指標であり、該圧縮強度が低いほど崩壊性は良好である。
<Evaluation of disintegration>
The test pieces obtained in each Example and Comparative Example were heat-treated at 800 ° C. for 15 minutes and 30 minutes, respectively. Then, it cooled to room temperature (15 degreeC), and measured the physical property (compressive strength and bulk density) of the test piece after heat processing like the previous measuring method. The compressive strength of the test piece after the heat treatment is an index of mold disintegration, and the lower the compressive strength, the better the disintegration.

「実施例1」
<鋳型用組成物の製造>
(A)成分として珪砂(三菱商事建材(株)製、フリーマントル新砂)100質量部に、(B)成分として30質量%硫酸を0.025質量部添加し、品川式万能攪拌機((株)品川工業所製、MIXER)で1分間混練した。これに、(C)成分としてエチレングリコールジアセテートを0.15質量部添加し、品川式万能攪拌機で1分間混練した。これに、(D)成分として珪酸ナトリウム(モル比(SiO/NaO):2.50、ボーメ度:50(20℃))を1質量部添加し、品川式万能攪拌機で1分間混練して混練砂(鋳型用組成物)を得た。
"Example 1"
<Manufacture of mold composition>
(A) 0.025 parts by mass of 30% sulfuric acid as a component (B) is added to 100 parts by mass of silica sand (manufactured by Mitsubishi Corporation Building Materials Co., Ltd., free mantle new sand) as a component, and a Shinagawa universal agitator (Co., Ltd.) The mixture was kneaded with Shinagawa Kogyo MIXER for 1 minute. To this, 0.15 parts by mass of ethylene glycol diacetate as component (C) was added and kneaded for 1 minute with a Shinagawa universal stirrer. To this, 1 part by mass of sodium silicate (molar ratio (SiO 2 / Na 2 O): 2.50, Baume degree: 50 (20 ° C.)) was added as component (D), and kneaded for 1 minute with a Shinagawa universal agitator. Thus, kneaded sand (mold composition) was obtained.

<テストピース(鋳型)の製造>
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を用意し、得られた混練砂を直ちに温度15℃、湿度40%の条件下で木型に充填した。(D)成分を混練開始してから30分経過後に木型からテストピース(鋳型)を取り出した。
得られたテストピースについて、(D)成分を混練開始してから30分経過後(木型から取り出した直後)、1時間経過後、3時間経過後、24時間経過後の物性(圧縮強度と嵩密度)をそれぞれ測定した。結果を表1に示す。
別途、(D)成分を混練開始してから24時間経過後のテストピースを加熱処理して崩壊性の評価を行った。結果を表1に示す。
<Manufacture of test pieces (molds)>
A test piece production wooden mold having a mold with an inner diameter of 50 mm and a height of 50 mm was prepared, and the obtained kneaded sand was immediately filled into the wooden mold under the conditions of a temperature of 15 ° C. and a humidity of 40%. (D) The test piece (mold) was taken out from the wooden mold 30 minutes after the start of kneading of the component.
About the obtained test piece, after 30 minutes have passed since the start of kneading of the component (D) (immediately after removal from the wooden mold), after 1 hour, 3 hours, and 24 hours have passed (compressive strength and The bulk density was measured. The results are shown in Table 1.
Separately, the test piece 24 hours after the start of kneading of the component (D) was subjected to heat treatment to evaluate disintegration. The results are shown in Table 1.

「実施例2〜5」
(B)成分として、表1に示す種類のスルホン酸類の30質量%水溶液0.025質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表1に示す。
"Examples 2 to 5"
(B) Kneaded sand was produced in the same manner as in Example 1 except that 0.025 parts by mass of a 30% by mass aqueous solution of sulfonic acids of the type shown in Table 1 was used as a component, and the kneaded sand was used for testing. Pieces were manufactured and subjected to various measurements and evaluations. The results are shown in Table 1.

「実施例6」
実施例1と同様にして混練砂を製造した。
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を用意し、得られた混練砂を直ちに温度15℃、湿度40%の条件下で木型に充填した。(D)成分を混練開始してから10分経過後に10L/分の通気流量で(E)成分(炭酸ガス)を1分間通気させた後、直ちに木型からテストピース(鋳型)を取り出した。
得られたテストピースについて、(D)成分を混練開始してから11分経過後(木型から取り出した直後)、30分経過後、1時間経過後、3時間経過後、24時間経過後の物性(圧縮強度と嵩密度)をそれぞれ測定した。結果を表1に示す。
別途、(D)成分を混練開始してから24時間経過後のテストピースを加熱処理して崩壊性の評価を行った。結果を表1に示す。
"Example 6"
Kneaded sand was produced in the same manner as in Example 1.
A test piece production wooden mold having a mold with an inner diameter of 50 mm and a height of 50 mm was prepared, and the obtained kneaded sand was immediately filled into the wooden mold under the conditions of a temperature of 15 ° C. and a humidity of 40%. After 10 minutes from the start of kneading the component (D), the component (E) (carbon dioxide gas) was aerated at a flow rate of 10 L / min for 1 minute, and then the test piece (mold) was immediately removed from the wooden mold.
About the obtained test piece, after 11 minutes have passed since the start of kneading of the component (D) (immediately after removal from the wooden mold), after 30 minutes, 1 hour, 3 hours, and 24 hours Physical properties (compressive strength and bulk density) were measured. The results are shown in Table 1.
Separately, the test piece 24 hours after the start of kneading of the component (D) was subjected to heat treatment to evaluate disintegration. The results are shown in Table 1.

「比較例1」
(B)成分を用いなかった以外は、実施例1と同様にして混練砂を製造した。
得られた混練砂を用い、(D)成分を混練開始してから3時間経過後に木型からテストピースを取り出した以外は、実施例1と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表1〜3に示す。
"Comparative Example 1"
Kneaded sand was produced in the same manner as in Example 1 except that the component (B) was not used.
Using the obtained kneaded sand, a test piece was produced in the same manner as in Example 1 except that the test piece was taken out from the wooden mold 3 hours after the start of kneading of the component (D), and various measurements and evaluations were made. Went. The results are shown in Tables 1-3.

「比較例2」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液0.025質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表1に示す。
"Comparative Example 2"
A kneaded sand was produced in the same manner as in Example 1 except that 0.025 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used instead of the component (B), and a test piece was prepared using the kneaded sand. Were manufactured and subjected to various measurements and evaluations. The results are shown in Table 1.

Figure 2014208364
Figure 2014208364

表1および下記表2〜14中の配合比([B]/[D])は、(D)成分(珪酸ナトリウム)100質量部に対する無水物換算の(B)成分の配合量(質量部)である。また、配合比([C]/[D])は、(D)成分(珪酸ナトリウム)100質量部に対する(C)成分の配合量(質量部)である。   The blending ratio ([B] / [D]) in Table 1 and Tables 2 to 14 below is the blending amount of the component (B) in terms of anhydride with respect to 100 parts by weight of the component (D) (sodium silicate) (parts by mass). It is. The blending ratio ([C] / [D]) is the blending amount (parts by mass) of the component (C) with respect to 100 parts by weight of the component (D) (sodium silicate).

「実施例7〜11」
(B)成分として、表2に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液0.25質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表2に示す。
"Examples 7 to 11"
A kneaded sand was produced in the same manner as in Example 1 except that 0.25 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 2 was used as the component (B). Test pieces were produced using sand, and various measurements and evaluations were performed. The results are shown in Table 2.

「実施例12」
30質量%硫酸の添加量を0.25質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表2に示す。
"Example 12"
Kneaded sand was produced in the same manner as in Example 1 except that the addition amount of 30% by mass sulfuric acid was changed to 0.25 parts by mass. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 2.

「比較例3」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液0.25質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表2に示す。
“Comparative Example 3”
A kneaded sand was produced in the same manner as in Example 1 except that 0.25 part by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used instead of the component (B), and a test piece was prepared using the kneaded sand. Were manufactured and subjected to various measurements and evaluations. The results are shown in Table 2.

Figure 2014208364
Figure 2014208364

「実施例13〜17」
(B)成分として、表3に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液0.5質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表3に示す。
"Examples 13 to 17"
As the component (B), kneaded sand was produced in the same manner as in Example 1 except that 0.5 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 3 was used. Test pieces were produced using sand, and various measurements and evaluations were performed. The results are shown in Table 3.

「実施例18」
30質量%硫酸の添加量を0.5質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表3に示す。
"Example 18"
Kneaded sand was produced in the same manner as in Example 1 except that the addition amount of 30% by mass sulfuric acid was changed to 0.5 parts by mass. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 3.

「比較例4」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液0.5質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表3に示す。
“Comparative Example 4”
A kneaded sand was produced in the same manner as in Example 1 except that 0.5 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used instead of the component (B), and a test piece was produced using the kneaded sand. Were manufactured and subjected to various measurements and evaluations. The results are shown in Table 3.

Figure 2014208364
Figure 2014208364

「実施例19〜23」
(B)成分として、表4に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液0.6質量部を用いた以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表4に示す。
"Examples 19 to 23"
As the component (B), kneaded sand was produced in the same manner as in Example 1 except that 0.6 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 4 was used. Test pieces were produced using sand, and various measurements and evaluations were performed. The results are shown in Table 4.

「実施例24」
30質量%硫酸の添加量を0.6質量部に変更した以外、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表4に示す。
"Example 24"
Kneaded sand was produced in the same manner as in Example 1 except that the addition amount of 30% by mass sulfuric acid was changed to 0.6 parts by mass. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 4.

Figure 2014208364
Figure 2014208364

「実施例25〜29」
(B)成分として、表5に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液0.1質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表5に示す。
"Examples 25-29"
As component (B), 0.1 part by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 5 was used, and the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and silicic acid Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 5.

「実施例30」
30質量%硫酸の添加量を0.1質量部に変更し、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表5に示す。
"Example 30"
Except for changing the addition amount of 30 mass% sulfuric acid to 0.1 parts by mass, changing the addition amount of ethylene glycol diacetate to 0.6 parts by mass, and changing the addition amount of sodium silicate to 4 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 5.

「比較例5」
(B)成分を用いず、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。
得られた混練砂を用い、(D)成分を混練開始してから3時間経過後に木型からテストピースを取り出した以外は、実施例1と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表5〜7に示す。
"Comparative Example 5"
(B) Without using the component, the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and the addition amount of sodium silicate was changed to 4 parts by mass. Manufactured.
Using the obtained kneaded sand, a test piece was produced in the same manner as in Example 1 except that the test piece was taken out from the wooden mold 3 hours after the start of kneading of the component (D), and various measurements and evaluations were made. Went. The results are shown in Tables 5-7.

「比較例6」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液0.1質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表5に示す。
“Comparative Example 6”
Instead of the component (B), 0.1 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and the addition amount of sodium silicate was 4 Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 5.

Figure 2014208364
Figure 2014208364

「実施例31〜35」
(B)成分として、表6に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液1.0質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表6に示す。
"Examples 31-35"
As component (B), 1.0 part by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 6 was used, and the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and silicic acid Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 6.

「実施例36」
30質量%硫酸の添加量を1.0質量部に変更し、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表6に示す。
"Example 36"
Except for changing the addition amount of 30 mass% sulfuric acid to 1.0 mass parts, changing the addition amount of ethylene glycol diacetate to 0.6 mass parts, and changing the addition amount of sodium silicate to 4 mass parts. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 6.

「比較例7」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液1.0質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表6に示す。
“Comparative Example 7”
Instead of the component (B), 1.0 part by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and the addition amount of sodium silicate was 4 Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 6.

Figure 2014208364
Figure 2014208364

「実施例37〜41」
(B)成分として、表7に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液2.0質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表7に示す。
"Examples 37 to 41"
As component (B), 2.0 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 7 was used, and the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and silicic acid Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 7.

「実施例42」
30質量%硫酸の添加量を2.0質量部に変更し、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表7に示す。
"Example 42"
Except that the addition amount of 30 mass% sulfuric acid was changed to 2.0 parts by mass, the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and the addition amount of sodium silicate was changed to 4 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 7.

「比較例8」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液2.0質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表7に示す。
“Comparative Example 8”
Instead of component (B), 2.0 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, and the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass, and the addition amount of sodium silicate was 4 Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 7.

Figure 2014208364
Figure 2014208364

「実施例43〜47」
(B)成分として、表8に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液2.4質量部を用い、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表8に示す。
"Examples 43 to 47"
As component (B), 2.4 parts by mass of a 30% by mass aqueous acid (sulfuric acid or sulfonic acid) of the type shown in Table 8 was used, and the addition amount of ethylene glycol diacetate was changed to 0.6 parts by mass to obtain silicic acid. Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 8.

「実施例48」
30質量%硫酸の添加量を2.4質量部に変更し、エチレングリコールジアセテートの添加量を0.6質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表8に示す。
"Example 48"
Except for changing the addition amount of 30 mass% sulfuric acid to 2.4 parts by mass, changing the addition amount of ethylene glycol diacetate to 0.6 parts by mass, and changing the addition amount of sodium silicate to 4 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 8.

Figure 2014208364
Figure 2014208364

「実施例49〜53」
(B)成分として、表9に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液0.2質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表9に示す。
"Examples 49-53"
As component (B), 0.2 part by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 9 was used, and the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and silicic acid Except for changing the amount of sodium added to 8 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 9.

「実施例54」
30質量%硫酸の添加量を0.2質量部に変更し、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表9に示す。
"Example 54"
Implementation was performed except that the addition amount of 30% by mass sulfuric acid was changed to 0.2 parts by mass, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was changed to 8 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 9.

「比較例9」
(B)成分を用いず、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造した。
得られた混練砂を用い、(D)成分を混練開始してから3時間経過後に木型からテストピースを取り出した以外は、実施例1と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表9〜11に示す。
"Comparative Example 9"
(B) Without using the component, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was changed to 8 parts by mass. Manufactured.
Using the obtained kneaded sand, a test piece was produced in the same manner as in Example 1 except that the test piece was taken out from the wooden mold 3 hours after the start of kneading of the component (D), and various measurements and evaluations were made. Went. The results are shown in Tables 9-11.

「比較例10」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液0.2質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表9に示す。
"Comparative Example 10"
Instead of component (B), 0.2 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, and the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was 8 Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 9.

Figure 2014208364
Figure 2014208364

「実施例55〜59」
(B)成分として、表10に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液2.0質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表10に示す。
"Examples 55-59"
As component (B), 2.0 parts by mass of a 30% by mass aqueous solution of acid (sulfuric acid or sulfonic acid) shown in Table 10 was used, and the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and silicic acid Except for changing the amount of sodium added to 8 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 10.

「実施例60」
30質量%硫酸の添加量を2.0質量部に変更し、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表10に示す。
"Example 60"
Implementation was performed except that the addition amount of 30% by mass sulfuric acid was changed to 2.0 parts by mass, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was changed to 8 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 10.

「比較例11」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液2.0質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表10に示す。
"Comparative Example 11"
In place of the component (B), 2.0 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was 8 Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 10.

Figure 2014208364
Figure 2014208364

「実施例61〜65」
(B)成分として、表11に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液4.0質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表11に示す。
"Examples 61-65"
As component (B), 4.0 parts by mass of a 30% by mass aqueous acid (sulfuric acid or sulfonic acid) of the type shown in Table 11 was used, and the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass to obtain silicic acid. Except for changing the amount of sodium added to 8 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 11.

「実施例66」
30質量%硫酸の添加量を4.0質量部に変更し、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表11に示す。
"Example 66"
Implementation was performed except that the addition amount of 30% by mass sulfuric acid was changed to 4.0 parts by mass, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was changed to 8 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 11.

「比較例12」
(B)成分の代わりに、濃度30質量%に調整したクエン酸水溶液4.0質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表11に示す。
"Comparative Example 12"
Instead of component (B), 4.0 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used, the amount of ethylene glycol diacetate added was changed to 1.2 parts by mass, and the amount of sodium silicate added was 8 parts. Except for changing to parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 11.

Figure 2014208364
Figure 2014208364

「実施例67〜71」
(B)成分として、表12に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液4.8質量部を用い、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表12に示す。
"Examples 67-71"
As the component (B), 4.8 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 12 was used, and the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass to obtain silicic acid. Except for changing the amount of sodium added to 8 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 12.

「実施例72」
30質量%硫酸の添加量を4.8質量部に変更し、エチレングリコールジアセテートの添加量を1.2質量部に変更し、珪酸ナトリウムの添加量を8質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表12に示す。
"Example 72"
Implementation was performed except that the addition amount of 30% by mass sulfuric acid was changed to 4.8 parts by mass, the addition amount of ethylene glycol diacetate was changed to 1.2 parts by mass, and the addition amount of sodium silicate was changed to 8 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 12.

Figure 2014208364
Figure 2014208364

「実施例73〜77」
(B)成分として、表13に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液1.0質量部を用い、エチレングリコールジアセテートの添加量を0.2質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表13に示す。
"Examples 73-77"
As component (B), 1.0 part by mass of a 30% by mass aqueous solution of acid (sulfuric acid or sulfonic acid) shown in Table 13 was used, and the addition amount of ethylene glycol diacetate was changed to 0.2 part by mass, and silicic acid Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 13.

「実施例78」
30質量%硫酸の添加量を1.0質量部に変更し、エチレングリコールジアセテートの添加量を0.2質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表13に示す。
"Example 78"
Except that the addition amount of 30 mass% sulfuric acid was changed to 1.0 parts by mass, the addition amount of ethylene glycol diacetate was changed to 0.2 parts by mass, and the addition amount of sodium silicate was changed to 4 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 13.

Figure 2014208364
Figure 2014208364

「実施例79〜83」
(B)成分として、表14に示す種類の酸(硫酸またはスルホン酸類)の30質量%水溶液1.0質量部を用い、エチレングリコールジアセテートの添加量を1.0質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造し、該混練砂を用いてテストピースを製造し、各種測定および評価を行った。結果を表14に示す。
"Examples 79-83"
As component (B), 1.0 part by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acid) shown in Table 14 was used, and the addition amount of ethylene glycol diacetate was changed to 1.0 part by mass, and silicic acid Except for changing the addition amount of sodium to 4 parts by mass, kneaded sand was produced in the same manner as in Example 1, test pieces were produced using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 14.

「実施例84」
30質量%硫酸の添加量を1.0質量部に変更し、エチレングリコールジアセテートの添加量を1.0質量部に変更し、珪酸ナトリウムの添加量を4質量部に変更した以外は、実施例1と同様にして混練砂を製造した。該混練砂を用いた以外は、実施例6と同様にしてテストピースを製造し、各種測定および評価を行った。結果を表14に示す。
"Example 84"
Except that the addition amount of 30 mass% sulfuric acid was changed to 1.0 parts by mass, the addition amount of ethylene glycol diacetate was changed to 1.0 parts by mass, and the addition amount of sodium silicate was changed to 4 parts by mass. Kneaded sand was produced in the same manner as in Example 1. A test piece was produced in the same manner as in Example 6 except that the kneaded sand was used, and various measurements and evaluations were performed. The results are shown in Table 14.

Figure 2014208364
Figure 2014208364

表1〜14から明らかなように、各実施例の混練砂(鋳型用組成物)から得られたテストピースは、鋳型として充分な強度の圧縮強度を示した。また、加熱処理後のテストピースの圧縮強度が低く、優れた崩壊性を有していた。
特に、表1〜4、5〜8、9〜12をそれぞれ比較すると、(B)成分の配合量が増えるにしたがって崩壊性が向上することが分かった。また、(D)成分100質量部に対して(B)成分の配合量が18質量部であると、鋳型の圧縮強度がやや低下することが分かった。
また、表6、13、14を比較すると、(D)成分100質量部に対して(C)成分の配合量が5質量部、および25質量部であると、鋳型の圧縮強度がやや低下することが分かった。なお、実施例1〜84の場合、(D)成分100質量部に対して(C)成分の配合量が5質量部、15質量部、25質量部のいずれかであるが、(C)成分の配合量が10質量部および20質量部の場合も、15質量部の場合とほぼ同様の結果が得られたことを確認した。すなわち、(C)成分の配合量が10〜20質量部の間では、鋳型の圧縮強度、嵩密度、崩壊性にほとんど変化がないことが分かった。
これらの特徴は、硬化剤として炭酸ガスを併用した場合も影響はなかった。しかも、炭酸ガスを併用することで、炭酸ガスを併用しない場合に比べて短時間でテストピースを木型から取り出すことができた。
As is clear from Tables 1 to 14, the test pieces obtained from the kneaded sand (molding composition) of each example exhibited a compressive strength sufficient for a mold. Moreover, the compressive strength of the test piece after heat processing was low, and it had the outstanding disintegration property.
In particular, when comparing Tables 1 to 4, 5 to 8, and 9 to 12, it was found that the disintegration property improved as the blending amount of the component (B) increased. Moreover, it turned out that the compression strength of a casting_mold | template falls a little that the compounding quantity of (B) component is 18 mass parts with respect to 100 mass parts of (D) component.
Further, when Tables 6, 13, and 14 are compared, when the blending amount of the component (C) is 5 parts by mass and 25 parts by mass with respect to 100 parts by mass of the component (D), the compressive strength of the mold is slightly lowered. I understood that. In the case of Examples 1 to 84, the blending amount of the component (C) is 5 parts by mass, 15 parts by mass, or 25 parts by mass with respect to 100 parts by mass of the component (D). It was confirmed that almost the same results as in the case of 15 parts by mass were obtained when the blending amount was 10 parts by mass and 20 parts by mass. That is, it was found that there was almost no change in the compression strength, bulk density, and disintegration property of the mold when the amount of component (C) was 10 to 20 parts by mass.
These characteristics were not affected even when carbon dioxide was used as a curing agent. Moreover, by using carbon dioxide gas in combination, the test piece could be removed from the wooden mold in a shorter time than when carbon dioxide gas was not used.

対して、(B)成分を用いずに混練砂(鋳型用組成物)を製造した比較例1、5、9、および(B)成分の代わりにクエン酸を用いて混練砂(鋳型用組成物)を製造した比較例2〜4、6〜8、10〜12では、加熱処理後のテストピースの圧縮強度が高く、崩壊性に劣っていた。

In contrast, Comparative Examples 1, 5, and 9 in which kneaded sand (mold composition) was produced without using component (B), and kneaded sand (mold composition) using citric acid instead of component (B) In Comparative Examples 2 to 4, 6 to 8, and 10 to 12 manufactured), the compressive strength of the test pieces after the heat treatment was high and the disintegration property was inferior.

Claims (7)

耐火性粒状材料と、硫酸及びスルホン酸類からなる群から選択される1種以上と、有機エステルと、水ガラスとを混合した、自硬性鋳型造型用組成物。   A self-hardening mold making composition comprising a mixture of a refractory granular material, one or more selected from the group consisting of sulfuric acid and sulfonic acids, an organic ester, and water glass. 耐火性粒状材料100質量部に対して、水ガラスを1〜8質量部配合した、請求項1に記載の自硬性鋳型造型用組成物。   The self-hardening mold making composition according to claim 1, wherein 1 to 8 parts by mass of water glass is blended with 100 parts by mass of the refractory granular material. 水ガラス100質量部に対して、硫酸及びスルホン酸類からなる群から選択される1種以上を無水物換算で0.75〜15質量部配合した、請求項1または2に記載の自硬性鋳型造型用組成物。   The self-hardening mold making according to claim 1 or 2, wherein one or more selected from the group consisting of sulfuric acid and sulfonic acids is blended in an amount of 0.75 to 15 parts by weight in terms of anhydride with respect to 100 parts by weight of water glass. Composition. 水ガラス100質量部に対して、有機エステルを10〜20質量部配合した、請求項1〜3のいずれか一項に記載の自硬性鋳型造型用組成物。   The self-hardening mold making composition according to any one of claims 1 to 3, wherein 10 to 20 parts by mass of an organic ester is blended with 100 parts by mass of water glass. 耐火性粒状材料と、硫酸及びスルホン酸類からなる群から選択される1種以上と、有機エステルとを混合して混合物を調製した後に、該混合物と水ガラスとを混合する、自硬性鋳型造型用組成物の製造方法。   For preparing a self-hardening mold, the mixture is prepared by mixing a fire-resistant granular material, one or more selected from the group consisting of sulfuric acid and sulfonic acids, and an organic ester, and then mixing the mixture with water glass. A method for producing the composition. 請求項1〜4のいずれか一項に記載の自硬性鋳型造型用組成物を鋳型製造用の型に充填し、前記自硬性鋳型造型用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 producing a mold with the composition for molding a self-hardening mold according to any one of claims 1 to 4 and curing the composition for mold making a self-hardening. 請求項1〜4のいずれか一項に記載の自硬性鋳型造型用組成物を鋳型製造用の型に充填し、炭酸ガスを通気させて前記自硬性鋳型造型用組成物を硬化させる、鋳型の製造方法。   A mold for molding comprising filling the mold for mold making according to any one of claims 1 to 4 into a mold for mold production, and allowing the carbon dioxide gas to pass through to cure the composition for mold making self-hardening. Production method.
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