JP6770528B2 - Molding kit - Google Patents

Description

The present invention relates to a mold molding kit and a mold molding binder composition.

In general, an acid-curable template is composed of a binder composition for molding containing an acid-curable resin and a curing agent composition containing sulfonic acid, sulfuric acid, phosphoric acid, etc. in fire-resistant particles such as silica sand. After adding and kneading these, the obtained kneaded sand is filled in a prototype such as a wooden mold, and the acid-curable resin is cured to produce the product. Furfuryl alcohol, furfuryl alcohol, urea, formaldehyde resin, furfuryl alcohol, formaldehyde resin, furfuryl alcohol, phenol, etc. are used as the acid curable resin. Formaldehyde resin and other known modified furan resins are used. Such a mold manufacturing method enables molding work with a high degree of freedom, and since high-quality castings can be manufactured due to the excellent thermal properties of the mold, machine parts, construction machine parts, automobile parts, etc. Widely used when casting castings of.

An important item in molding a mold or casting a desired casting using a mold is to improve the working environment during casting. Since an acid containing a sulfur atom such as organic sulfonic acid or sulfuric acid is used as a curing agent in the acid-curable mold, SOx such as sulfur dioxide and the thermal decomposition gas of other components at the time of casting deteriorate the working environment. There is a fear. Therefore, it is desired to suppress the generation of SOx.

Japanese Unexamined Patent Publication No. 2013-240827 discloses a technique for reducing the generation of SO ₂ gas by using 2,6-dihydroxybenzoic acid as a curing agent instead of an acid containing a sulfur atom.

Further, another important item in molding the mold or casting a desired casting using the mold includes the curing speed of the mold and the strength of the mold. If the curing rate of the mold is slow, the productivity of the mold will decrease, and if the strength of the mold is insufficient, the mold will crack or cracks will occur during casting, which may endanger the operator or result in casting. May become defective.

Japanese Unexamined Patent Publication No. 2013-151019 discloses a technique for improving the curing rate of a mold and the strength of a mold by using a binder composition for molding, which contains a furfural derivative and a flufurylated urea resin.

In addition, since the reaction rate is affected by temperature, the concentration of the curing agent may be adjusted in order to obtain a desired curing rate and mold strength. For example, when the temperature of the working environment is low, especially when the refractory particles are low, the reaction rate decreases, so the concentration of the curing agent in the curing agent composition is increased so that the desired curing rate and mold strength can be obtained. (For example, JP-A-62-130740, JP-A-53-129292).

However, when an acid containing a sulfur atom is used as a curing agent, if the amount of the acid used is increased in order to obtain a desired curing rate and template strength under low temperature conditions, the amount of SOx generated such as sulfur dioxide increases, and the work The environment deteriorates.

When, for example, 2,6-dihydroxybenzoic acid is used as a curing agent instead of the acid containing a sulfur atom, the amount of SOx generated can be suppressed, but the desired template strength cannot be obtained depending on the temperature of the working environment. There is.

To solve such a problem, a technique has been disclosed in which a furan aldehyde compound is contained in a binder composition to obtain sufficient template strength without using an acid containing a sulfur atom as a curing agent (for example,). WO2015 / 098642 pamphlet).

The mold molding kit of the present invention is a mold molding kit for producing a mold composition, which comprises a binder composition and a curing agent composition, and the binder composition is a furanaldehyde compound. It contains a condensate of and an aromatic hydroxy compound, and the curing agent composition contains an acid.

The mold-molding binder composition of the present invention is a mold-molding binder composition containing a condensate of a furanaldehyde compound and an aromatic hydroxy compound, and the aromatic hydroxy compound is two or more. It has a hydroxyl group.

Detailed description of the invention

When the furanaldehyde compound is contained in the binder composition, the unreacted furanaldehyde compound volatilizes during template curing, which deteriorates the working environment in the same manner as when an acid containing a sulfur atom is used as the curing agent. It became clear that there was a fear.

The present invention provides a mold molding kit and a mold molding binder composition capable of obtaining sufficient mold strength without deteriorating the working environment at the time of mold manufacturing.

The mold molding kit of the present invention is a mold molding kit for producing a mold composition, which comprises a binder composition and a curing agent composition, and the binder composition is a furanaldehyde compound. It contains a condensate of and an aromatic hydroxy compound, and the curing agent composition contains an acid.

The mold-molding binder composition of the present invention is a mold-molding binder composition containing a condensate of a furanaldehyde compound and an aromatic hydroxy compound, and the aromatic hydroxy compound is two or more. It has a hydroxyl group.

According to the present invention, it is possible to provide a mold molding kit and a mold molding binder composition capable of obtaining sufficient mold strength without deteriorating the working environment at the time of mold production.

Hereinafter, an embodiment of the present invention will be described.

<Molding kit>
The mold molding kit of the present embodiment is a mold molding kit for producing a mold composition, which comprises a binder composition and a curing agent composition, and the binder composition is furanaldehyde. It contains a condensate of the compound and an aromatic hydroxy compound, and the curing agent composition contains an acid. The mold molding kit can obtain sufficient mold strength without deteriorating the working environment at the time of mold manufacturing. The reason for achieving such an effect is not clear, but it can be considered as follows.

The reactivity of the condensate of the furan aldehyde compound and the aromatic hydroxy compound is higher than that of furfuryl alcohol, which is the main component of the conventional furan resin. Therefore, it is possible to manufacture a high-strength mold without using a conventional strong acid such as sulfuric acid or sulfonic acid. Further, by pre-condensing the furanaldehyde compound and the aromatic hydroxy compound, the amount of the furanaldehyde compound monomer itself can be reduced while maintaining the amount of the monomer unit of the furanaldehyde compound in the binder composition. , It is possible to prevent volatilization of the furanaldehyde compound during mold production. In addition, the non-uniformity of curing is corrected by the presence of the condensate dispersed in the mold. From these facts, it is considered that the mold molding kit of the present embodiment can obtain sufficient mold strength without deteriorating the working environment at the time of mold production.

[Binder composition]
The binder composition contains a condensate of a furanaldehyde compound and an aromatic hydroxy compound.

[Condensate of furan aldehyde compound and aromatic hydroxy compound]
From the viewpoint of improving the template strength, the furan aldehyde compound is preferably at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural, and is composed of furfural and 5-hydroxymethylfurfural. At least one selected from the group is more preferable, and furfural is further preferable.

The aromatic hydroxy compound can be used without particular limitation as long as it is an aromatic hydroxy compound used for molding a mold, but from the viewpoint of improving the strength of the mold, an aromatic hydroxy compound having no carboxyl group may be used. preferable. Examples of the aromatic hydroxy compound include phenol, cresol, xylenol, cumylphenol, nonylphenol, butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, resorcin, bisphenol A, bisphenol F, bisphenol C, catechol, hydroquinone, and the like. At least one selected from the group consisting of pyrogallol and a condensate of fluoroglycin, phenols and formaldehyde can be exemplified, and among these, those having two or more hydroxyl groups are preferable from the viewpoint of improving template strength, and pyrogallol and At least one selected from the group consisting of resorcin is more preferable, and resorcin is further preferable.

When a condensate of the furanaldehyde compound and the aromatic hydroxy compound is obtained, it is preferable to use an alkaline catalyst such as potassium hydroxide as a reaction catalyst. From the viewpoint of improving the template strength and reducing the odor of the furanaldehyde compound, it is preferable to use 0.001 to 0.1 mol of the alkali catalyst with respect to 1 mol of the aromatic hydroxy compound, and 0.003 to 0.08. It is more preferable to use mol, and it is further preferable to use 0.01 mol to 0.07 mol.

The weight average molecular weight (Mw) of the condensate of the furanaldehyde compound and the aromatic hydroxy compound is preferably 190 to 7,000, more preferably 300 to 6,000, and 500 to 4 from the viewpoint of improving the template strength. 000 is more preferred. In this specification, the weight average molecular weight is measured by the method described in Examples.

The content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass from the viewpoint of improving the template strength. % Or more is more preferable. The content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is preferably 70% by mass or less, more preferably 60% by mass or less, and 50% by mass from the viewpoint of improving the template strength. % Or less is more preferable. The content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, from the viewpoint of improving the template strength. It is preferable, and more preferably 5 to 50% by mass.

[Other ingredients]
The binder composition may contain other components as long as the effects of the mold molding kit of the present embodiment are not impaired. Examples of the other components include the following components.

(Franaldehyde compound)
The binder composition may contain the furanaldehyde compound. The furanaldehyde compound may be left as an unreacted component when the condensate of the furanaldehyde compound and the aromatic hydroxy compound is produced, or may be added separately. However, if the content of the furanaldehyde compound in the binder composition is large, the unreacted furanaldehyde compound may volatilize during mold curing, which may deteriorate the working environment. Therefore, the content of the furanaldehyde compound in the binder composition is preferably 10% by mass or less, more preferably 0.5% by mass or less.

(Aromatic hydroxy compound)
The binder composition may contain the aromatic hydroxy compound. The aromatic hydroxy compound may be one that remains as an unreacted component when the condensate of the furan aldehyde compound and the aromatic hydroxy compound is produced, or one that is added separately. The content of the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of improving the template strength. The content of the aromatic hydroxy compound in the binder composition is preferably 10% by mass or less, more preferably 7% by mass or less, from the viewpoint of improving the template strength.

(One or more compounds selected from the group consisting of urea and urea derivatives)
From the viewpoint of improving the template strength, the binder composition may contain one or more compounds selected from the group consisting of urea and urea derivatives (hereinafter, also referred to as "urea and the like").

The one or more compounds selected from the group consisting of urea and urea derivatives in the binder composition is one selected from the group consisting of urea and urea derivatives that have not undergone a condensation reaction with formaldehyde, furfuryl alcohol, or the like. The above compounds may be those that remain as unreacted components or those that have been added separately.

One or more compounds selected from the group consisting of urea and urea derivatives include, for example, urea; alkylene urea such as ethylene urea, propylene urea, butylene urea, and hydantin; methyl urea, 1,1-dimethyl urea, 1,3. -Alkyl urea such as dimethyl urea; cyclohexyl urea such as cyclohexyl urea and 1,3-dicyclohexylurea; arylurea such as phenylurea, 1,1-diphenylurea and 1,3-diphenylurea; and 2-hydroxyethylurea and the like. Hydroxyalkylurea having 2 or more carbon atoms in the alkyl group; azodicarboxylic amide and the like can be mentioned. These compounds can be used alone or in admixture of two or more. Urea and ethylene urea are preferable from the viewpoint of improving the curing rate, improving the mold strength, and reducing the amount of formaldehyde generated, and urea is more preferable from the viewpoint of economy.

The content of urea or the like in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, from the viewpoint of improving the mold strength. The content of urea or the like in the binder composition is preferably 8% by mass or less, more preferably 7% by mass or less, and 6% by mass from the viewpoint of solubility of urea or the like in the binder composition. The following is more preferable. The content of urea or the like in the binder composition is 0.5 to 8% by mass from the viewpoint of improving the curing rate of the template and the solubility of urea in the binder composition. Preferably, 1 to 7% by mass is more preferable, and 1.5 to 6% by mass is further preferable.

(Acid curable resin)
The binder composition may contain a conventionally known acid-curable resin as a binder component. Examples of the acid-curable resin include furfuryl alcohol, a condensate of furfuryl alcohol, a condensate of furfuryl alcohol and aldehydes, a condensate of furfuryl alcohol and urea and aldehydes (urea-modified furan resin), and urea and ethylene. One selected from the group consisting of a condensate of urea and aldehydes (urea-ethyleneurea cocondensate resin), a condensate of melamine and aldehydes, and a condensate of urea and aldehydes, or from these groups An example comprises a mixture of two or more selected species. Further, those composed of two or more kinds of copolymers selected from these groups can also be used. Of these, from the viewpoint of improving the curing speed of the mold and improving the strength of the mold, furfuryl alcohol, a condensate of furfuryl alcohol, a condensate of furfuryl alcohol, urea and aldehydes, and a condensate of urea, ethylene urea and aldehydes. It is preferable to use one or more selected from the above, as well as cocondensates thereof. Since furfuryl alcohol can be produced from plants, which are non-petroleum resources, it is preferable to use furfuryl alcohol from the viewpoint of the global environment.

The content of the acid-curable resin in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 25% by mass or more, from the viewpoint of improving the mold strength. From the same viewpoint, the content of the acid-curable resin in the binder composition is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. From the same viewpoint, the content of the acid-curable resin in the binder composition is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 25 to 85% by mass.

(Curing accelerator)
The binder composition may contain a curing accelerator from the viewpoint of improving the mold strength. As the curing accelerator, one or more selected from the group consisting of the compound represented by the following general formula (1) (hereinafter referred to as the curing accelerator (1)) and the aromatic dialdehyde from the viewpoint of improving the template strength. Is preferable.

〔式中、Ｘ_１及びＸ_２は、それぞれ水素原子、ＣＨ_３又はＣ_２Ｈ_５の何れかを表す。〕

[In the formula, X ₁ and X ₂ represent either a hydrogen atom, CH ₃ or C ₂ H ₅ , respectively. ]

Examples of the curing accelerator (1) include 2,5-bishydroxymethylfuran, 2,5-bismethoxymethylfuran, 2,5-bisethoxymethylfuran, 2-hydroxymethyl-5-methoxymethylfuran, and 2-. Examples thereof include hydroxymethyl-5-ethoxymethylfuran and 2-methoxymethyl-5-ethoxymethylfuran. Of these, 2,5-bishydroxymethylfuran is preferably used from the viewpoint of improving the template strength.

Examples of the aromatic dialdehyde include terephthalaldehyde, phthalaldehyde, isophthalaldehyde and the like, and derivatives thereof. The derivatives thereof mean a compound having a substituent such as an alkyl group on the aromatic ring of an aromatic compound having two formyl groups as a basic skeleton. From the viewpoint of improving the mold strength, terephthalaldehyde and derivatives of terephthalaldehyde are preferable, and terephthalaldehyde is more preferable.

The content of the curing accelerator in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, from the viewpoint of improving the template strength. The content of the curing accelerator in the binder composition is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass, from the viewpoint of solubility of the curing accelerator and improvement of mold strength. The following is more preferable.

[water]
The binder composition may further contain water. For example, when synthesizing various condensates such as a condensate of furfuryl alcohol and aldehydes, an aqueous solution of a raw material is used or condensed water is produced. Therefore, the condensate is usually in the form of a mixture with water. Obtained at. When using such a condensate in the binder composition, water may be removed by topping or the like, if necessary, but it is intentionally removed at the time of production as long as the curing reaction rate can be maintained. There is no need. Further, water may be further added for the purpose of adjusting the viscosity of the binder composition and the composition for molding to be easy to handle.

When water is further added for the purpose of adjusting the viscosity of the binder composition to be easy to handle, the content of water in the binder composition is preferably 0% by mass or more, more preferably 0.5% by mass or more. It is preferable, and 0.7% by mass or more is more preferable. However, from the viewpoint of improving the curing rate of the mold, the content of water in the binder composition is preferably 30% by mass or less, more preferably 5% by mass or less, and further preferably 3.5% by mass or less. The content of water in the binder composition is preferably 0 to 30% by mass, preferably 0 to 30% by mass, from the viewpoint of adjusting the viscosity of the binder composition to be easy to handle and improving the curing rate of the mold. .5 to 5% by mass is more preferable, and 0.7 to 3.5% by mass is further preferable.

The binder composition may further contain an additive such as a silane coupling agent. For example, it is preferable that the binder composition contains a silane coupling agent because the final strength of the obtained mold can be further improved. Examples of the silane coupling agent include N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl)-. Aminosilanes such as γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, Epoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilane, mercaptosilane, sulfidesilane, metharoxysilane, acryloxisilane and the like are used. Aminosilane, epoxysilane, and ureidosilane are preferred. More preferably, aminosilane and epoxysilane. Among the aminosilanes, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane is preferable. Among the epoxy silanes, 3-glycidoxypropylmethyldimethoxysilane is preferable.

The content of the silane coupling agent in the binder composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving the mold strength. From the same viewpoint, the content of the silane coupling agent in the binder composition is preferably 5% by mass or less, more preferably 4% by mass or less. From the same viewpoint, the content of the silane coupling agent in the binder composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass.

The binder composition of the present embodiment is preferably so-called self-hardening. Specifically, those which are liquid at 25 ° C. are preferable, and those having a viscosity at that time of 1 to 5000 mPa · s are more preferable.

[Curing agent composition]
The curing agent composition contains an acid from the viewpoint of preventing deterioration of the working environment during mold curing and from the viewpoint of improving the mold strength.

[acid]
The acid is not particularly limited as long as it is an acid capable of curing the binder composition. Examples of the acid include carboxylic acids such as 2,6-dihydroxybenzoic acid, oxalic acid, maleic acid, pyruvate, malonic acid, 2-furancarboxylic acid, phthalic acid, fumaric acid, lactic acid, citric acid, and malic acid, and xylene. Use one or more conventionally known sulfonic acid compounds such as sulfonic acid (particularly m-xylene sulfonic acid), toluene sulfonic acid (particularly p-toluene sulfonic acid), and methane sulfonic acid, phosphoric acid, and sulfuric acid. it can. In order to improve the mold strength, it is preferable to use an acid containing sulfur such as sulfonic acid and sulfuric acid as a curing agent. However, when a sulfur-containing acid such as sulfonic acid or sulfuric acid is used as a curing agent, SOx gas is generated during casting. Therefore, the content of the sulfur-containing acid in the curing agent composition is preferably 60% by mass or less, preferably 30. It is more preferably mass% or less, further preferably 10 mass% or less, and preferably 1 mass% or less. In such a case, the amount of SOx gas generated during casting can be reduced to zero. From the viewpoint of improving the strength of the template while suppressing SOx gas, the acid is preferably a carboxylic acid, and among the carboxylic acids, at least one selected from the group consisting of 2,6-dihydroxybenzoic acid, oxalic acid, and maleic acid. The above is more preferable, and oxalic acid is further preferable.

The content of the acid in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength according to the temperature of the working environment and the temperature of the refractory particles, but in general, it is generally adjusted. From the viewpoint of improving the mold strength, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 20% by mass or more is further preferable. Similarly, the content of the acid in the curing agent composition is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, from the viewpoint of improving the mold strength. The content of the acid in the curing agent composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass from the viewpoint of improving the mold strength.

[Other ingredients]
The curing agent composition may contain other components as long as the effects of the molding kit of the present embodiment are not impaired. Examples of the other components include the following components.

The curing agent composition and the molding composition may contain one or more solvents selected from the group consisting of alcohols and ether alcohols. Of these, alcohols are more preferred.

From the viewpoint of improving the template strength, the alcohols are preferably methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and benzyl alcohol, and the ether alcohols are ethylene glycol monoethyl ether and ethylene glycol mono. Butyl ether, ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, and ethylene glycol monophenyl ether are preferable.

The content of the solvent in the curing agent composition is appropriately adjusted in order to obtain a desired reaction rate and mold strength according to the temperature of the working environment and the temperature of the fire-resistant particles, but in general, it is generally adjusted. From the viewpoint of improving the mold strength and dissolving the curing agent composition, 5% by mass or more is preferable, 10% by mass or more is more preferable, and 20% by mass or more is further preferable. From the same viewpoint, the content of the solvent in the curing agent composition is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. From the same viewpoint, the content of the solvent in the curing agent composition is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass.

The state of the curing agent composition at the time of use does not matter. For example, in the case of a solid, it may be used by coating it on refractory particles, but it is preferably liquid at the time of use, and more preferably liquid at 25 ° C.

The ratio of the binder composition to the curing agent composition is preferably 20 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the binder composition from the viewpoint of improving the template strength. More than 30 parts by mass is more preferable, and 30 parts by mass or more is further preferable. From the same viewpoint, the ratio of the binder composition to the curing agent composition is preferably 100 parts by mass or less, preferably 90 parts by mass or less, based on 100 parts by mass of the binder composition. Is more preferable, and 80 parts by mass or less is preferable. The ratio of the binder composition to the curing agent composition is preferably 20 to 100 parts by mass with respect to 100 parts by mass of the binder composition from the viewpoint of improving the template strength. 25 to 90 parts by mass is more preferable, and 30 to 80 parts by mass is further preferable.

The mold molding kit of the present embodiment is suitably used for molding a self-hardening mold. Here, the self-hardening mold is a mold in which when the binder composition and the curing agent are mixed with sand, the polymerization reaction proceeds with the passage of time and the mold is cured. The temperature of the sand used at that time is in the range of −20 ° C. to 50 ° C., preferably 0 ° C. to 40 ° C. For sand at such a temperature, the mold can be appropriately cured by selecting an appropriate amount of a curing agent and adding it to the sand.

<Composition for molding>
The molding composition of the present embodiment contains the binder composition and the curing agent composition constituting the mold molding kit. The mold-molding composition can obtain sufficient mold strength without deteriorating the working environment at the time of mold production.

[Other ingredients]
The molding composition may be added with an acid curable resin, a curing accelerator, water, additives such as a silane coupling agent, an acidic substance, a solvent and the like to the extent that the effects of the present embodiment are not impaired. .. Additives such as acid-curable resin, curing accelerator, water, silane coupling agent, acidic substances, and solvent may be used in the components that can be used in the binder composition and in the curing agent composition. The same components and amounts that can be used can be used.

<Mold manufacturing method>
The method for producing a mold of the present embodiment includes a mixing step of mixing the binder composition and the curing agent composition constituting the mold molding kit with the refractory particles. The mold manufacturing method can obtain sufficient mold strength without deteriorating the working environment at the time of mold manufacturing.

[Refractory particles]
As the refractory particles, one or more conventionally known ones such as silica sand, chromate sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand can be used, and used fire resistance. Collected particles and regenerated particles can also be used. Among these, it is preferable to contain silica sand.

In the mixing step, the order in which the binder composition, the curing agent composition, and the refractory particles are added and mixed is not particularly limited, and the binder composition and the curing agent composition are mixed. After producing the molding composition, the molding composition and the refractory particles may be mixed, and the binder composition, the curing agent composition, and the refractory particles are added and mixed, respectively. However, from the viewpoint of storage stability and mold productivity, it is preferable to mix the binder composition, the curing agent composition, and the refractory particles to obtain a mold composition. Further, from the viewpoint of improving the mold strength, it is preferable to add the curing agent composition to the refractory particles and mix them, and then add and mix the binder composition. When two or more kinds of curing agent compositions are used, each curing agent composition may be mixed and then added, or each curing agent composition may be added separately.

The ratio of the fire-resistant particles, the binder composition, and the curing agent composition can be appropriately set in order to obtain a desired mold strength according to the temperature of the working environment and the temperature of the fire-resistant particles, but is generally used. From the viewpoint of improving the mold strength, the binder composition is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the fire resistant particles, and from the viewpoint of economic efficiency and the improvement of casting quality, the fire resistance 3.0 parts by mass or less is preferable, and 1.5 parts by mass or less is more preferable with respect to 100 parts by mass of the sex particles. From the viewpoint of improving the mold strength, the curing agent composition is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, and from the viewpoint of economic efficiency and casting quality, with respect to 100 parts by mass of the refractory particles. From the viewpoint of improvement, 2.0 parts by mass or less is preferable, and 1.0 part by mass or less is more preferable with respect to 100 parts by mass of the refractory particles. Further, the ratio of the refractory particles, the binder composition and the curing agent composition is 100 parts by mass of the refractory particles from the viewpoint of improving the mold strength, the economic efficiency and the casting quality. On the other hand, the binder composition is preferably 0.5 to 3.0 parts by mass, more preferably 0.5 to 1.5 parts by mass. From the viewpoint of improving the mold strength, economy, and casting quality, the curing agent composition is preferably 0.10 to 2.0 parts by mass with respect to 100 parts by mass of the refractory particles. 20 to 1.0 parts by mass is more preferable.

[Other ingredients]
In the mixing step, an acid curable resin, a curing accelerator, water, additives such as a silane coupling agent, an acidic substance, a solvent and the like may be added to the extent that the effects of the present embodiment are not impaired. Additives such as acid-curable resin, curing accelerator, water, silane coupling agent, acidic substances, and solvent may be used in the components that can be used in the binder composition and in the curing agent composition. The same components and amounts that can be used can be used.

As a method of mixing each raw material in the mixing step, a known general method can be used. For example, a method of adding each raw material by a batch mixer and kneading, or a method of supplying each raw material to a continuous mixer and kneading. There is a way to do it.

In the mold manufacturing method of the present embodiment, the mold can be manufactured by using the conventional mold manufacturing process as it is except for the mixing step. As a preferable method for producing a mold, a mixing step of mixing the binder composition and the curing agent composition constituting the mold molding kit with fire-resistant particles, and the mold composition are packed in a mold and said to be said. Examples thereof include a method for producing a mold having a curing step of curing the composition for a mold.

With respect to the embodiments described above, the present invention further discloses the following compositions, production methods, or uses.

<1> A mold molding kit for producing a mold composition comprising a binder composition and a curing agent composition, wherein the binder composition is a furanaldehyde compound and an aromatic hydroxy compound. A mold molding kit containing the condensate of the above and the curing agent composition containing an acid.
<2> The furan aldehyde compound is preferably at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural, and is preferably selected from the group consisting of furfural and 5-hydroxymethylfurfural. <1> Molding kit, in which at least one type is more preferable, and furfural is further preferable.
<3> The mold molding kit according to <1> or <2>, wherein the aromatic hydroxy compound is preferably an aromatic hydroxy compound having no carboxyl group.
<4> The aromatic hydroxy compound is phenol, cresol, xylenol, cumylphenol, nonylphenol, butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, resorcin, bisphenol A, bisphenol F, bisphenol C, catechol, At least one selected from the group consisting of hydroquinone, pyrogallol, and a condensate of fluoroglycin, phenols and formaldehyde is preferable, one having two or more hydroxyl groups is more preferable, and one selected from the group consisting of pyrogallol and resorcin. The mold molding kit according to any one of <1> to <3>, wherein at least one or more is more preferable, and resorcin is even more preferable.
<5> The weight average molecular weight (Mw) of the condensate of the furanaldehyde compound and the aromatic hydroxy compound is preferably 190 to 7,000, more preferably 300 to 6,000, and further preferably 500 to 4,000. The mold molding kit according to any one of <1> to <4>.
<6> The content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. Preferably, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, 1 to 70% by mass is preferable, 3 to 60% by mass is more preferable, and 5 to 50% by mass is further preferable. The mold molding kit according to any one of <1> to <5>.
<7> The mold molding kit according to any one of <1> to <6>, wherein the binder composition preferably further contains the furanaldehyde compound.
<8> The mold molding according to any one of <1> to <7>, wherein the content of the furanaldehyde compound in the binder composition is preferably 10% by mass or less, more preferably 0.5% by mass or less. kit.
<9> The mold molding kit according to any one of <1> to <8>, wherein the binder composition preferably further contains the aromatic hydroxy compound.
<10> The content of the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 10% by mass or less, and more preferably 7% by mass or less. The mold molding kit according to any one of <1> to <9>.
<11> The mold molding kit according to any one of <1> to <10>, wherein the binder composition preferably contains one or more compounds selected from the group consisting of urea and urea derivatives.
<12> One or more compounds selected from the group consisting of the urea and the urea derivative are urea; alkylene urea such as ethylene urea, propylene urea, butylene urea, and hydantin; methyl urea, 1,1-dimethyl urea, 1, Alkyl urea such as 3-dimethyl urea; cyclohexyl urea such as cyclohexyl urea and 1,3-dicyclohexyl urea; aryl urea such as phenyl urea, 1,1-diphenyl urea and 1,3-diphenyl urea; 2-hydroxyethyl urea and the like. Hydroxyalkylurea having 2 or more carbon atoms in the alkyl group; at least one selected from the group consisting of azodicarboxylic amide is preferable, urea and ethylene urea are more preferable, and urea is further preferable <1> to <11>. Urea molding kit described in Crab.
<13> The content of urea or the like in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and 8% by mass or less. Preferably, 7% by mass or less is more preferable, 6% by mass or less is further preferable, 0.5 to 8% by mass is preferable, 1 to 7% by mass is more preferable, and 1.5 to 6% by mass is further preferable <1>. ~ <12> The mold molding kit according to any one of the above.
<14> The mold molding kit according to any one of <1> to <13>, wherein the binder composition further contains an acid curable resin.
<15> The acid-curable resin is a furfuryl alcohol, a condensate of furfuryl alcohol, a condensate of furfuryl alcohol and aldehydes, a condensate of furfuryl alcohol, urea and aldehydes (urea-modified furan resin), urea. Condensation product of ethylene urea and aldehydes (condensation resin of urea / ethylene urea), condensation product of melamine and aldehydes, and condensation product of urea and aldehydes, or one selected from the group. It is preferable that at least one selected from the group consisting of a mixture of two or more kinds selected from the group and two or more kinds of cocondensates selected from these groups, and a condensate of furfuryl alcohol and furfuryl alcohol. , One or more selected from the condensate of furfuryl alcohol, urea and aldehydes, and the condensate of urea, ethylene urea and aldehydes, and at least one selected from the group consisting of these cocondensates are more preferable. , The molding kit according to <14>, wherein furfuryl alcohol is more preferable.
<16> The content of the acid-curable resin in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 25% by mass or more, and preferably 95% by mass or less. , 90% by mass or less is more preferable, 85% by mass or less is further preferable, 5 to 95% by mass is more preferable, 10 to 90% by mass is more preferable, and 25 to 85% by mass is further preferable to <14> or <15>. The described mold molding kit.
<17> The mold molding kit according to any one of <1> to <16>, wherein the binder composition further contains a silane coupling agent.
<18> The silane coupling agent is N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (amino). Aminosilanes such as ethyl) -γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyldimethoxy. Selected from the group consisting of epoxysilanes such as methylsilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilane, mercaptosilane, sulfidesilane, metharoxysilane, and acryloxisilane. At least one kind is preferable, at least one kind selected from the group consisting of aminosilane, epoxysilane and ureidosilane is more preferable, and at least one kind selected from the group consisting of aminosilane and epoxysilane is further preferable, and N-β is more preferable. The template molding kit according to <17>, wherein at least one selected from the group consisting of − (aminoethyl) -γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane is more preferable.
<19> The content of the silane coupling agent in the binder composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 5% by mass or less, and 4% by mass or less. The mold molding kit according to <17> or <18>, wherein 0.01 to 5% by mass is more preferable, and 0.05 to 4% by mass is more preferable.
<20> The binder composition preferably is liquid at 25 ° C., and more preferably has a viscosity of 1 to 5000 mPa · s at that time. <1> to <19>. Molding kit.
<21> The acid is a carboxylic acid such as 2,6-dihydroxybenzoic acid, oxalic acid, maleic acid, pyruvate, malonic acid, 2-furancarboxylic acid, phthalic acid, fumaric acid, lactic acid, citric acid, and malic acid. , Xylene sulfonic acid (particularly m-xylene sulfonic acid), toluene sulfonic acid (particularly p-toluene sulfonic acid), sulfonic acid compounds such as methane sulfonic acid, phosphoric acid, and at least one selected from the group consisting of sulfuric acid. Species or more are preferable, at least one selected from the group consisting of 2,6-dihydroxybenzoic acid, oxalic acid, and maleic acid is more preferable, and oxalic acid is further preferable, according to any one of <1> to <20>. Molding kit.
<22> The content of the sulfur-containing acid in the curing agent composition is preferably 60% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, still more preferably 1% by mass or less. The mold molding kit according to any one of <1> to <21>.
<23> The content of the acid in the curing agent composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 80% by mass or less, and preferably 70% by mass. The following is more preferable, 60% by mass or less is further preferable, 5 to 80% by mass is preferable, 10 to 70% by mass is more preferable, and 20 to 60% by mass is further preferable. Molding kit.
<24> The mold molding kit according to any one of <1> to <23>, wherein the curing agent composition preferably further contains a solvent.
<25> The solvent is preferably methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and benzyl alcohol, and the ether alcohols are ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol monohexyl. The mold molding kit according to <24>, wherein at least one selected from the group consisting of ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, and ethylene glycol monophenyl ether is preferable.
<26> The content of the solvent in the curing agent composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 90% by mass or less, and preferably 80% by mass. The molding according to <24> or <25>, wherein the following is more preferable, 70% by mass or less is further preferable, 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable. Kit for.
<27> The mold molding kit according to any one of <1> to <26>, wherein the curing agent composition is liquid, preferably liquid at 25 ° C.
<28> The ratio of the binder composition to the curing agent composition is preferably 20 parts by mass or more, preferably 25 parts by mass or more, based on 100 parts by mass of the binder composition. More preferably, 30 parts by mass or more is further preferable, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is preferable, 20 to 100 parts by mass is preferable, and 25 to 90 parts by mass is more preferable. The mold molding kit according to any one of <1> to <27>, wherein 30 to 80 parts by mass is more preferable.
<29> A mold molding composition containing a binder composition and a curing agent composition constituting the mold molding kit according to any one of <1> to <28>.
<30> The ratio of the binder composition to the curing agent composition is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, based on 100 parts by mass of the binder composition. Preferably, 30 parts by mass or more is further preferable, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is preferable, 20 to 100 parts by mass is preferable, and 25 to 90 parts by mass is more preferable. The composition for molding according to <28> or <29>, wherein ~ 80 parts by mass is more preferable.
<31> A method for producing a mold, which comprises a mixing step of mixing the binder composition and the curing agent composition constituting the mold molding kit according to any one of <1> to <28> with refractory particles.
<32> The ratio of the fire-resistant particles, the binder composition, and the curing agent composition is 0.5 parts by mass or more of the binder composition with respect to 100 parts by mass of the fire-resistant particles. Preferably, it is preferably 3.0 parts by mass or less, more preferably 1.5 parts by mass or less, preferably 0.5 to 3.0 parts by mass, more preferably 0.5 to 1.5 parts by mass, and the curing agent composition. The product is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, and 0.10 to 2.0 parts by mass. The method for producing a mold according to <31>, wherein 0.25 to 1.0 parts by mass is preferable.
<33> Use of the kit according to any one of <1> to <28> for manufacturing a mold.
<34> A mold-molding binder composition containing a condensate of a furanaldehyde compound and an aromatic hydroxy compound, wherein the aromatic hydroxy compound has two or more hydroxyl groups. object.
<35> The furan aldehyde compound is preferably at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural, and is preferably selected from the group consisting of furfural and 5-hydroxymethylfurfural. A binder composition for molding <34>, in which at least one or more is more preferable, and furfural is further preferable.
<36> The binder composition for molding <34> or <35>, wherein the aromatic hydroxy compound is preferably at least one selected from the group consisting of pyrogallol and resorcin, and resorcin is more preferable.
<37> The weight average molecular weight (Mw) of the condensate of the furanaldehyde compound and the aromatic hydroxy compound is preferably 190 to 7,000, more preferably 300 to 6,000, and further preferably 500 to 4,000. The binder composition for molding according to any one of <34> to <36>, which is preferable.
<38> The content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. Preferably, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, 1 to 70% by mass is preferable, 3 to 60% by mass is more preferable, and 5 to 50% by mass is further preferable. The binder composition for molding according to any one of <34> to <37>.
<39> The binder composition for molding according to any one of <34> to <38>, wherein the binder composition preferably further contains the furanaldehyde compound.
<40> The mold molding according to any one of <34> to <39>, wherein the content of the furanaldehyde compound in the binder composition is preferably 10% by mass or less, more preferably 0.5% by mass or less. Binder composition.
<41> The binder composition for molding according to any one of <34> to <40>, wherein the binder composition preferably further contains the aromatic hydroxy compound.
<42> The content of the aromatic hydroxy compound in the binder composition is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 10% by mass or less, and more preferably 7% by mass or less. The binder composition for molding according to any one of <34> to <41>.
<43> The binder for molding according to any one of <34> to <42>, wherein the binder composition preferably contains one or more compounds selected from the group consisting of urea and urea derivatives. Composition.
<44> One or more compounds selected from the group consisting of the urea and the urea derivative are urea; alkylene urea such as ethylene urea, propylene urea, butylene urea, and hydantin; methyl urea, 1,1-dimethyl urea, 1, Alkyl urea such as 3-dimethyl urea; cyclohexyl urea such as cyclohexyl urea and 1,3-dicyclohexyl urea; aryl urea such as phenyl urea, 1,1-diphenyl urea and 1,3-diphenyl urea; 2-hydroxyethyl urea and the like. Hydroxyalkylurea having 2 or more carbon atoms in the alkyl group; at least one selected from the group consisting of azodicarboxylic amide is preferable, urea and ethylene urea are more preferable, and urea is further preferable <34> to <43>. The binder composition for molding described in Urea.
<45> The content of urea or the like in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and 8% by mass or less. Preferably, 7% by mass or less is more preferable, 6% by mass or less is further preferable, 0.5 to 8% by mass is preferable, 1 to 7% by mass is more preferable, and 1.5 to 6% by mass is further preferable <34>. ~ <44> The binder composition for molding according to any one of.
<46> The binder composition for molding according to any one of <34> to <45>, wherein the binder composition further contains an acid curable resin.
<47> The acid-curable resin is a furfuryl alcohol, a condensate of furfuryl alcohol, a condensate of furfuryl alcohol and aldehydes, a condensate of furfuryl alcohol, urea and aldehydes (urea-modified furan resin), urea. Condensation product of ethylene urea and aldehydes (condensation resin of urea / ethylene urea), condensation product of melamine and aldehydes, and condensation product of urea and aldehydes, or one selected from the group. It is preferable that at least one selected from the group consisting of a mixture of two or more kinds selected from the group and two or more kinds of cocondensates selected from these groups, and a condensate of furfuryl alcohol and furfuryl alcohol. , One or more selected from the condensate of furfuryl alcohol, urea and aldehydes, and the condensate of urea, ethylene urea and aldehydes, and at least one selected from the group consisting of these cocondensates are more preferable. , Fulfuryl alcohol is more preferable. The binder composition for molding according to <46>.
<48> The content of the acid-curable resin in the binder composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 25% by mass or more, and preferably 95% by mass or less. , 90% by mass or less is more preferable, 85% by mass or less is further preferable, 5 to 95% by mass is more preferable, 10 to 90% by mass is more preferable, and 25 to 85% by mass is further preferable to <46> or <47>. The binder composition for molding described.
<49> The binder composition for molding according to any one of <34> to <48>, wherein the binder composition further contains a silane coupling agent.
<50> The silane coupling agent is N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (amino). Aminosilanes such as ethyl) -γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyldimethoxy. Selected from the group consisting of epoxysilanes such as methylsilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilane, mercaptosilane, sulfidesilane, metharoxysilane, and acryloxisilane. At least one kind is preferable, at least one kind selected from the group consisting of aminosilane, epoxysilane and ureidosilane is more preferable, and at least one kind selected from the group consisting of aminosilane and epoxysilane is further preferable, and N-β is more preferable. The binder for molding according to <49>, wherein at least one selected from the group consisting of- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane is more preferable. Composition.
<51> The content of the silane coupling agent in the binder composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 5% by mass or less, and 4% by mass or less. The binder composition for molding according to <49> or <50>, wherein 0.01 to 5% by mass is more preferable, and 0.05 to 4% by mass is more preferable.
<52> The binder composition preferably is liquid at 25 ° C., and more preferably has a viscosity of 1 to 5000 mPa · s at that time. <34> to <51>. Cinder composition for molding.
A composition for molding, which comprises the binder composition for molding and the curing agent composition according to any one of <53> and <34> to <52>.
<54> The composition for molding in <53>, wherein the curing agent composition contains an acid.
<55> The acid is a carboxylic acid such as 2,6-dihydroxybenzoic acid, oxalic acid, maleic acid, pyruvate, malonic acid, 2-furancarboxylic acid, phthalic acid, fumaric acid, lactic acid, citric acid, and malic acid. , Xylene sulfonic acid (particularly m-xylene sulfonic acid), toluene sulfonic acid (particularly p-toluene sulfonic acid), sulfonic acid compounds such as methane sulfonic acid, phosphoric acid, and at least one selected from the group consisting of sulfuric acid. <54> Molding composition, preferably at least one species, more preferably at least one selected from the group consisting of 2,6-dihydroxybenzoic acid, oxalic acid, and maleic acid, and even more preferably oxalic acid.
<56> The content of the sulfur-containing acid in the curing agent composition is preferably 60% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, still more preferably 1% by mass or less. <54> to <55> any of the molding compositions for molding.
<57> The content of the acid in the curing agent composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 80% by mass or less, and preferably 70% by mass. The following is more preferable, 60% by mass or less is further preferable, 5 to 80% by mass is preferable, 10 to 70% by mass is more preferable, and 20 to 60% by mass is further preferable. Any of <54> to <56> molding. Composition for.
<58> The composition for molding according to any one of <53> to <57>, wherein the curing agent composition preferably further contains a solvent.
<59> The solvent is preferably methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and benzyl alcohol, and the ether alcohols are ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol monohexyl. The molding composition according to <58>, wherein at least one selected from the group consisting of ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, and ethylene glycol monophenyl ether is preferable. ..
<60> The content of the solvent in the curing agent composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 90% by mass or less, and preferably 80% by mass. The molding according to <58> or <59>, wherein the following is more preferable, 70% by mass or less is further preferable, 5 to 90% by mass is preferable, 10 to 80% by mass is more preferable, and 20 to 70% by mass is further preferable. Composition for.
<61> The composition for molding according to any one of <53> to <60>, wherein the curing agent composition is liquid, preferably liquid at 25 ° C.
<62> The ratio of the binder composition to the curing agent composition is preferably 20 parts by mass or more, preferably 25 parts by mass or more, based on 100 parts by mass of the binder composition. More preferably, 30 parts by mass or more is further preferable, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is preferable, 20 to 100 parts by mass is preferable, and 25 to 90 parts by mass is more preferable. The composition for molding according to any one of <53> to <61>, wherein 30 to 80 parts by mass is more preferable.
<63> A mold composition containing the mold molding composition according to any one of <53> to <62> and refractory particles.
<64><34> A method for producing a mold, which comprises a mixing step of mixing the mold-molding binder composition and the curing agent composition according to any one of <34> to <52> with refractory particles.
<65> The method for producing a mold according to <64>, wherein the curing agent composition is a curing agent composition used for the mold molding composition according to any one of <53> to <62>.
<66> The ratio of the fire-resistant particles, the binder composition, and the curing agent composition is 0.5 parts by mass or more of the binder composition with respect to 100 parts by mass of the fire-resistant particles. Preferably, it is preferably 3.0 parts by mass or less, more preferably 1.5 parts by mass or less, preferably 0.5 to 3.0 parts by mass, more preferably 0.5 to 1.5 parts by mass, and the curing agent composition. The product is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, and 0.10 to 2.0 parts by mass. A method for producing a mold of <64> or <65>, preferably 0.20 to 1.0 parts by mass.
<67> Use for producing a mold of the composition according to any one of <53> to <62>.

Hereinafter, examples and the like that specifically demonstrate the present invention will be described.

<Evaluation method>
[Furfuryl alcohol / furfural content of binder composition]
The measurement was performed by gas chromatography. (Create a calibration curve with furfuryl alcohol and furfural)
Measurement condition:
-Internal standard solution: 1,6-hexanediol-Column: PEG-20M Chromosorb WAW DMCS 60/80 mes-h (manufactured by GL Sciences)
-Column temperature: 80 to 200 ° C (8 ° C / min)
・ Injection temperature: 210 ℃
・ Detector temperature: 250 ℃
-Carrier gas: 50 mL / min (He)

[Weight average molecular weight of condensate (Mw)]
The weight average molecular weight (Mw) of the condensate was measured by GPC (gel permeation chromatography) under the following conditions.
(A) Sample preparation: The sample was dissolved in tetrahydrofuran (THF) to prepare a sample for GPC.
(B) Column: TSKguardcolum H _XL- L, TSKgel G3000H _XL , TSKgel G2500H _XL were connected.
(C) Standard substance: Monodisperse polystyrene with known molecular weight (manufactured by Tosoh Corporation)
(D) Eluate: THF (flow rate: 1.0 mL / min)
(E) Temperature: 25 ° C.
(F) Detector: Ultraviolet spectrophotometer (wavelength: 285 nm)

<Preparation example>
[Production of condensate of furan aldehyde compound and aromatic hydroxy compound]
[Production of Furfural / Resorcinol Condensate 1]
89 parts by mass of furfural, 169 parts by mass of resorcin, and 234 parts by mass of furfuryl alcohol were mixed in a three-necked flask, and the pH was adjusted to 9 with a 48% aqueous potassium hydroxide solution. Then, the reaction was carried out at 40 ° C. for 8 hours to obtain a furfural resorcin reaction product 1. The reaction product contains 6 parts by mass of unreacted furfural, 74 parts by mass of resorcin, and 234 parts by mass of furfuryl alcohol, and the portion excluding each component is the furfural-resorcin condensate 1 (molar ratio of furfural to resorcin Furfural / resorcin) = 0.60, weight average molecular weight = 1,020).

[Production of Furfural / Resorcinol Condensate 2]
143 parts by mass of furfural, 119 parts by mass of resorcin, and 238 parts by mass of furfuryl alcohol were mixed in a three-necked flask, and the pH was adjusted to 7 with a 48% aqueous potassium hydroxide solution. Then, the reaction was carried out at 120 ° C. for 4 hours to obtain a furfural resorcin reaction product 2. The reaction product contains 39 parts by mass of unreacted furfural and 238 parts by mass of furfuryl alcohol, and the portion excluding each component is furfural-resorcin condensate 2 (molar ratio of furfural to resorcin (furfural / resorcin) = 1 .40, weight average molecular weight = 5,080).

[Structure of condensate]
The sample was dissolved in deuterated acetone to prepare a sample for ¹³ C-NMR. The sample was measured by ¹³ C-NMR, and a peak showing tertiary carbon, which is a reaction point between furfural and resorcinol, was observed around 35 to 40 ppm. From this result, it was confirmed that the furfural-resorcin condensate is a compound having a repeating unit represented by the following general formula 2.

[Production of furfural-pyrogallol condensate]
89 parts by mass of furfural, 194 parts by mass of pyrogallol, and 234 parts by mass of furfuryl alcohol were mixed in a three-necked flask, and the pH was adjusted to 9 with a 48% aqueous potassium hydroxide solution. Then, the reaction was carried out at 40 ° C. for 8 hours to obtain a furfural-pyrogallol reaction product. The reaction product contained 18 parts by mass of unreacted furfural, 101 parts by mass of pyrogallol, and 234 parts by mass of furfuryl alcohol, and the portion excluding each component was a furfural-pyrogallol condensate (molar ratio of furfural to pyrogallol (furfural). / Pyrogallol) = 0.60, weight average molecular weight = 940).

[Production of condensate A]
100 parts by mass of furfuryl alcohol, 35 parts by mass of paraformaldehyde and 13 parts by mass of urea are mixed in a three-necked flask, adjusted to pH 9 with a 25% aqueous sodium hydroxide solution, heated to 100 ° C., and then reacted at the same temperature for 1 hour. After that, the pH was adjusted to 4.5 with 37% hydrochloric acid, and the reaction was further carried out at 100 ° C. for 1 hour. Then, the pH was adjusted to 7 with a 25% aqueous sodium hydroxide solution, 5 parts by mass of urea was added, and the mixture was reacted at 100 ° C. for 30 minutes to obtain a reaction product. The unreacted furfuryl alcohol was determined by the above analysis method, and the portion excluding the unreacted furfuryl alcohol was designated as a condensate A. The composition of the condensate A was 89% by mass of the urea-modified furan resin and 11% by mass of water.

[Condensate B (formaldehyde / phenol condensate)]
A commercially available novolak type phenol resin (formaldehyde / phenol (molar ratio) = 0.9, weight average molecular weight = 1,520) was used.

[Production of condensate C]
100 parts by mass of 37% formaldehyde solution, 106 parts by mass of ethylene urea, and 25 parts by mass of urea were mixed in a three-necked flask and reacted at 100 ° C. for 3 hours to obtain a condensate C. The composition of the condensate C was 66% by mass of the urea-ethyleneurea cocondensate resin and 34% by mass of water.

<Examples 1 to 4 and Comparative Examples 1 to 5>
[Manufacturing of binder composition]
The furfural-resorcin condensate 1, furfural-pyrogallol condensate, furfural, resorcin, pyrogallol, FFA, condensate A, formaldehyde-phenol condensate, and silane coupling agent shown in Table 1 were mixed in a predetermined mass ratio and carried out. The binder compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were produced. In Table 1, "FFA" means furfuryl alcohol and "silane coupling agent" means N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane.

[Manufacturing of curing agent composition]
Sulfuric acid, xylene sulfonic acid, and water were mixed in the predetermined mass ratios shown in Table 1, respectively, to prepare the curing agent compositions of Examples 1 to 4 and Comparative Examples 1 to 5.

[Manufacturing of mold composition]
Under the conditions of 25 ° C. and 55% RH, 0.40 parts by mass of the curing agent composition shown in Table 1 was added to 100 parts by mass of fresh silica sand (freemantle) and mixed, and then the caking shown in Table 1 was added. 1.0 part by mass of the agent composition was added and these were mixed to obtain a mold composition.

<Examples 5 and 6, Comparative Example 6>
The furfural-resorcin condensate 2, furfural, FFA, condensate B, and silane coupling agent shown in Table 2 were mixed in a predetermined mass ratio to prepare the binder compositions of Example 3 and Comparative Example 5. In Table 2, "FFA" means furfuryl alcohol and "silane coupling agent" means 3-glycidoxypropylmethyldimethoxysilane.

[Manufacturing of curing agent composition]
Oxalic acid, p-toluenesulfonic acid, and methanol shown in Table 2 were mixed at predetermined mass ratios to prepare the curing agent compositions of Examples 5 and 6 and Comparative Example 6.

[Manufacturing of mold composition]
Under the conditions of 25 ° C. and 55% RH, 0.48 parts by mass of the curing agent composition shown in Table 2 was added to 100 parts by mass of fresh silica sand (freemantle) and mixed, and then the caking shown in Table 2 was added. 1.28 parts by mass of the agent composition was added, and these were mixed to obtain a mold composition.

<Test example>
Immediately after kneading, the mold composition is filled in a cylindrical test piece frame having a diameter of 50 mm and a height of 50 mm, and when 1 hour has passed, the mold is removed, and the compressive strength (MPa) is determined by the method described in JIS Z 2601. It was measured. “Compression strength after 1 hour” is defined, and the higher the value, the better the mold strength. Further, the same test piece frame was separately filled, and when 3 hours had passed, the die was removed, and 24 hours after filling, the compression strength (MPa) was measured by the method described in JIS Z 2601. “Compression strength after 24 hours” is set, and the higher the value, the better the mold strength. The odor of furfural was evaluated according to the following criteria.
3: There is almost no odor of furfural, and molding is possible 2: The odor of furfural is slightly felt, but molding is possible 1: The odor of furfural is strong, and the results of molding difficulty are shown in Tables 1 and 2.

Claims (16)

A mold molding kit for producing a mold composition, which comprises a binder composition and a curing agent composition.
The binder composition contains a condensate of a furanaldehyde compound and an aromatic hydroxy compound.
The curing agent composition contains an acid,
The furan aldehyde compound is at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural.
The aromatic hydroxy compound is an aromatic hydroxy compound having two or more hydroxyl groups and no carboxyl group.
A mold molding kit in which the content of sulfur-containing acid in the curing agent composition is 30% by mass or less . The molding kit according to claim 1, wherein the aromatic hydroxy compound is at least one selected from the group consisting of pyrogallol and resorcin. The mold molding kit according to claim 1 or 2 , wherein the weight average molecular weight (Mw) of the condensate of the furanaldehyde compound and the aromatic hydroxy compound is 190 to 7,000. The template according to any one of claims 1 to 3, wherein the content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition is 1% by mass or more and 70% by mass or less. Molding kit. Any of claims 1 to 4 , wherein the acid is at least one selected from the group consisting of sulfuric acid, xylene sulfonic acid, toluene sulfonic acid, methane sulfonic acid, 2,6-dihydroxybenzoic acid, oxalic acid, and maleic acid. The mold molding kit according to item 1. The invention according to any one of claims 1 to 5, wherein the binder composition further contains at least one selected from the group consisting of urea, a urea-modified furan resin, and a urea / ethylene-urea cocondensate resin. Molding kit. A mold molding composition containing the binder composition and the curing agent composition constituting the mold molding kit according to any one of claims 1 to 6 . A mold composition containing the mold molding composition according to claim 7 and refractory particles. A method for producing a mold, which comprises a mixing step of mixing the binder composition and the curing agent composition constituting the mold molding kit according to any one of claims 1 to 6 with refractory particles. A molding binder composition containing a condensate of a furanaldehyde compound and an aromatic hydroxy compound.
The furan aldehyde compound is at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural.
The aromatic hydroxy compounds, possess two or more hydroxyl groups, and aromatic hydroxy compounds der Ru binder composition for mold formation without the carboxyl group. The binder composition for molding according to claim 10 , wherein the aromatic hydroxy compound is at least one selected from the group consisting of pyrogallol and resorcin. The binder composition for molding according to claim 10 or 11 , wherein the weight average molecular weight (Mw) of the condensate of the furanaldehyde compound and the aromatic hydroxy compound is 190 to 7,000. The item according to any one of claims 10 to 12, wherein the content of the condensate of the furanaldehyde compound and the aromatic hydroxy compound in the binder composition for molding is 1% by mass or more and 70% by mass or less. The binder composition for molding described. A composition for molding, which comprises the binder composition for molding and the curing agent composition according to any one of claims 10 to 13 . A mold composition containing the mold molding composition according to claim 14 and refractory particles. A method for producing a mold, which comprises a mixing step of mixing the binder composition for molding, the curing agent composition, and the refractory particles according to any one of claims 10 to 13 .