WO2020203752A1 - 鋳型材料組成物及びそれを用いた鋳型の製造方法 - Google Patents

鋳型材料組成物及びそれを用いた鋳型の製造方法 Download PDF

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Publication number
WO2020203752A1
WO2020203752A1 PCT/JP2020/013986 JP2020013986W WO2020203752A1 WO 2020203752 A1 WO2020203752 A1 WO 2020203752A1 JP 2020013986 W JP2020013986 W JP 2020013986W WO 2020203752 A1 WO2020203752 A1 WO 2020203752A1
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Prior art keywords
mold
material composition
water glass
neutralizing agent
coating layer
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PCT/JP2020/013986
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English (en)
French (fr)
Japanese (ja)
Inventor
海川　善久
智宏 高間
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旭有機材株式会社
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Application filed by 旭有機材株式会社 filed Critical 旭有機材株式会社
Priority to JP2021511987A priority Critical patent/JP7473533B2/ja
Priority to CN202080025084.8A priority patent/CN113646107B/zh
Priority to MX2021011818A priority patent/MX2021011818A/es
Publication of WO2020203752A1 publication Critical patent/WO2020203752A1/ja
Priority to JP2023180759A priority patent/JP7692459B2/ja
Priority to JP2024025108A priority patent/JP2024051009A/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions 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
    • B22C1/10—Compositions 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/18—Compositions 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening

Definitions

  • the present invention relates to a mold material composition and a method for producing a mold using the same, and in particular, a mold material composition capable of providing a mold having excellent disintegration property after casting and easy regeneration of recovered fire-resistant aggregate. It relates to a product and a method capable of advantageously producing a mold exhibiting such excellent properties.
  • a coated sand formed by coating a refractory aggregate with a predetermined binder is used for the purpose. It is known that it is obtained by molding into the shape of.
  • the binder used for forming the coating layer in such a template material composition includes a water-soluble inorganic binder such as water glass and sodium phosphate, as well as a phenol resin, a furan resin, and a urethane resin.
  • Organic binders using resins such as these have been clarified, and various methods for molding self-hardening molds using these binders have been proposed.
  • a mold material composition composed of an inorganic binder such as water glass has a lower organic content than a mold material composition using an organic binder. It is known that the generation of various gases due to heat during molding and casting is advantageously suppressed, and problems such as odor are unlikely to occur.
  • fire-resistant aggregate (sand) should be recovered from the mold after casting, and the recovered sand should be regenerated by roasting. Then, the inorganic binder remaining on the surface of the recovered sand cannot be burned, but on the contrary, it is sintered and sticks firmly to the surface of the refractory aggregate (sand). Is inherent in the problem of difficulty.
  • the mold material composition using water glass as an inorganic binder the water glass is vitrified by the heat during casting, and the sand recovered after casting is subjected to roasting treatment and polishing treatment.
  • the conventional mold material composition using an inorganic binder also has an inherent problem that the disintegration property of the mold obtained by using the mold material composition is not sufficient.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-64422 proposes a mold disintegrant composition composed of an acidic solution as a composition for disintegrating a water glass mold, and such a mold disintegrant.
  • a method has been proposed in which the composition is brought into contact with a water glass mold after pouring to disintegrate the mold.
  • the water glass may remain on the surface of the recovered refractory aggregate (sand).
  • the mold disintegrant composition disclosed in the patent document is an acidic solution, there is a risk of corroding a metal casting apparatus or the obtained casting.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2015-514466
  • a crushed casting sand is mixed and stirred in water at 5 ° C. to 70 ° C. to obtain the same from the casting sand.
  • a method including a mixing step of separating the adhered binder has been proposed.
  • the regeneration treatment method disclosed in the patent document is applied to a cast sand mold in which water glass is used as a binder (binder), for example, treated water containing a large amount of alkaline components due to water glass is applied. There is a problem that further labor is required for handling and disposing (treating) the treated water.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2017-77570
  • Patent Document 4 Japanese Patent Laid-Open No. 2010-519022
  • water glass is vitrified and deactivated by firing the recovered casting sand at a high temperature.
  • it is necessary to bake it at a high temperature of 900 ° C. or higher, and from the viewpoint of energy efficiency during regeneration, it cannot be said that this is an efficient method.
  • the present invention has been made in the context of such circumstances, and the problem to be solved is that a mold having good disintegration property can be advantageously formed and recovered after casting. It is an object of the present invention to provide a mold material composition capable of easily regenerating a refractory aggregate (sand) to be formed. Another object of the present invention is to provide a method capable of advantageously producing a useful mold by using a mold material composition having such excellent properties.
  • the present invention can be suitably carried out in various aspects as listed below, and each aspect described below can be adopted in any combination. It is possible. It should be noted that the aspects or technical features of the present invention are not limited to those described below, but can be recognized based on the invention idea that can be grasped from the description of the entire specification. , Should be understood.
  • a template material composition wherein the decomposition product produced by heating during casting contains at least an alkali component of the water glass and a neutralizing agent that causes a neutralization reaction.
  • the neutralizing agent is an organic halogen compound or a phosphoric acid ester.
  • Quantitative amount that the decomposition product generated by heating during casting neutralizes the alkaline component of the water glass so that the ratio of the alkaline component of the water glass after casting becomes 15% by mass or less.
  • a solid first coating layer containing the neutralizing agent is formed so as to cover the surface of the refractory aggregate, and the first coating layer is coated.
  • Aspects (1) to Aspect (1) to which a second coating layer composed of a binder composition containing the binder is formed.
  • a method for producing a mold which comprises filling the mold in a mold, holding the mold in the mold, and hardening the solidified mold to obtain a desired mold.
  • a method for producing a mold characterized in that a desired casting mold is obtained by filling the molding mold with water vapor, holding the mold in the molding mold, and solidifying or curing the mold.
  • a desired casting mold is obtained by filling the molding mold with water vapor, holding the mold in the molding mold, and solidifying or curing the mold.
  • water is added thereto to moisten the mold material composition, and the wet mold material composition is filled in the mold.
  • a method for producing a mold which comprises obtaining a desired mold by holding the mold in such a molding mold and solidifying or curing the mold.
  • the template material composition As described above, in the template material composition according to the present invention, (a) a refractory aggregate, (b) a binder containing water glass as an essential component, and (c) decomposition caused by heating during casting.
  • the product is composed of a neutralizing agent that causes a neutralizing reaction with the alkaline component of water glass as an essential component. Therefore, when casting is carried out using a mold formed of such a mold material composition, the mold is heated by a molten metal (generally heated to a temperature exceeding 300 ° C.), and the decomposition product produced by the neutralizing agent by such heating. However, by causing a neutralization reaction with the alkaline component of the water glass, the water glass becomes physically fragile, so that the disintegration property of the mold after casting becomes good.
  • the mold material composition is made of a refractory aggregate (coated sand) covered with a coating layer.
  • a refractory aggregate coated sand
  • the mold material composition is made of a refractory aggregate (coated sand) covered with a coating layer.
  • dissolution of the coating layer on the surface of the coated sand due to the high temperature alkaline component is effectively prevented, and as a result, re-welding (sintering) between the coated sand particles due to heating during pouring is advantageously suppressed. Will be done.
  • the fire-resistant aggregate (sand) recovered after casting using a mold made of the mold material composition of the present invention all or a part of the alkaline component of water glass is neutralized. Therefore, when regenerating the recovered sand from the deactivated area, it is not necessary to perform a high-temperature firing treatment or a neutralization treatment using an acid to remove the alkaline component.
  • the alkaline component of the water glass is neutralized, the recovered refractory aggregate grains are fragile, so that the advantage of easy regeneration by polishing can be enjoyed. You can do it.
  • the mold material composition according to the present invention includes a mold material composition that exhibits a wet state and a mold material that exhibits a dry state depending on the state of a layer (coating layer) containing a binder containing water glass as an essential component. It is roughly divided into compositions.
  • the mold material composition exhibiting a dry state has good room temperature fluidity, whereas the mold material composition exhibiting a wet state does not have such room temperature fluidity. ..
  • the "mold material composition having room temperature fluidity and exhibiting a dry state” in the present invention is a mold material from which a measured value can be obtained when the dynamic angle of repose is measured regardless of the water content. It means a composition.
  • This dynamic rest angle means that the template material composition is housed in a cylinder in which one end in the axial direction is closed with a transparent plate material (for example, in a container having a diameter of 7.2 cm and a height of 10 cm). (Put the mold material composition up to half of its volume), hold it so that the axis is horizontal, and rotate it around the horizontal axis at a constant speed (for example, 25 rpm) to flow in the cylinder.
  • the slope of the mold material composition layer is flat, and the angle formed between the slope and the horizontal plane.
  • the dynamic angle of repose is preferably 80 ° or less, more preferably 45 ° or less, and even more preferably 30 ° or less.
  • a dynamic angle of repose of 45 ° or less can be easily realized.
  • the mold material composition is moist, it does not flow in the cylinder and the slope of the mold material composition layer is not formed as a flat surface, and as a result, the dynamic angle of repose cannot be measured. Is classified as a template material composition exhibiting a wet state.
  • the template material composition having room temperature fluidity and exhibiting a dry state is a solid water glass whose water content constitutes a binder contained in a coating layer covering the surface of a refractory aggregate.
  • the amount is preferably 5 to 55% by mass, more preferably 10 to 50% by mass, and most preferably 20 to 50% by mass with respect to the amount.
  • the water content in this mold material composition becomes less than the amount corresponding to 5% by mass with respect to the solid content of the water glass in the coating layer, the water glass is vitrified and water is added again at the time of molding.
  • the template material composition may not be in a dry state.
  • the template material composition may exhibit a dry state depending on the type of the water glass. Whether it corresponds to the mold material composition exhibiting a dry state or the template material composition exhibiting a wet state is determined by the presence or absence of the above-mentioned room temperature fluidity.
  • the method for measuring the water content in the template material composition is not particularly limited, and a known method can be appropriately adopted.
  • the water content thereof is 70 to 400 with respect to the solid content of water glass as a binder. It is desirable that the amount corresponds to the proportion of mass%, more preferably 80 to 300% by mass, and most preferably 90 to 200% by mass.
  • the water content in this mold material composition is less than the amount corresponding to 70% by mass with respect to the solid content of the water glass, the viscosity of the water glass becomes high, and it becomes difficult to mix uniformly during kneading, and it becomes uniform. Mold cannot be obtained.
  • the mold material composition may be in the form of a slurry, and as a result, it may not be possible to fill the mold. Further, even if it can be filled, it may take time to dry in the molding die.
  • the refractory aggregate constituting the mold material composition of the present invention is a refractory substance that functions as a base material of the mold, and various refractory granules or particles that have been conventionally used for the mold. Any powdery material can be used. Specifically, special sands such as alumina sand, olivine sand, zircon sand, and chromite sand, as well as ferrochrome slag and ferronickel slag, as well as silica sand and recycled silica sand.
  • special sands such as alumina sand, olivine sand, zircon sand, and chromite sand, as well as ferrochrome slag and ferronickel slag, as well as silica sand and recycled silica sand.
  • Slag-based particles such as converter slag
  • artificial particles such as alumina-based particles andglasse-based particles and their regenerated particles
  • alumina balls magnesia clinker and the like.
  • these refractory aggregates may be fresh sand, or recycled sand or recovered sand that has been used once or multiple times as casting sand for molding a mold, and further, such regeneration. There is no problem even if it is mixed sand made by adding new sand to sand or recovered sand and mixing them. Then, such a refractory aggregate is generally used as having a particle size of about 40 to 200 in AFS index, preferably having a particle size of about 50 to 150.
  • the refractory aggregate is preferably spherical, and specifically, the grain shape coefficient is preferably 1.2 or less, more preferably 1.0 to 1.1.
  • the grain shape coefficient of the aggregate used here is generally adopted as a measure for indicating the outer shape of the particles, and is also called a grain size index. The closer the value is to 1, the more spherical the particle shape is. It means getting closer to (true sphere).
  • Such a grain shape coefficient is represented by a value calculated using the sand surface area measured by various known methods, and is, for example, a sand surface area measuring instrument (manufactured by George Fisher). Is used to measure the actual surface area of sand grains per gram, which is divided by the theoretical surface area. The theoretical surface area is the surface area when it is assumed that all the sand grains are spherical.
  • a binder containing water glass as an essential component is used as the binder to be blended in the refractory aggregate as described above.
  • the water glass is a water-soluble silicic acid compound, and examples of such a silicic acid compound include sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, lithium silicate, and silicic acid. Ammonium and the like can be mentioned, but among them, sodium silicate (sodium silicate) is particularly advantageously used in the present invention.
  • the binder as long as water glass is used as an essential component, various water-soluble binders such as thermosetting resins, sugars, proteins, synthetic polymers, salts and inorganic polymers can be used in combination. It is possible.
  • the proportion of water glass in the entire binder is preferably 60% by mass or more, more preferably 80% by mass or more, most preferably 80% by mass or more, based on the solid content. It is preferably 90% or more by mass. Water glass can also be used in the state of hydrate.
  • sodium silicate is usually classified into the types of Nos. 1 to 5 according to the molar ratio of SiO 2 / Na 2 O and used.
  • sodium silicate No. 1 has a molar ratio of SiO 2 / Na 2 O of 2.0 to 2.3
  • sodium silicate No. 2 has a molar ratio of SiO 2 / Na 2 O.
  • the molar ratio is 2.4 to 2.6
  • sodium silicate No. 3 has a molar ratio of SiO 2 / Na 2 O of 2.8 to 3.3
  • sodium silicate No. 4 has a molar ratio of SiO 2 / Na 2 O of 3.3 to 3.5
  • sodium silicate No. 5 has a molar ratio of SiO 2 / Na 2 O.
  • sodium silicate Nos. 1 to 3 are also specified in JIS-K-1408. Then, in the present invention, these various sodium silicates may be used alone or in combination, or may be mixed to prepare a molar ratio of SiO 2 / Na 2 O. It is possible.
  • the molar ratio of SiO 2 / Na 2 O is not limited to the range specified by sodium silicate Nos. 1 to 5 described above, and may be, for example, in the range of 0.8 to 4.0. Just do it.
  • sodium silicate constituting water glass used as a binder generally has a molar ratio of SiO 2 / Na 2 O in order to advantageously obtain the desired template material composition. It is desirable that it is 9 or more, preferably 2.0 or more, more preferably 2.1 or more, and in the above-mentioned classification of sodium silicate, sodium silicate corresponding to Nos. 1 and 2 is used particularly advantageously. It will be.
  • Such sodium silicate No. 1 and No. 2 respectively provide a template material composition having stable and good characteristics even in a wide range of sodium silicate concentration in water glass.
  • the upper limit of the molar ratio of SiO 2 / Na 2 O in such sodium silicate is appropriately selected according to the characteristics of water glass in the form of an aqueous solution, but is generally 3.5 or less. , It is preferably 3.2 or less, and more preferably 2.7 or less.
  • the molar ratio of SiO 2 / Na 2 O is smaller than 1.9, the viscosity of the water glass becomes low, especially in the dry state, and unless the water content is considerably lowered, the mold material composition is used. It may be difficult to dry, while if it is greater than 3.5, the solubility in water will decrease, the adhesion area will not be increased, and the strength of the final mold will decrease. There is a fear.
  • the water glass used in the present invention means a solution of a silicic acid compound in a state of being dissolved in water, and is used in the state of a stock solution as purchased on the market, or water is added to such a stock solution. It will be used in a diluted state after being added.
  • the non-volatile content water glass component
  • solid content the non-volatile content obtained by removing volatile substances such as water and solvent from such water glass
  • solid content obtained by removing volatile substances such as water and solvent from such water glass
  • solid content the non-volatile content obtained by removing volatile substances such as water and solvent from such water glass
  • the higher the proportion of such solid content (nonvolatile content) the higher the concentration of the silicic acid compound in the water glass.
  • the solid content of the water glass used in the present invention corresponds to the amount excluding the amount of water in the undiluted solution when it is composed only of the undiluted solution, while the undiluted solution is converted into water.
  • the amount excluding the amount of water in the stock solution and the amount of water used for dilution corresponds to the solid content of the water glass used. It becomes.
  • the solid content in such water glass will be an appropriate ratio depending on the type of the water glass component (soluble silicic acid compound) and the like, but is preferably a ratio of 20 to 50% by mass. It is desirable that it is contained in.
  • the refractory aggregate is uniformly and uniformly mixed (kneaded) with the refractory aggregate in the dry state.
  • a coating of water glass components can be formed, and the aggregate and water glass can be mixed uniformly and evenly in a wet state, whereby the target mold can be advantageously molded. It will be possible.
  • the heating temperature is raised in the dry state in order to dry the mold material composition.
  • it is necessary to lengthen the heating time which causes problems such as energy loss.
  • the time required for heating in the molding die becomes long, which causes a problem of prolonging the molding cycle of the mold.
  • the proportion of solid content in the water glass becomes too high, it becomes difficult to uniformly cover the surface of the fire-resistant aggregate with the water glass component in the dry state, and the viscosity of the water glass in the wet state.
  • the solid content is 50% by mass or less because it becomes too high and it becomes difficult to mix the aggregate and water glass evenly and evenly, which causes a problem in improving the characteristics of the target mold. Therefore, it is desirable to prepare water glass in the form of an aqueous solution so that the water content is 50% by mass or more.
  • the measurement of the solid content in the water glass is carried out as follows. That is, 10 g of the sample was placed in a sample dish made of aluminum foil (length: 9 cm, width: 9 cm, height: 1.5 cm), weighed, and placed on a heating plate held at 180 ⁇ 1 ° C. After leaving for a minute, the sample dish is inverted and left on the heating plate for another 20 minutes.
  • Solid content (mass%) ⁇ [Mass of sample dish after drying (g) -Mass of sample dish (g)] / [Mass of sample dish before drying (g) -Mass of sample dish (g)] ⁇ x 100
  • the amount of water glass used is too small, it becomes difficult to form a coating layer on the surface of the fire-resistant aggregate in the mold material composition exhibiting a dry state, while the wet state is formed.
  • the aggregate cannot be covered with water glass in the form of an aqueous solution, and there is a risk that solidification or hardening of the mold material composition at the time of mold molding will not proceed sufficiently.
  • the amount of water glass used is too large, an extra amount of water glass adheres to the surface of the fire-resistant aggregate in the dry state, making it difficult to form a uniform coating layer and a mold material.
  • compositions will stick to each other and form agglomerates (composite particles), and in a wet state, an excess amount of water glass may become uneven during mold molding, which may hinder the uniform physical properties of the mold.
  • the physical properties of the finally obtained mold may be adversely affected, and in addition, there may be a problem that it is difficult to remove sand from the core after casting the metal.
  • a predetermined neutralizing agent is used and configured as an essential component together with the above-mentioned refractory aggregate and a binder containing water glass as an essential component.
  • a predetermined neutralizing agent is used and configured as an essential component together with the above-mentioned refractory aggregate and a binder containing water glass as an essential component.
  • the template material composition of the present invention is formed by the template material composition of the present invention by blending a predetermined neutralizing agent (a neutralizing agent in which a decomposition product generated by heating causes a neutralizing reaction with an alkaline component of water glass).
  • a predetermined neutralizing agent a neutralizing agent in which a decomposition product generated by heating causes a neutralizing reaction with an alkaline component of water glass.
  • the mold is heated by the molten metal (generally heated to a temperature exceeding 300 ° C.), and the decomposition product produced by the neutralizing agent due to the heating during such casting is the alkaline component of water glass. It will neutralize some or all of the above. Since water glass becomes physically fragile by neutralizing a part or all of the alkaline component of water glass, it is formed by using the template material composition according to the present invention. In the molded mold, the disintegration property after being subjected to casting becomes good.
  • the mold material composition is made of refractory aggregate (coated sand) covered with a coating layer.
  • dissolution of the coating layer on the surface of the coated sand due to the high temperature alkaline component is effectively prevented, and thus re-welding (sintering) between the coated sand particles due to heating during pouring is advantageously suppressed. Will be done.
  • a part or all of the alkaline component of water glass is neutralized.
  • the recovered sand when the recovered sand is regenerated from the deactivated state, a high-temperature firing treatment for removing the alkaline component, a neutralization treatment using an acid, or the like becomes unnecessary. Furthermore, since the alkaline component of water glass is neutralized and the coating layer on the surface of the coated sand becomes brittle, the recovered refractory aggregate grains become brittle, which has the advantage of being easily regenerated by polishing. Can also be enjoyed.
  • the alkaline component of water glass is contained in the solid content of water glass, and is dissolved in the water contained in water glass, and the alkali metal ions generated there are the decomposition products of the neutralizing agent. It will cause a neutralization reaction. Further, it is clear from the above-mentioned "mold material composition exhibiting a dry state" that water remains in the water glass contained therein even in the mold material composition in a dry state.
  • the neutralizing agent used in the present invention is one in which a decomposition product generated by heating during casting causes a neutralization reaction with an alkaline component of water glass. More specifically, it is not decomposed by heating (generally heating at 300 ° C or lower) during preparation (manufacturing) or molding of the mold material composition, but by heating with molten metal during casting (at a temperature exceeding 300 ° C). decomposed by heating) of the resulting decomposition products, alkali components of water glass (e.g., compounds that neutralize Na 2 O) in the case of sodium silicate is used as a neutralizing agent in the present invention.
  • alkali components of water glass e.g., compounds that neutralize Na 2 O
  • sodium silicate is used as a neutralizing agent in the present invention.
  • the decomposition referred to here means complete decomposition, and even if a compound partially starts to decompose when heated at 300 ° C. or lower, the temperature at which it completely decomposes exceeds 300 ° C.
  • the decomposition product causes a neutralization reaction with the alkaline component of water glass, it can be used as the neutralizing agent of the present invention.
  • Any compound having such properties can be used as a neutralizing agent in the present invention without particular limitation, but an organic halogen compound or a phosphoric acid ester is preferably used, and particularly preferably. Organic halogen compounds are used.
  • the organic halogen compound is decomposed by heating with a molten metal during casting (heating at a temperature exceeding 300 ° C.) to release halogen, and the released halogen reacts with sodium in water glass to cause water glass.
  • the alkaline component will be neutralized.
  • an organic chlorine compound or an organic bromine compound is most preferably used as a neutralizing agent in the present invention.
  • the neutralizing agent when the neutralizing agent is produced according to the production method described later, it will be present in a uniformly dispersed state in the coating layer. Therefore, for example, when an acid as a neutralizing agent is blended. The uneven distribution of the neutralizing agent, which is a problem in the present invention, does not occur in the present invention.
  • the organic halogen compound used as a neutralizing agent includes chlorinated paraffin, chlorinated diphenyl, chlorinated ethane, chlorinated polyethylene, chlorinated polyphenyl, chlorinated diphenyl, vinyl chloride, and perchlorocyclopentadecanone.
  • Tetrachlorobisphenol A trischloroethyl phosphate, trisdichloropropyl phosphate, tris- ⁇ -chloropropyl phosphate and other organic chlorine compounds; brominated paraffin, brominated polyphenyl, tetrabromoethane, tetrabromobenzene, decabromodiphenyl oxide.
  • Bromine compounds exemplifies organic fluorine compounds such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylenetetrafluoroethylene copolymer, ethylenechlorotrifluoroethylene copolymer, polyvinylidene fluoride, and polychlorotrifluoroethylene. Can be done.
  • TPP triphenyl phosphate
  • TCP tricresyl phosphate
  • TXP trixylenyl phosphate
  • CDP cresyldiphenyl phosphate
  • XDP phosphoridiphenyl phosphate
  • XDP resosinol-bis- (diphenyl phosphate)
  • 2-ethylhexyl diphenyl phosphate dimethyl methyl phosphate
  • triallyl phosphate leophose
  • alkyl phosphate alkyl phosphate
  • the amount of the neutralizing agent used (blended amount) as described above is too small, the amount of the alkaline component in the water glass neutralized by heating at the time of casting is inevitably small. Therefore, there is a risk that the effects of the present invention cannot be enjoyed advantageously. Therefore, in the present invention, in the predetermined neutralizing agent, the decomposition product generated by heating during casting neutralizes the alkaline component of the water glass, so that the ratio of the alkaline component of the water glass after casting is 15 mass by mass. It is preferable that the mixture is contained in the template material composition in a quantitative ratio such as% or less.
  • the ratio of the alkaline component (Na 2 O) in SiO 2 + Na 2 O) is 15% by mass or less, the water glass solidifies and the alkaline component (Na 2 O) is not eluted from the solidified water glass. Therefore, it is possible to enjoy the effects of the present invention more advantageously.
  • the solidification of water glass (sodium silicate) can be technically understood by those skilled in the art in view of the conventionally known Na 2 O-SiO 2 phase diagram.
  • additives in addition to the above-mentioned predetermined neutralizing agent, various known additives can be appropriately contained in the template material composition, if necessary.
  • additives include surfactants, lubricants, inorganic oxide particles, carbonates and / or borates, moisture resistance improvers and the like.
  • the water permeability in other words, the wettability of the mold material composition to water can be improved.
  • a surfactant mediates between the supplied water and the water glass. Even if there is, the entire mold material composition is effectively moistened, and therefore, 1) the time for supplying water to the mold material composition (for example, when water is supplied by steam). , The aeration time of water vapor) can be suppressed to the minimum necessary, and 2) the amount of water supplied to the molding mold (molding cavity) can be suppressed to a small amount.
  • the amount of the surfactant contained in the template material composition is preferably 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the solid content of the water glass. It is preferably 0.5 to 15.0 parts by mass, and particularly preferably 0.75 to 12.5 parts by mass. If the amount of the surfactant contained is too small, the above-mentioned effects may not be enjoyed advantageously. On the other hand, if the amount of the surfactant is too large, the amount of the surfactant used depends on the amount used. No improvement in effectiveness was observed, and it is not a good idea from the viewpoint of cost effectiveness.
  • any of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a silicone-based surfactant and a fluorine-based surfactant can be used.
  • Specific examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, and benzethonium chloride.
  • examples of anionic surfactants include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl- ⁇ -alanine salt, N-acylglutamate, alkyl ether carboxylate, and acyl.
  • alkyl sulfonate alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosulfate ester salt, alkyl sulfoacetate, ⁇ -olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol Sulfate ester salt, secondary higher alcohol sulfate ester salt, alkyl ether sulfate salt, secondary higher alcohol ethoxysulfate, polyoxyethylene alkylphenyl ether sulfate salt, monoglyculfate, fatty acid alkylolamide sulfate ester salt, alkyl ether phosphorus Examples thereof include acid ester salts and alkyl phosphate ester salts.
  • amphoteric surfactant examples include carboxybetaine type, sulfobetaine type, aminocarboxylic acid salt, imidazolinium betaine and the like.
  • nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether (for example, Emargen 911), polyoxyethylene sterol ether, and polyoxyethylene lanolin derivative.
  • Polyoxyethylene polyoxypropylene alkyl ether eg, New Pole PE-62
  • polyoxyethylene glycerin fatty acid ester polyoxyethylene castor oil, hardened castor oil
  • polyoxyethylene sorbitan fatty acid ester polyoxyethylene sorbitol fatty acid ester
  • Polyethylene glycol fatty acid ester fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide, acetylene glycol, Examples include acetylene alcohol.
  • silicone-based surfactants those having a siloxane structure as a non-polar moiety are referred to as silicone-based surfactants, and those having a perfluoroalkyl group are further referred to as fluorosurfactants.
  • silicone-based surfactants include polyester-modified silicone, acrylic-terminated polyester-modified silicone, polyether-modified silicone, acrylic-terminated polyether-modified silicone, polyglycerin-modified silicone, and aminopropyl-modified silicone. Be done.
  • the fluorine-based surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylic acid salts, perfluoroalkyl phosphates, perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, and perfluoroalkyl groups. Examples include contained oligomers.
  • various surfactants as described above can be used alone or in combination of two or more. However, some surfactants react with water glass, and the surface activity may decrease or disappear over time. Therefore, anionic surfactants and nonionic surfactants that do not react with water glass. Sexual surfactants and silicone-based surfactants will be used particularly advantageously in the template material compositions of the present invention.
  • a lubricant as an additive so that it is present on the surface of the refractory aggregate of the mold material composition.
  • the presence of such a lubricant can advantageously improve the fluidity of the template material composition.
  • the amount of the lubricant contained in the template material composition according to the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of water glass, and among them, 0.3. It is preferably about 8 parts by mass, and particularly preferably 0.5 to 5 parts by mass. If the amount of the lubricant contained is too small, the above-mentioned effects may not be enjoyed advantageously, while if the amount of the lubricant is too large, the mold strength may decrease, and further, the mold strength may decrease. , It is not a good idea from the viewpoint of cost effectiveness.
  • Examples of the lubricant used in the present invention include waxes such as paraffin wax, synthetic polyethylene wax, and montanic acid wax; fatty acid amides such as stearic acid amide, oleic acid amide, and erucate amide; methylenebisstearic acid amide, and the like.
  • Alkylene fatty acid amides such as ethylenebis stearic acid amide; stearic acid, stearyl alcohol; stearic acid metal salts such as lead stearate, zinc stearate, calcium stearate, magnesium stearate; monoglyceride stearate, stearyl stearate, hardened oil, etc. It is possible to use.
  • calcium stearate and the like are particularly preferably used.
  • the template material composition of the present invention can also contain inorganic oxide particles.
  • the size of the inorganic oxide particles used in the present invention is preferably smaller than that of the refractory aggregate constituting the template material composition, and specifically, the average particle diameter is 0.01 ⁇ m or more and 300 ⁇ m.
  • inorganic oxide particles having a size of 0.3 ⁇ m or more and 200 ⁇ m or less, particularly preferably 0.5 ⁇ m or more and 100 ⁇ m or less are used.
  • the average particle size can be obtained from the particle size distribution measured by a laser diffraction type particle size distribution measuring device or the like.
  • the content of the inorganic oxide particles in the template material composition is generally 5 to 200 parts by mass, preferably 5 to 200 parts by mass, based on 100 parts by mass of the solid content of the binder containing water glass as an essential component.
  • the ratio is 10 to 100 parts by mass.
  • the inorganic oxide particles used in the present invention may be spherical particles or non-spherical particles, but the use of spherical particles more favorably enjoys the above-mentioned compounding effect of the inorganic oxide particles.
  • such spherical particles may have a spherical shape that is generally recognized, and are not necessarily required to have a true spherical shape, but usually have a sphericity of 0.5 or more. Those having a value of 0.7 or more, and more preferably those having a value of 0.9 or more are advantageously used.
  • the sphericity is the aspect ratio (minor axis / major axis ratio) obtained from the projected shape of 10 single particles randomly selected in the observation using a scanning electron microscope. It means the average value.
  • the inorganic oxide particles are dissolved by the supplied moisture.
  • protrusions on the surface of the inorganic oxide particles collide with the refractory aggregates and other inorganic oxide particles, etc.
  • the material constituting the inorganic oxide particles is not particularly limited, but is preferably an inorganic metal oxide.
  • particles made of the inorganic metal oxide particles made of silicon dioxide, aluminum oxide, titanium oxide, etc. are advantageously used.
  • the silicon dioxide particles contain strongly alkaline water glass.
  • the binder can react with the silanol groups formed on the surface of the silicon dioxide, and upon evaporation of water, a strong bond is formed between the silicon dioxide and the solidified binder. It can be said that it is preferable in that the mold strength can be improved.
  • silicon dioxide there are two types of silicon dioxide, crystalline and amorphous, but amorphous is preferable, and the amorphous silicon dioxide is precipitated silica, calcined silica produced in an electric arc or by flame hydrolysis.
  • Silica produced by thermal decomposition of ZrSiO 4
  • silicon dioxide produced by oxidizing metallic silicon with a gas containing oxygen
  • quartz glass powder which is a spherical particle produced from crystalline quartz by melting and subsequent quenching, and the like. It can be illustrated. Of course, these can be used alone, and it is also possible to use a mixture of two or more kinds.
  • silicon dioxide is treated as an inorganic metal oxide. Further, the silicone resin particles may be added instead of or in combination with the inorganic oxide particles.
  • the template material composition of the present invention it is preferable to use at least one of carbonate and borate.
  • Carbonate releases carbon dioxide due to the heat generated by molding and casting, causing cracks in the binder film of water glass and breaking the binder film of water glass, which makes it easier for the mold to collapse and the generated carbon dioxide.
  • the hydroxyl group (-OH) in the water glass reacts with the tetraborate ion or metaborate ion generated from the borate due to the heat generated by molding and casting, and the hydroxyl group (-OH) in the water glass reacts.
  • By closing OH it becomes difficult to redissolve, and thus softening of the viscous membrane of water glass can be prevented.
  • the amount of carbonate and / or borate as described above contained in the template material composition shall be 0.5 to 50 parts by mass with respect to 100 parts by mass of the solid content of water glass. Of these, 1 to 20 parts by mass is preferable, and 2 to 15 parts by mass is particularly preferable. If the amount of carbonate and / or borate contained is too small, the above-mentioned effects may not be advantageously enjoyed, while the amount of carbonate and / or borate is large. Even if it passes, the improvement of the effect is not recognized according to the amount used, and further, from the viewpoint of cost effectiveness, it is not a good idea. In addition, carbonate and borate may be used in combination.
  • examples of such carbonates include zinc carbonate, basic zinc carbonate, iron carbonate, manganese carbonate, copper carbonate, aluminum carbonate, barium carbonate, magnesium carbonate, calcium carbonate, lithium carbonate, potassium carbonate, sodium carbonate and the like.
  • borates include sodium tetraborate, potassium tetraborate, lithium tetraborate, ammonium tetraborate, calcium tetraborate, strontium tetraborate, silver tetraborate, sodium metaborate, etc.
  • examples thereof include potassium metaborate, lithium metaborate, ammonium metaborate, calcium metaborate, silver silver metaborate, copper metaborate, lead metaborate, magnesium metaborate and the like.
  • basic zinc carbonate, sodium tetraborate, and potassium metaborate are advantageously used.
  • a moisture resistance improver may be further contained as another additive.
  • a moisture resistance improver By impregnating the water glass with a moisture resistance improving agent, it is possible to improve the moisture resistance of the finally obtained mold.
  • the moisture resistance improver used in the present invention may be any as long as it is conventionally used in a template material composition such as coated sand, as long as it does not impair the effect of the present invention. , Can be used.
  • sulfates such as sodium sulfate, potassium sulfate, lithium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, titanium sulfate, aluminum sulfate, zinc sulfate, copper sulfate, sodium phosphate, sodium hydrogen phosphate, etc.
  • the total amount of such a moisture resistance improver to be used is generally preferably about 0.5 to 50 parts by mass with respect to 100 parts by mass of the solid content of the water glass. It is more preferably about 20 parts by mass, and particularly preferably 2 to 15 parts by mass. In order to advantageously enjoy the effect of adding the moisture resistance improver, it is desirable that the amount used is 0.5 parts by mass or more, while if the amount added is too large, the aggregate is bonded by water glass. It is desirable that the amount is 50 parts by mass or less because it may hinder and cause problems such as a decrease in the strength of the finally obtained template.
  • a coupling agent that strengthens the bond between the refractory aggregate and water glass For example, a silane coupling agent, a zircon coupling agent, and a titanium coupling agent. Etc. can be used.
  • a silane coupling agent a zircon coupling agent, and a titanium coupling agent. Etc. can be used.
  • mold release agents paraffin, wax, light oil, machine oil, spindle oil, insulating oil, waste oil, vegetable oil, fatty acid ester, organic acid, graphite fine particles, mica, ⁇ ⁇ , fluorine-based mold release agent, silicone-based mold release agent. Agents and the like can also be used.
  • Each of these other additives is contained in an amount of 5% by mass or less, preferably 3% by mass or less, based on the solid content of the water glass.
  • a coating layer containing a binder containing water glass as an essential component and a predetermined neutralizing agent is formed.
  • a mold material composition composed of coated sand (CS) formed on the surface of a fire-resistant aggregate (sand) (hereinafter referred to as "single-layer structure CS (mold material composition)") and 2) fire resistance.
  • a solid first coating layer containing a predetermined neutralizing agent is formed on the surface of the sex aggregate (sand), and a binder containing water glass as an essential component is contained on the first coating layer.
  • a mold material composition composed of coated sand (CS) on which a second coating layer is formed hereinafter, referred to as "CS (mold material composition) having a two-layer structure" can be produced.
  • a single-layer structure CS template material composition
  • it is generally used as a binder for fire-resistant aggregate.
  • Water glass and a predetermined neutralizing agent are kneaded or mixed together with an additive used as necessary to uniformly mix the surface of the fire-resistant aggregate with water glass containing a neutralizing agent or the like.
  • the coating layer of the water glass composition stickiness containing water glass as an essential component
  • a method of forming a coating layer (a coating layer containing a binder and a predetermined neutralizing agent) will be adopted.
  • the evaporation of water in the coating layer needs to be carried out rapidly before the solidification or hardening of the water glass progresses. Therefore, the water glass in the form of an aqueous solution is used as opposed to the refractory aggregate. It is desirable to remove the water content within 5 minutes, more preferably within 3 minutes after adding (mixing) the mixture to obtain a dry powdered template material composition. If the evaporation time is long, the mixing (kneading) cycle is long, the productivity of the mold material composition is lowered, and the water glass is in contact with CO 2 in the air for a long time, resulting in deactivation. This is because there is a high risk of causing problems.
  • fire resistance is one of the effective means for rapidly evaporating the water content in the water glass.
  • a method is preferably adopted in which the aggregate is preheated and then kneaded or mixed with water glass in the form of an aqueous solution, a predetermined neutralizing agent, or the like so as to be mixed.
  • the water in the water glass is vaporized extremely quickly by the heat of such refractory aggregate. Therefore, the water content of the obtained template material composition can be effectively reduced, and a dry powder having room temperature fluidity can be advantageously obtained.
  • the preheating temperature of the refractory aggregate is appropriately selected according to the water content of the water glass, the blending amount thereof, etc., but in general, a temperature of about 100 to 160 ° C. is preferable. A temperature of about 100 to 140 ° C. is adopted. If this preheating temperature is too low, it will not be possible to effectively evaporate the water and it will take time to dry. Therefore, it is desirable to adopt a temperature of 100 ° C. or higher, and the preheating temperature is high. If it is too high, the water glass component will solidify or harden when the obtained mold material composition is cooled, and in addition, composite particle formation will proceed. Therefore, the function as the mold material composition, particularly the final There will be a problem with physical properties such as the strength of the mold obtained in.
  • the neutralizing agent contained in the coating layer together with the water glass and other additives used as necessary such as a surfactant and a lubricant, are used. It may be added to the refractory aggregate in a state of being mixed with water glass in advance and kneaded, or it may be added separately from the water glass at the time of kneading and kneaded, and further, the water glass at the time of kneading. It may be kneaded by adding a time lag between the addition and the addition of the above.
  • the coating layer in the dry mold material composition of the present invention is, for example, in a state where water glass and a neutralizing agent are mixed, or from the surface of the refractory aggregate to the outside. While the concentration of the solid content (nonvolatile content) of the glass gradually decreases or increases, the concentration of the neutralizing agent or the like gradually increases or decreases, and the form is composed of the glass. Further, water glass as a binder may be diluted with water in order to adjust its viscosity. Further, at the time of kneading or mixing, water glass and water may be added individually without any problem.
  • CS mold material composition
  • template material composition template material composition
  • the first coating layer may be composed of only a predetermined neutralizing agent, and from the viewpoint of dispersion of the neutralizing agent and isolation from water glass, the first coating layer may be composed of a predetermined neutralizing agent. It can also be composed of a neutralizing agent and an organic compound.
  • the organic compound is contained in the first coating layer located directly above the refractory aggregate, when the molten metal is poured into a mold using the mold material composition having such a constitution, the first is The organic compound contained in one coating layer is thermally decomposed and gasified, and the generated gas advantageously destroys the solidified or cured product of water glass at the joint portion between the refractory aggregate particles. , The disintegration property of the mold is excellent. Further, when the organic compound contained in the first coating layer is thermally decomposed and gasified, the solidified or cured product of water glass existing on the fire-resistant aggregate particles is released from the inside (by the internal pressure of the gas).
  • a neutralizing agent such as a phosphoric acid ester that reacts with water glass to promote curing
  • a CS template material composition
  • the neutralizing agent and the water glass react with each other to promote curing more than necessary. That can be prevented.
  • the film thickness of the solid first coating layer formed on the surface of the refractory aggregate is 0.1 to 6 ⁇ m, preferably 0.2 to 5 ⁇ m, more preferably 0.3. It is set to about 3 ⁇ m, more preferably 0.5 to 2 ⁇ m. If the film thickness is thinner than 0.1 ⁇ m, it may be difficult to form the coating layer, and it may be difficult to gasify the inside of the second coating layer made of the binder composition containing water glass. On the other hand, if it is thicker than 6 ⁇ m, an odor may be generated by the organic compound.
  • the film thickness of the first coating layer As a method for measuring the film thickness of the first coating layer, cast sand in which fire-resistant aggregate particles on which the first coating layer is formed is embedded in an epoxy resin or the like and cut using a cutting device such as an ion cutter. Examples thereof include a method in which the cross section of the particles is observed using an optical machine such as an optical microscope or an electron microscope, 10 cross-sectional particles are randomly selected, and the film thickness of the coating layer is measured.
  • the refractory aggregate particles are spherical, the film thickness may be calculated from the average particle diameter of the refractory aggregate particles and the amount of the refractory aggregate particles and the organic compound added.
  • the organic compound used in the present invention is not only capable of forming a solid coating layer on the surface of fire-resistant aggregate particles, but also in a solid state together with a predetermined neutralizing agent.
  • the coating layer is not particularly limited as long as it can be formed, but it is preferably at least one selected from the group consisting of a crosslinkable resin and a cured product thereof, a thermoplastic resin, and a carbohydrate.
  • a crosslinkable resin and a cured product thereof are advantageously used from the viewpoint of maintaining the strength of the coated sand (CS).
  • Crosslinkable curable resin is, for example, heated or heated in the presence or absence of a curing agent such as hexamethylenetetramine, organic ester, organic acid, carbon dioxide gas, peroxide, metal ion, amine, etc. or a curing catalyst. It exhibits crosslink curability under non-heating (normal temperature) and forms a mold by binding fire-resistant aggregate particles to each other.
  • a curing agent such as hexamethylenetetramine, organic ester, organic acid, carbon dioxide gas, peroxide, metal ion, amine, etc. or a curing catalyst. It exhibits crosslink curability under non-heating (normal temperature) and forms a mold by binding fire-resistant aggregate particles to each other.
  • Specific examples of such crosslinkable curable resins include phenol-based resins, phenol-urethane-based resins, epoxy resins, melamine resins, unsaturated polyester resins, and polyfunctional acrylamide-based resins (see JP-A-7-106421).
  • Unsaturated alkyd resin, unsaturated fatty acid-modified alkyd resin, diallyl phthalate resin, and if necessary, a resin in which these resins are combined can be mentioned.
  • a novolak type or resol type phenolic resin or a phenolic urethane resin used in combination with a polyisocyanate compound is particularly preferable.
  • the cured product of the crosslink curable resin is a product in which the molecular weight is increased to a polymer compound by subjecting a low molecular weight crosslink curable resin to a curing reaction.
  • the cured product of the cross-curable resin has 1) suppression of softening of the coating layer due to heat and improved mold strength, and 2) necessary for pre-curing. Since the amount of heat is consumed, the heat is effectively used for thermal decomposition, and the thermal decomposition is accelerated, so that the disintegration property of the mold is further improved, and 3) the gas accompanying the curing is released in advance. Therefore, there is an advantage that the amount of gas generated during casting can be suppressed.
  • thermoplastic resin specifically, polyvinyl alcohol, polyvinyl acetate, polystyrene, styrene acrylonitrile copolymer, styrene / butadiene / acrylonitrile copolymer, ethylene vinyl acetate copolymer, polymethyl
  • thermoplastic resin specifically, polyvinyl alcohol, polyvinyl acetate, polystyrene, styrene acrylonitrile copolymer, styrene / butadiene / acrylonitrile copolymer, ethylene vinyl acetate copolymer, polymethyl
  • polyvinyl alcohol polyvinyl acetate, polystyrene, ethylene vinyl acetate copolymer, polymethylmethacrylate, cellulose acetate, and polycarbonate are particularly preferable from the viewpoint of solvent solubility (depositionability).
  • carbohydrate specifically, those composed of glucose, fructose, galactose, lactose, sucrose, maltose, trehalose, starch, glycogen, cellulose and the like can be mentioned.
  • trehalose, starch and glycogen are particularly preferable from the viewpoint of film forming property.
  • organic compounds include acrylamide, N-methylolacrylamide, diacrylamide dimethyl ether, methylenebisacrylamide, ethylenebisacrylamide, ethylene glycoldiacrylamide and the like.
  • the organic compound contained in the first coating layer on the surface of the refractory aggregate particles is a polymer compound (polymer, a large amount) from the viewpoint of coating property on the refractory aggregate particles.
  • Body is preferable.
  • polymer compounds (polymers, multimers) having a weight average molecular weight of 300 or more, preferably 300 to 100,000,000, more preferably 500 to 50,000,000, and even more preferably 800 to 2000000000 are preferably used.
  • Even organic compounds not included in the category of polymer compounds (polymers, multimers) are preferably those having a molecular weight of 300 or more from the viewpoint of surface stability of the solid coating layer, and are fire-resistant aggregates. From the viewpoint of coating property on particles, those of 100,000,000 or less are preferable.
  • a water-insoluble or water-insoluble organic compound is advantageously used, and a water-insoluble organic compound is particularly suitable as an organic compound contained in the solid first coating layer. is there.
  • a water-insoluble organic compound is particularly suitable as an organic compound contained in the solid first coating layer. is there.
  • the solubility in 100 g of water at 25 ° C. is 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.1% by mass.
  • the following organic compounds are used as the organic compounds contained in the solid coating layer.
  • the solubility means the amount of the organic compound dissolved in the solvent (water) when 10 g of the organic compound was added with 100 g of water at 25 ° C., stirred for 1 hour, and allowed to stand for another 1 hour. It is a thing.
  • the water-insoluble organic compound is an organic compound that is insoluble in water.
  • a solid layer composed of only a predetermined neutralizing agent is formed on the surface of the refractory aggregate as the first coating layer
  • various conventionally known methods are used. From among them, those according to the form and characteristics of the neutralizing agent are appropriately selected and adopted.
  • the neutralizing agent has a property of melting without decomposition at a temperature lower than the temperature heated at the time of casting (hereinafter referred to as the temperature in this paragraph), it is referred to as a fire-resistant aggregate.
  • the neutralizer is mixed while being heated to the temperature to form a layer of the molten neutralizer on the surface of the fire-resistant aggregate, and then cooled to neutralize the surface of the fire-resistant aggregate. It is possible to form a solid first coating layer composed of the agent.
  • a solid organic compound and a predetermined neutralizing agent are added to and mixed with a fire-resistant aggregate heated to 130 to 180 ° C. to heat the fire-resistant aggregate.
  • a method of forming a solid coating layer containing a predetermined neutralizing agent is added to an organic compound as it is or dissolved in a solvent such as methanol to make it liquid, and a liquid substance containing a predetermined neutralizing agent is added to a fire-resistant aggregate.
  • a crosslinkable resin is used as the organic compound, for example, after forming a solid first coating layer according to the above-mentioned coating method, further heating and / or a curing agent or curing is performed. By adding a catalyst, the crosslinkable curable resin may be cured to increase the molecular weight of the crosslinkable curable resin contained in the first coating layer.
  • the crosslinkable curable resin is cured by heating, for example, it is placed in a constant temperature bath at 120 ° C. to 300 ° C. for reaction curing for about 5 to 60 minutes, or the cast sand is heated to 150 ° C. to 300 ° C. and 120 ° C.
  • the mold material composition obtained by curing the crosslinkable resin contained in the coating layer has a strong neck between the refractory aggregate particles (sand particles), and may be integrally agglomerated or form composite particles. Therefore, in order to improve the surface condition of the refractory aggregate coated with the first coating layer, it is preferable to carry out reaction curing with a speed kneader (speed muller) having kneading and a high rotation speed. Further, if the mixture is kneaded for a long time, peeling may occur and fine powder may be generated.
  • speed kneader speed muller
  • the curing agent or the curing catalyst includes, for example, hexamethylenetetramine, an organic ester, an organic acid, a carbon dioxide gas, a peroxide, a metal ion, and the like. Amine or the like is used.
  • the crosslinkable curable resin is a phenol urethane resin, it can be cured by mixing the phenol resin and the polyisocyanate resin. Even when the crosslinkable resin is cured using a curing agent, it is desirable to perform reaction curing while kneading with a kneader.
  • the CS template material composition
  • the CS has a "two-layer structure" that does not have room temperature fluidity and exhibits a wet state.
  • it is manufactured according to the following procedure. That is, water glass as a binder is uniformly mixed with the refractory aggregate provided with the first coating layer by kneading or mixing it with an additive as necessary.
  • a template material composition consisting of a mixture of a refractory aggregate provided with a solid first coating layer containing a neutralizing agent of water and a liquid binder composition containing water glass, in other words.
  • a template material composition is obtained in which a second coating layer of a binder composition containing water glass is formed so as to coat the first coating layer on the surface of the refractory aggregate.
  • Various conditions at the time of mixing are appropriately determined according to the type of the aqueous water-soluble inorganic binder, the amount of water, etc., and the temperature at the time of mixing is generally room temperature to 40 ° C. It is said to be a degree.
  • the water content thereof is adjusted so that the obtained mold material composition exhibits an appropriate wet state. Specifically, it is adjusted so as to be more than 55% by mass of the solid content of the water glass, preferably 70 to 900% by mass, and more preferably 95 to 500% by mass.
  • the mold material composition having a moisture content adjusted in this way and exhibiting a wet state according to the present invention the mold material composition exhibiting a wet state by blow air when filling the mold during mold molding.
  • the water content of the mold material composition can be measured by the Karl Fischer method or the weight change when heated by a dryer or the like.
  • CS template material composition having a two-layer structure
  • CS template material composition having a two-layer structure
  • the fire-resistant bone As the outermost layer on the surface of the material, a method of forming a coating layer of a water glass composition (a second coating layer containing a binder containing water glass as an essential component) will be adopted. In such a method, the evaporation of water in the second coating layer needs to be carried out rapidly before the solidification or hardening of the water glass proceeds, so that the water in the form of an aqueous solution is used with respect to the refractory aggregate.
  • the mold material composition is first placed in a molding cavity of a mold that gives a target mold.
  • solidification or curing of the filled mold material composition exhibiting a wet state proceeds, and a target mold can be obtained.
  • the refractory aggregate particles constituting the mold material composition are present in the surroundings.
  • An aggregate (composite) of refractory aggregates having an integral mold shape is formed by bonding and connecting to each other through water glass contained in the binder composition.
  • a predetermined curing agent may be introduced into the cavity in a liquid state or a gaseous state.
  • water glass is usually solidified by evaporation to dryness of water if no additive is added, and is cured if a curing agent is added.
  • the template composed of an aggregate (combined) of coated sand can be either a solidified product of such coated sand (solidified product) or a cured product obtained by curing with a curing agent (cured product). It includes.
  • a molding mold in a state of being preheated (preheated) to a predetermined temperature and maintained at that temperature. After that, it is preferable to fill the cavity of the molding mold with the mold material composition so that the mold material composition is heated.
  • preheating the molding die in this way, it is possible to accelerate the drying of the mold material composition and shorten the molding time.
  • 80 to 300 ° C. preferably 100 to 200 ° C., more preferably 120 to 180 ° C. is adopted.
  • the holding temperature is preferably 80 ° C. or higher, and the bond between the refractory aggregate particles is sufficient.
  • the temperature is preferably 300 ° C. or lower from the viewpoint of preventing the occurrence of the problem that the water content evaporates before being formed and the template strength is not developed.
  • hot air or superheated steam is blown into the mold to promote the evaporation of water, and the filling phase (mold material composition) in the mold is ventilated.
  • a method of squeezing is preferably adopted.
  • a carrier gas composed of at least one of carbon dioxide, argon, nitrogen, and helium is used to more advantageously promote the solidification or curing of the mold material composition while the mold material composition is held in the mold.
  • a carrier gas composed of at least one of carbon dioxide, argon, nitrogen, and helium is used to more advantageously promote the solidification or curing of the mold material composition while the mold material composition is held in the mold.
  • carbon dioxide acts as a curing agent
  • argon, nitrogen and helium act as a solidification accelerator.
  • the ventilation of hot air or superheated steam and the ventilation of carrier gas may be performed only by one of them, but it is also possible to carry out both of them, and in that case, of the hot air or superheated steam.
  • Techniques such as ventilation and carrier gas ventilation at the same time, carrier gas ventilation after hot air or superheated steam ventilation, or hot air or superheated steam after carrier gas ventilation are adopted.
  • hot air and / or carrier gas is ventilated at any timing as long as it is being held in the molding die.
  • the curing agent to be applied is introduced into the molding mold.
  • a method of solidifying or curing the mold material composition or a method of solidifying or curing the mold material composition by reducing the pressure in the molding mold filled with the mold material composition can also be adopted. Is.
  • the introduction of the curing agent into the mold is to proceed the curing by the reaction between the curing agent and another binder (for example, a water-soluble inorganic binder) used in combination with water glass.
  • another binder for example, a water-soluble inorganic binder
  • a method of introducing the curing agent a method of adding a curing agent to the mold material composition before filling into the molding mold and filling the mold material composition to which the curing agent is added into the molding mold, and Any method of introducing the curing agent by aerating the curing agent as a carrier gas into the mold material composition filled in the molding die can be adopted. Further, while the product is held in the mold, curing by the curing agent proceeds.
  • a carrier gas consisting of at least one of carbon dioxide, argon, nitrogen and helium can be blown into the mold.
  • Examples of the curing agent used therein include organic acids such as carbon dioxide (carbonated water), sulfuric acid, hydrochloric acid, nitrate, phosphoric acid, oxalic acid, carboxylic acid, and paratoluenesulfonic acid, methyl formate, ethyl formate, and propyl formate.
  • Examples include esters such as ⁇ -butyrolactone, ⁇ -propion lactone, ethylene glycol diacetate, diethylene glycol diacetate, glycerin diacetate, triacetin, and propylene carbonate, and monohydric alcohols such as methanol, ethanol, butanol, hexanol, and octanol. Can be done.
  • these curing agents can be used alone, or two or more kinds of these curing agents can be mixed and used.
  • the method of depressurizing the inside of the molding die is to dry and solidify the coated sand filled in the cavity of the molding die by such depressurization.
  • the depressurizing method for example, a method of depressurizing the inside of the molding die by a known suction means can be mentioned.
  • heating of the molding die is not always required, but it is preferable to heat the molding die in order to promote solidification or curing more advantageously.
  • the first method is to moisten a mold material composition exhibiting a dry state by kneading it with water at a molding site, and to obtain the wet state mold material composition.
  • the mold is filled into the mold cavity that provides the mold and the mold is heated to a temperature of 80-300 ° C. so that the filled mold material composition is retained in the mold until it dries.
  • This is a water addition method.
  • the second method after filling a mold material composition in a dry state into a molding cavity of a molding mold that gives a target mold, water vapor is blown into the molding cavity to fill the mold material composition.
  • the molds such as molds and wooden molds, which are filled with the mold material composition having room temperature fluidity and exhibiting a dry state, are preheated, thereby. Kneading with water and drying of the mold material composition moistened by steam can proceed advantageously.
  • the preheating temperature is generally preferably 80 to 300 ° C., preferably 90 to 250 ° C., more preferably 100 to 200 ° C. in the first method, and 80 to 200 ° C. in the second method.
  • a temperature of about ° C., preferably 90 to 150 ° C., more preferably about 100 to 140 ° C. is desirable. If the heat retention temperature is too high, it becomes difficult for steam to pass to the surface of the molding mold, while if the temperature is too low, it takes time to dry the molded mold.
  • the mold material composition in a dry state is transported to a molding site, which is a mold manufacturing site. After that, at the molding site, water is added to moisten the mold, and then the obtained mold material composition exhibiting the wet state is filled in the mold to exhibit the above wet state.
  • the target mold is molded in the same manner as in the case of molding the material composition, but in this step, water is added to the mold material composition in a dry state to moisten it. It is an extremely simple operation because it is sufficient to moisten the mold material composition by simply putting the mold material composition in a dry state and a predetermined amount of water into an appropriate mixer and mixing them.
  • the mold material composition may be preheated to 40 ° C. to 100 ° C. before use by adding water.
  • water one or more selected from other additives, a curing accelerator, and a water-soluble inorganic binder for readjusting the mold strength may be added together.
  • the other additive or the like is a liquid, water may be contained in the liquid.
  • the temperature of the steam is generally about 80 to 150 ° C., more preferably 95. It is about 120 ° C.
  • a steam temperature of particularly around 100 ° C. is advantageously adopted.
  • the pressure of the water vapor to be ventilated a value of about 0.01 to 0.3 MPa, more preferably about 0.02 to 0.1 MPa in gauge pressure is advantageously adopted.
  • the ventilation time generally, a ventilation time of about 2 seconds to about 60 seconds is adopted.
  • hot air or superheated steam is blown into the molding die in order to positively dry the packed phase composed of the wet mold material composition, and the packed phase is formed.
  • a method of allowing ventilation is preferably adopted.
  • the solidification or curing of the packed phase is more advantageous.
  • the above-mentioned curing agent may be aerated in the form of gas or mist, and the curing agent may be solidified or solidified by neutralizing water glass (and other water-soluble inorganic binders). It is possible to promote curing more.
  • the curing agent may be ventilated at the same time as the aeration of hot air or the like in the first method, and at the same time as the aeration of water vapor or the aeration of hot air or the like in the second method.
  • the pressure inside the molding die may be reduced. By such a reduced pressure, the mold material composition filled in the cavity of the molding mold is dried and solidified.
  • the depressurizing method include a method of depressurizing the inside of the molding mold by a known suction means. Further, when the pressure inside the molding die is reduced, hot air or superheated steam may be blown into the molding die in order to promote the evaporation of water.
  • any of the molds obtained according to the above-mentioned production method and the molds obtained according to other production methods are described below. It is possible to advantageously enjoy the excellent effects described. That is, when such a mold is used for casting, the mold is heated by the molten metal (generally heated to a temperature exceeding 300 ° C.), and the decomposition product produced by the neutralizing agent by such heating is combined with the alkaline component of water glass. By causing a neutralization reaction between them, the water glass becomes physically fragile, and the disintegration property of the mold after casting becomes good.
  • the molten metal generally heated to a temperature exceeding 300 ° C.
  • a molten metal injection port 2 at the upper part and a skirting board fixing part 4 at the lower part (this part is a discharge port for waste core from a casting), which is made of self-hardening sand at room temperature in advance.
  • a circular aerial core 10 (diameter: 5 cm, height) having a skirting board portion 8 produced by using each CS in a semi-cracked hollow main mold 6 (cavity diameter: 6 cm, height: 6 cm) having S: 5 cm) is adhesively fixed by the skirting board fixing portion 4, and then the half-cracked hollow main molds 6 are adhesively fixed to each other to prepare a sand mold 12 for a casting test.
  • a molten aluminum alloy (temperature: 710 ⁇ 5 ° C.) was poured from the molten metal injection port 2 of the sand mold 12 for casting test to solidify it, and then the main mold 6 was broken to eliminate the circular waste shown in FIG.
  • the casting 16 having the core discharge port 14 (diameter: 1.6 cm) is taken out.
  • the obtained casting 16 is impacted (striked) for 3 seconds at a time with an air hammer at a pressure of 0.2 MPa, and is discharged from the discharge port 14. ..
  • the number of hits until 100% of the core is discharged is counted and evaluated according to the criteria shown below.
  • ⁇ The sand removal rate became 100% by hitting 1 to 5 times.
  • ⁇ The sand removal rate became 100% by hitting 6 to 10 times.
  • X The sand removal rate did not reach 100% even after 10 hits.
  • -Abrasion peeling test 100 g of the refractory aggregate (recovered sand) constituting the circular aerial core, which was taken out in the above-mentioned disintegration test, was placed in a ball mill and polished for 1 hour. Then, sieving with 200 mesh for 1 minute was performed to separate the refractory aggregate into the exfoliated fine powder, the amount of the obtained fine powder was measured, and the ease of exfoliation in the recovered sand was determined according to the criteria shown below. Evaluate on a 3-point scale.
  • ⁇ The amount of fine powder is 0.3% by mass or more with respect to the mass of the refractory aggregate.
  • ⁇ The amount of fine powder is 0.1% by mass or more and less than 0.3% by mass with respect to the mass of the refractory aggregate.
  • X The amount of fine powder is less than 0.1% by mass with respect to the mass of the refractory aggregate.
  • each coated sand (CS) are as follows.
  • -Refractory aggregate Alumina-based spherical aggregate (Product name: Espal # 60, manufactured by Yamakawa Sangyo Co., Ltd.)
  • Refractory aggregate Fratary silica sand (Flatary No. 6)
  • -Water glass No. 1 sodium silicate (Product name, manufactured by Fuji Chemical Co., Ltd., SiO 2 / Na 2 O molar ratio: 2.1, solid content: 45% by mass)
  • -Water glass No. 2 sodium silicate (Product name, manufactured by Fuji Chemical Co., Ltd., SiO 2 / Na 2 O molar ratio: 2.5, solid content: 41% by mass)
  • -Water glass No.
  • wet CS 1- A water glass aqueous solution having a solid component (concentration) of 41% was prepared using water glass (No. 2 sodium silicate).
  • the refractory aggregate (Espearl # 60) was put into a Shinagawa universal stirrer (5DM-r type, manufactured by Dalton Co., Ltd.) at room temperature, and the above water glass aqueous solution was applied to 100 parts of the refractory aggregate.
  • a coating layer containing water glass and a neutralizing agent (chlorinated paraffin) is provided on the surface of the refractory aggregate by taking it out after stirring and mixing until it becomes uniform.
  • a template material composition (wet state CS: CS1a) to be presented was obtained.
  • wet CS 10- A mold material that exhibits a wet state according to the same procedure as in Production Example 1 above, except that 0.13 part of vinyl chloride (lyuron paste) is used as a neutralizing agent in Production Example 1 of wet state CS.
  • the composition (CS10a) was obtained.
  • wet CS 17- After heating the fire-resistant aggregate (Espearl # 60) to a temperature of about 60 ° C., it is put into a whirl mixer (manufactured by Enshu Iron Works Co., Ltd.), and further, a neutralizing agent (neutralizing agent () Empara 70) was added at a ratio of 0.10 parts, 0.20 parts of aromatic polyester polyol (manufactured by Kawasaki Kasei Co., Ltd., trade name: MAXIMOL RDK-133), and polyisocyanate (MDI, Mitsui Kagaku SKC).
  • a neutralizing agent neutralizing agent () Empara 70) was added at a ratio of 0.10 parts, 0.20 parts of aromatic polyester polyol (manufactured by Kawasaki Kasei Co., Ltd., trade name: MAXIMOL RDK-133), and polyisocyanate (MDI, Mitsui Kagaku SKC).
  • the template material composition (wet state CS: CS1a to CS20a) exhibiting a wet state according to the present invention contains a predetermined neutralizing agent. Therefore, it is recognized that the mold obtained by using them is excellent in disintegration property, and the amount of alkali remaining in the refractory aggregate (recovered sand) recovered after casting is sufficiently low. Furthermore, the evaluation in the polishing peeling test is also good, and it is confirmed that the polishing treatment of the recovered sand is easy.
  • a mold that exhibits a dry state in which a coating layer containing water glass and a neutralizing agent (chlorinated paraffin) is provided on the surface of the refractory aggregate by stirring and mixing until uniform.
  • a material composition dry CS: CS1b was obtained.
  • Example II (Examples 21 to 31, Comparative Examples 6 to 9)- CS1b to CS15b (temperature: 20 ° C.) manufactured according to each of the above procedures are put into a Shinagawa universal stirrer (5DM-r type, manufactured by Dalton Corporation) at room temperature, and water is further added to CS 100.
  • a moistened CS was prepared by adding the mixture in a stirrer at a ratio of 1.0 part to a part and stirring the mixture.
  • the wet CS taken out from the stirrer is filled in a molding die heated to 150 ° C., then held in the molding die, and the CS filled in the molding die is solidified (cured).
  • the dry CS (CS12b to CS15b), which is a template material composition exhibiting a dry state and does not contain a predetermined neutralizing agent, is 1) CS12b to CS14b.
  • CS15b it was found that the mold obtained by using them had poor disintegration property and the amount of alkali remaining in the recovered sand was large.
  • CS15b the mold was molded in the first place. It is confirmed that it cannot be done.
  • Example III (Examples 32 to 36, Comparative Examples 10 to 11)- CS1b, CS6b, CS9b to CS12b, CS15b (temperature: 20 ° C.) manufactured according to each of the above procedures are blown into a molding die heated to 110 ° C. at a gauge pressure of 0.3 MPa. After filling, steam at a temperature of 99 ° C. was blown for 4 seconds under a gauge pressure of 0.05 MPa, and the coated sand (CS) phase filled in the molding die was aerated. Then, after the aeration of such steam is completed, hot air having a temperature of 150 ° C.
  • the mold material compositions dry CS: CS1b, CS6b, CS9b to CS11b are aerated with water vapor in a molding die. Even if there is, as in the case of the mold material composition (wet state CS: CS1a to CS20a) exhibiting a wet state according to the present invention, since it contains a predetermined neutralizing agent, the disintegration of the mold obtained by using them It is recognized that the properties are excellent and the amount of alkali remaining in the fire-resistant aggregate (recovered sand) recovered after casting is sufficiently low. Furthermore, the evaluation in the polishing peeling test is also good, and it is confirmed that the polishing treatment of the recovered sand is easy.
  • the dry CS (CS12b, CS15b) which is a template material composition exhibiting a dry state and does not contain a predetermined neutralizing agent is found in 1) CS12b. Therefore, it was found that the mold obtained by using them had poor disintegration property and that the amount of alkali remaining in the recovered sand was large. 2) In addition, in CS15b, the mold could not be molded in the first place. It is confirmed that it is a thing.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
PCT/JP2020/013986 2019-03-29 2020-03-27 鋳型材料組成物及びそれを用いた鋳型の製造方法 WO2020203752A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025063245A1 (ja) * 2023-09-21 2025-03-27 花王株式会社 乾態の無機コーテッドサンド、乾態の無機コーテッドサンドの製造方法および鋳型の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6448638A (en) * 1987-08-17 1989-02-23 Ryobi Ltd Production of collapsible core
WO2015194550A1 (ja) * 2014-06-20 2015-12-23 旭有機材工業株式会社 鋳型の製造方法及び鋳型
WO2018147419A1 (ja) * 2017-02-10 2018-08-16 旭有機材株式会社 鋳型材料組成物及びこれを用いた鋳型の製造方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE553251A (enrdf_load_stackoverflow) * 1955-12-16
JPS5015734A (enrdf_load_stackoverflow) * 1973-06-15 1975-02-19
JPS5113319A (ja) * 1974-07-23 1976-02-02 Kubota Ltd Mizugarasukeiimonosunahaisano shorihoho
US4834165A (en) * 1987-08-03 1989-05-30 Ryobi Ltd. Collapsible core and method for producing the collapsible core feasible for high speed high pressure casting
JPH0768343A (ja) * 1994-08-08 1995-03-14 Asahi Organic Chem Ind Co Ltd アルミニウム合金鋳物の製造方法
CN1071159C (zh) * 1995-11-08 2001-09-19 花王株式会社 砂型用粘结剂、型砂组合物和砂型的制造方法
JP4551047B2 (ja) * 2002-02-08 2010-09-22 三菱自動車工業株式会社 消失模型鋳造法における貫通細孔部に充填して使用する中子形成用組成物
JP4323187B2 (ja) * 2003-02-27 2009-09-02 旭有機材工業株式会社 鋳型用有機粘結剤及びこれを用いて得られる鋳物砂組成物並びに鋳型
JP4688618B2 (ja) * 2005-09-22 2011-05-25 株式会社木村鋳造所 浸硫防止塗型剤
DE102006049379A1 (de) * 2006-10-19 2008-04-24 Ashland-Südchemie-Kernfest GmbH Phosphorhaltige Formstoffmischung zur Herstellung von Giessformen für die Metallverarbeitung
DE102007008149A1 (de) * 2007-02-19 2008-08-21 Ashland-Südchemie-Kernfest GmbH Thermische Regenerierung von Gießereisand
DE102007051850B4 (de) * 2007-10-30 2025-08-28 Ask Chemicals Gmbh Verfahren zur Herstellung von Gießformen für die Metallverarbeitung unter Verwendung einer Formstoffmischung mit verbesserter Fliessfähigkeit
EP2476495B1 (en) * 2009-09-10 2019-05-22 Lignyte Co., Ltd. Method of manufacturing casting mold using binder coated refractories
JP5672550B2 (ja) * 2011-06-21 2015-02-18 ミンテックジャパン株式会社 タンディッシュコーティング材及びこれを用いてタンディッシュをコーティングする方法
DE102012104934A1 (de) * 2012-06-06 2013-12-12 Ask Chemicals Gmbh Forstoffmischungen enthaltend Bariumsulfat
DE102012020509A1 (de) * 2012-10-19 2014-06-12 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
JP6193884B2 (ja) * 2012-12-19 2017-09-06 旭有機材株式会社 コーテッドサンド及びその製造方法並びに鋳型の製造方法
CN104338893B (zh) * 2013-07-26 2016-08-17 沈阳铸造研究所 一种具有高流动性的水玻璃砂及其制备方法
CN103495693A (zh) * 2013-10-16 2014-01-08 合肥市田源精铸有限公司 一种耐高温易溃散型砂及其制备方法
CN106077439A (zh) * 2016-08-18 2016-11-09 江阴联华铸造有限公司 一种火车铝合金铸件铸造用易溃散水玻璃芯砂及其制备方法
CN107774878A (zh) * 2017-12-19 2018-03-09 江西瑞冠精密铸造有限公司 一种精密铸造用模具的配料及其制备工艺

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6448638A (en) * 1987-08-17 1989-02-23 Ryobi Ltd Production of collapsible core
WO2015194550A1 (ja) * 2014-06-20 2015-12-23 旭有機材工業株式会社 鋳型の製造方法及び鋳型
WO2018147419A1 (ja) * 2017-02-10 2018-08-16 旭有機材株式会社 鋳型材料組成物及びこれを用いた鋳型の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025063245A1 (ja) * 2023-09-21 2025-03-27 花王株式会社 乾態の無機コーテッドサンド、乾態の無機コーテッドサンドの製造方法および鋳型の製造方法

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