JP6114599B2 - Carbon dioxide curable composition for mold making and method for producing mold - Google Patents
Carbon dioxide curable composition for mold making and method for producing mold Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 27
- 239000001569 carbon dioxide Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 42
- 235000019353 potassium silicate Nutrition 0.000 claims description 23
- 239000008187 granular material Substances 0.000 claims description 15
- 238000005273 aeration Methods 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 82
- 239000004576 sand Substances 0.000 description 69
- 238000012360 testing method Methods 0.000 description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 238000005259 measurement Methods 0.000 description 30
- 238000005266 casting Methods 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 26
- 239000004115 Sodium Silicate Substances 0.000 description 20
- 229910052911 sodium silicate Inorganic materials 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 150000003460 sulfonic acids Chemical class 0.000 description 12
- 239000011734 sodium Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Mold Materials And Core Materials (AREA)
Description
本発明は、炭酸ガス硬化性鋳型造型用組成物、及び鋳型の製造方法に関する。 The present invention relates to a carbon dioxide curable composition for molding a mold and a method for producing the 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（炭酸ガス硬化性鋳型）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, special molds include thermosetting molds, self-hardening molds, and gas-curing molds (carbon dioxide-curing molds). 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.
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炭酸ガス硬化性鋳型造型用組成物、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 carbon dioxide gas curable mold molding composition and a mold production method.
本発明は以下の態様を有する。
［１］耐火性粒状材料と、硫酸と、水ガラスとを混合した、炭酸ガス硬化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］に記載の炭酸ガス硬化性鋳型造型用組成物。
［３］水ガラス１００質量部に対して、硫酸を無水物換算で０．７５〜１５質量部配合した、［１］または［２］に記載の炭酸ガス硬化性鋳型造型用組成物。
［４］［１］〜［３］のいずれか一項に記載の炭酸ガス硬化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炭酸ガス硬化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] and the refractory particulate material, and sulfuric acid were mixed with water glass, carbon dioxide curing mold formation composition.
[2] The composition for carbon dioxide curable mold making 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] with respect to water glass 100 parts by weight, were blended 0.75 to 15 parts by mass of sulfuric acid equivalent to anhydride, [1] or carbon dioxide gas curable mold formation composition according to [2].
[4] The carbon dioxide curable mold making composition according to any one of [1] to [3] is filled in a mold for producing a mold, and carbon dioxide gas is passed through to mold the carbon dioxide curable mold. A method for producing a mold, wherein the composition is cured.
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炭酸ガス硬化性鋳型造型用組成物、及び鋳型の製造方法を提供できる。 According to the present invention, a carbon dioxide gas curable mold capable of obtaining a mold that maintains a sufficient strength until casting, has excellent disintegration after casting, and has a good working environment during casting and dismantling. A molding composition and a method for producing a mold can be provided.
「炭酸ガス硬化性鋳型造型用組成物」
本発明の炭酸ガス硬化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、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、本発明の炭酸ガス硬化性鋳型造型用組成物と、炭酸ガス（以下、「（Ｅ）成分」ともいう。）と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。
"CO2 gas curable molding composition"
The carbon dioxide gas curable mold-forming composition of the present invention (hereinafter also referred to as “template composition”) includes a refractory granular material (hereinafter also referred to as “component (A)”), sulfuric acid and sulfonic acids. 1 or more selected from the group consisting of (hereinafter also referred to as “component (B)”) and water glass (hereinafter also referred to as “component (D)”).
In the following specification, the “mold” is formed using the carbon dioxide curable mold-forming composition of the present invention and carbon dioxide (hereinafter also referred to as “component (E)”). It will be. “Mold strength” refers to the strength of the mold from casting to casting.
＜（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.
＜（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、ＳｉＯ２とＭ（Ｍ＝Ｋ２ＯまたはＮａ２Ｏ）のモル比（ＳｉＯ２／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）成分と、（Ｄ）成分との配合比（（Ｂ）成分：（Ｄ）成分）は０．７５：８〜１５：１であることが好ましく、０．７５：４〜１５：３であることがより好ましい。（Ｂ）成分の比率が多いほど、鋳型の崩壊性が良好となる。一方、（Ｂ）成分の比率が少ないほど、鋳型の強度が良好となる。 Moreover, it is preferable that the compounding ratio ((B) component: (D) component) of (B) component of an anhydride conversion and (D) component is 0.75: 8-15: 1, 0.75 : 4 to 15: 3 is more preferable. The greater the proportion of component (B), the better the mold disintegration. On the other hand, the smaller the ratio of component (B), the better the strength of the mold.
＜炭酸ガス硬化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）成分と（Ｂ）成分と（Ｄ）成分とを混合することで得られる。混合の順序は、（Ｂ）成分または（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）成分と（Ｂ）成分と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。また、（Ａ）成分に（Ｂ）成分と（Ｄ）成分とを同時に添加してこれらを混合してもよい。
なお、（Ａ）成分を最後に混合すると、すなわち（Ｂ）成分と（Ｄ）成分とを混合した後で（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 Carbon Dioxide-Curable Mold Molding Composition>
The mold composition of the present invention can be obtained by mixing the above-described component (A), component (B), and component (D). The order of mixing is preferably that (B) component or (D) component is mixed last, (D) component is mixed last, that is, (A) component and (B) component are mixed. It is particularly preferable to mix the mixture and component (D) after preparing the mixture. Further, the component (B) and the component (D) may be simultaneously added to the component (A) and mixed.
When (A) component is mixed last, that is, (B) component and (D) component are mixed and then (A) component is mixed, curing starts before mixing (A) component. Therefore, the component (A) is difficult to mix uniformly.
「鋳型の製造方法」
本発明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、（Ｅ）成分（炭酸ガス）を通気させて鋳型用組成物を硬化させること鋳型を製造する。
鋳型を製造する方法としては、ガス硬化鋳型造型法を採用する。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"
In the mold production method 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 the component (E) (carbon dioxide gas) is vented to cure the mold composition. Making a mold.
As a method for producing the mold, a gas curing mold making method is adopted. That is, when a predetermined mold for mold making is filled with the mold composition and the component (E) is vented, the mold composition is cured by the action of the curing agent. 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＞
本発明によれば、炭酸ガス硬化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）を用いる。また、本発明の炭酸ガス硬化性鋳型造型用組成物は、（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、鋳型を造型する際に用いる（Ｅ）成分（炭酸ガス）との硬化作用により硬化する。よって、本発明の炭酸ガス硬化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, the component (D) (water glass), which is an inorganic binder, is used as a binder in a carbon dioxide curable mold-forming composition. In addition, the carbon dioxide gas curable mold making composition of the present invention comprises (B) component (one or more selected from the group consisting of sulfuric acid and sulfonic acids) and (E) component ( Cured by carbon dioxide gas). Therefore, the carbon dioxide curable mold-forming composition of the present invention is a mold that maintains a sufficient strength until casting, has excellent disintegration after casting, and has a good working environment during casting and dismantling. It is possible to obtain. 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、鋳型を造型する際に用いる（Ｅ）成分（炭酸ガス）は、鋳型用組成物を鋳型製造用の型に充填してから鋳型用組成物と接触させることができる。また、（Ｄ）成分の硬化剤として（Ｅ）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。
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 component (D) (water glass). 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 (E) (carbon dioxide gas) used when forming the mold can be brought into contact with the mold composition after filling the mold composition with the mold composition. Further, when only the component (E) 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.
（Ｅ）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（Ｅ）成分と反応すると、（Ｄ）成分からＮａやＫが引き抜かれ、（Ｅ）成分との炭酸塩（例えば、Ｎａ２ＣＯ３やＫ２ＣＯ３）を形成する。この炭酸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 (E), the mechanism by which the cast mold is vitrified is considered as follows.
When the component (D) reacts with the component (E), Na and K are extracted from the component (D) to form carbonates (for example, Na 2 CO 3 and K 2 CO 3 ) with the component (E). This carbonate is decomposed by heat at the time of pouring, and Na and K which are decomposition products 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（Ｎａ２ＳＯ４やＫ２ＳＯ４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−ＳＯ３Ｎａ以外の部分は注湯時の熱で分解するが、Ｎａ＋はＳＯ３ −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、（Ｅ）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（Ｅ）成分でも（Ｄ）成分を硬化させるので、（Ｅ）成分と接触する前の鋳型用組成物の可使時間を充分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 (E) but also the component (B) is cured with the component (D), so vitrification during pouring is suppressed and the disintegration during disassembly is excellent. In addition, since the component (D) is cured not only with the component (B) but also with the component (E), the pot life of the mold composition before contacting with the component (E) can be sufficiently secured, and until the time of casting. The strength of the mold 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）成分の配合量と、鋳型用組成物を充填した型に（Ｅ）成分を通気させる際の通気量（通気流量×通気時間）とに依存する。（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、（Ｂ）成分の配合量が少な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（Ｅ）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）成分の配合量が上述した範囲内であったり、（Ｅ）成分の通気流量や通気時間が上述した範囲内であったりすれば、（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 is based on the blending amount of component (B) and the amount of ventilation when the component (E) is vented to the mold filled with the mold composition. Aeration flow rate x aeration time). 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 blending amount of the component (B) decreases, the strength of the mold increases while the disintegration property decreases.
If about 50 to 80% of the total component (D) is cured with the component (B) and the rest is cured with the component (E), the balance between strength and disintegration becomes better. If the blending amount of the component (B) is within the range described above, or if the aeration flow rate or the ventilation time of the component (E) is within the range described above, the curing rate of the component (D) can be easily controlled, A better balance between strength and disintegration.
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）成分は（Ｂ）成分と（Ｅ）成分との硬化作用によって硬化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. In addition, since the component (D) is cured by the curing action of the components (B) and (E), it has excellent disintegration properties after casting, and dust is hardly generated during disassembly. 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炭酸ガス硬化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。 Moreover, since the composition for molds of the present invention is for carbon dioxide curable mold making, it can be applied not only to small molds but also to large molds.
また、本発明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。 Further, according to the method for producing a mold of the present invention, since the mold composition of the present invention is used, while maintaining a sufficient strength until casting, it has excellent disintegration after casting, and at the time of casting or dismantling A mold having a good working environment can be obtained.
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。
なお、実施例２〜５、７〜１０、１２〜１５、１７〜２０、２２〜２５、２７〜３０、３２〜３５、３７〜４０、４２〜４５、４７〜５０、５２〜５５、５７〜６０、６２〜６５、６７〜７０は参考例である。
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.
In addition, Examples 2-5, 7-10, 12-15, 17-20, 22-25, 27-30, 32-35, 37-40, 42-45, 47-50, 52-55, 57- Reference numerals 60, 62 to 65, and 67 to 70 are reference examples.
＜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／ｃｍ３）＝テストピースの質量（ｇ）／木型内容積（ｃｍ３）・・・（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、（Ｄ）成分として珪酸ナトリウム（モル比（ＳｉＯ２／Ｎａ２Ｏ）：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., Freemantle Shinsuna) as a component. The mixture was kneaded with Shinagawa Kogyo MIXER for 1 minute. 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。その後、１０Ｌ／分の通気流量で（Ｅ）成分（炭酸ガス）を１分間通気させて混練砂を硬化させ、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、（Ｅ）成分の通気開始から約２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、（Ｅ）成分の通気開始から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%. Thereafter, the component (E) (carbon dioxide gas) was aerated at a flow rate of 10 L / min for 1 minute to cure the kneaded sand, and the test piece (mold) was immediately removed from the wooden mold.
About the obtained test piece, physical properties (compressive strength and bulk density) after about 2 minutes from the start of aeration of the component (E), 1 hour, 3 hours, and 24 hours were measured. The results are shown in Table 1.
Separately, the test piece 24 hours after the start of ventilation of the component (E) 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.
「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、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１〜３に示す。
“Comparative Example 1”
(B) Except not having used a component, kneading sand was manufactured like Example 1, a test piece was manufactured using this kneading sand, and various measurement and evaluation were performed. 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.
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。 The blending ratio ([B] / [D]) in Table 1 and Tables 2-14 below is the blending amount (mass part) of the component (B) in terms of anhydride with respect to 100 mass parts of the component (D) (sodium silicate) It is.
「実施例６〜１０」
（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 6 to 10"
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.
「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.
「実施例１１〜１５」
（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 11 to 15"
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.
「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.
「実施例１６〜２０」
（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 16 to 20"
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２１〜２５」
（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、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 21 to 25"
Example 1 except that 0.1 part by weight of a 30% by weight aqueous solution of the acid (sulfuric acid or sulfonic acid) shown in Table 5 was used as the component (B), and the amount of sodium silicate added was changed to 4 parts by weight. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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５〜７に示す。
"Comparative Example 5"
(B) A kneaded sand was produced in the same manner as in Example 1 except that the amount of sodium silicate added was changed to 4 parts by mass without using the component, a test piece was produced using the kneaded sand, and various measurements were performed. And evaluated. 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、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”
(B) Kneaded sand in the same manner as in Example 1 except that 0.1 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used and the amount of sodium silicate added was changed to 4 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 5.
「実施例２６〜３０」
（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、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 26 to 30"
Example 1 except that 1.0 part by weight of a 30% by weight aqueous solution of the acid (sulfuric acid or sulfonic acid) shown in Table 6 was used as the component (B), and the amount of sodium silicate added was changed to 4 parts by weight. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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”
(B) Kneaded sand in the same manner as in Example 1 except that 1.0 part by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used and the amount of sodium silicate added was changed to 4 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 6.
「実施例３１〜３５」
（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、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 31-35"
Example 1 except that 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 as the component (B), and the addition amount of sodium silicate was changed to 4 parts by mass. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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"
(B) Kneaded sand in the same manner as in Example 1 except that 2.0 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used and the amount of sodium silicate added was changed to 4 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 7.
「実施例３６〜４０」
（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、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 36 to 40"
Example 1 except that 2.4 parts by weight of a 30% by weight acid (sulfuric acid or sulfonic acid) solution of the type shown in Table 8 was used as the component (B), and the amount of sodium silicate added was changed to 4 parts by weight. Kneaded sand was produced in the same manner as described above, 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４１〜４５」
（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、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 41 to 45"
Example 1 except that 0.2 parts by mass of a 30% by mass aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 9 was used as the component (B), and the addition amount of sodium silicate was changed to 8 parts by mass. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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９〜１１に示す。
"Comparative Example 9"
(B) A kneaded sand was produced in the same manner as in Example 1 except that the amount of sodium silicate added was changed to 8 parts by mass without using the component, a test piece was produced using the kneaded sand, and various measurements were performed. And evaluated. 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、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"
(B) Kneaded sand in the same manner as in Example 1 except that 0.2 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass was used and the amount of sodium silicate added was changed to 8 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 9.
「実施例４６〜５０」
（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、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 46 to 50"
Example 1 except that 2.0 parts by weight of a 30% by weight aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 10 was used as the component (B), and the amount of sodium silicate added was changed to 8 parts by weight. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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"
(B) Kneaded sand in the same manner as in Example 1 except that 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 sodium silicate was changed to 8 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 10.
「実施例５１〜５５」
（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、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 51-55"
Example 1 except that 4.0 parts by mass of a 30% by weight aqueous solution (sulfuric acid or sulfonic acid) of the type shown in Table 11 was used as the component (B), and the amount of sodium silicate added was changed to 8 parts by mass. Kneaded sand was produced in the same manner as described above, test pieces were produced using the kneaded sand, 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、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”
(B) Kneaded sand in the same manner as in Example 1 except that 4.0 parts by mass of an aqueous citric acid solution adjusted to a concentration of 30% by mass and the amount of sodium silicate added was changed to 8 parts by mass. A test piece was manufactured using the kneaded sand, and various measurements and evaluations were performed. The results are shown in Table 11.
「実施例５６〜６０」
（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、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 56 to 60"
Example 1 except that 4.8 parts by mass of a 30% by weight aqueous solution of acids (sulfuric acid or sulfonic acids) shown in Table 12 was used as the component (B), and the amount of sodium silicate added was changed to 8 parts by mass. Kneaded sand was produced in the same manner as described above, 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６１〜６５」
（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、（Ｅ）成分の通気流量を２Ｌ／分に変更し、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 61-65"
As the 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 aeration flow rate of the component (E) was changed to 2 L / min. Except for changing the addition amount 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６６〜７０」
（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、（Ｅ）成分の通気流量を４０Ｌ／分に変更し、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 66 to 70"
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 14 was used, and the aeration flow rate of component (E) was changed to 40 L / min. Except for changing the addition amount 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.
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、（Ｅ）成分の通気流量が２Ｌ／分、および４０Ｌ／分であると、鋳型の圧縮強度が低下することが分かった。なお、実施例１〜７０の場合、（Ｅ）成分の通気流量が２Ｌ／分、１０Ｌ／分、４０Ｌ／分のいずれかであるが、（Ｅ）成分の通気流量が５Ｌ／分および３０Ｌ／分の場合も、１０Ｌ／分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、（Ｅ）成分の通気流量が５〜３０Ｌ／分の間では、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。
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 were compared, it was found that the compression strength of the mold decreased when the flow rate of the component (E) was 2 L / min and 40 L / min. In the case of Examples 1 to 70, the aeration flow rate of the component (E) is 2 L / min, 10 L / min, or 40 L / min, but the aeration flow rate of the component (E) is 5 L / min and 30 L / min. In the case of minutes, it was confirmed that almost the same result as in the case of 10 L / min was obtained. That is, it was found that the compression strength, bulk density, and disintegration property of the mold hardly changed when the flow rate of the component (E) was 5 to 30 L / min.
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。
On the other hand, Comparative Examples 1, 5, 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.
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