JPH06182487A - Production of sand core - Google Patents

Abstract

PURPOSE:To provide the sand core having excellent coatability even if a sand core prototype is solidified by using a worm box method. CONSTITUTION:The sand core prototype is obtd. by compounding the org. acid salt, such as calcium acetate, and phthalic acid esters, such as dibutyl phthalate, or fatty acid esters at the time of molding the sand core. The surface of the sand core prototype is then subjected to uniform coating by immersion into a coating agent, etc., and is dried, by which the sand core having the excellent coatability is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sand core having excellent pressure resistance and excellent coating property for use in high pressure die casting of a casting having an undercut portion, such as a closed deck type automobile engine. It is about. More specifically, by blending a liquid organic compound having an interfacial tension of at least 2.0 mN / m or more with the coating agent at the time of molding by the warm box method, the same coating agent can be thickened only once on the surface of the sand core mold. The present invention relates to a method for producing a sand core that can be coated and is also suitable for high pressure casting.

Here, the excellent coating property means that when the sand core prototype is coated with the coating agent, the coating agent does not penetrate deeply into the sand core prototype as a thin liquid spreading inside the sand core prototype. , Or, without being repelled from the surface of the sand core prototype, only the surface layer of the sand core prototype is uniformly and firmly formed with a predetermined thickness, and easily and firmly so that it does not peel off. That is, it is to be sufficiently coated to withstand the high casting pressure during casting.

[0003]

2. Description of the Related Art Conventionally, when a die-cast casting is used to produce a cast product such as a closed-deck type automobile engine block or other aluminum alloy or magnesium alloy having an undercut portion, a collapsible sand core is used. Die casting is performed by using. When a collapsible sand core is to be obtained, the sand is first solidified into the desired shape, then the coating agent is applied to the surface of the solid sand core prototype, and when the molten metal is cast under high pressure Prevent the child from being damaged and the molten metal from entering the sand core.
After casting, it has been attempted to disintegrate the sand core with little force so that the sand core can be easily taken out, and the sand can be fully taken out to every corner. Of course, in that case, various attempts have been made in the past, such as the components of the sand core prototype, the method of hardening the sand, the components of the coating agent, the method of coating, etc., but the ones that are not sufficiently satisfactory have not yet been obtained. Is.

Among them, as a method of solidifying sand to obtain a sand core prototype, a hard-box method, a warm box method,
Shell mold method, cold box method, etc. are available.
As the Hardox method, for example, Japanese Patent Publication No. Sho 64-989.
The technique described in Japanese Patent No. 8 is known. In this method, the sand core prototype is composed of sand, an acid-curable resin, and a binder whose main component is an oxidant,
Hardened by sulfur dioxide.

[0005]

In the above-mentioned Hardox method, when the sand core prototype is obtained by hardening the sand shaped into a desired shape, it is hardened by using sulfur dioxide, that is, sulfurous acid gas. Therefore, since sulfur dioxide is used,
Due to the poor working environment, the use of gas that adversely affects the human body is not preferred in Japanese factories. Moreover, even if sulfurous acid gas is used, it is difficult to install auxiliary equipment for that purpose in order to prevent the human body from being adversely affected and the working environment from being deteriorated. Also subject to legal restrictions.

Therefore, the present inventor has decided to review the merit of the warm box method using a curing agent instead of the oxidizing agent and the sulfurous acid gas. In the warm box method, instead of using sulfurous acid gas to solidify a mixture of sand and a binder to obtain a sand core prototype, for example, in a mold for sand core prototype molding heated to 90 to 240 ° C. Then, a mixture of sand and a binder is blown with compressed air and heat-cured to mold the mixture. However,
In this case, even if the same coating agent as was used in the above Hardox method was applied to the sand core prototype, the coating agent would penetrate into the sand core prototype, resulting in a sufficient No thick coating layer was obtained.

[0007]

In the present invention, sand,
An interfacial tension between a furan resin, a curing agent for heat curing of the resin and an organic acid salt, and a slurry-like coating agent composed of a powdery refractory-based neutral water dispersion is at least 2.0 mN / m. There is a process of molding a sand core prototype using a liquid organic compound that does not dissolve in each other and has a boiling point higher than the molding temperature, and a neutral material containing powdery refractory as a main component on the surface of the sand core prototype A sand core having an excellent coating is obtained by a step of coating a slurry-like coating agent comprising an aqueous dispersion and a step of drying the sand core obtained by the coating.

The organic acid salt blended when the sand core prototype is formed is a salt formed between an organic acid and an inorganic ion. Formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, Oxalic acid, fumaric acid, maleic acid, succinic acid, tartaric acid, citric acid, butanetetracarboxylic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, benzenesulfonic acid, carboxylic acid such as toluenesulfonic acid,
Anions of organic acids such as sulfonic acid and Li ⁺ , Na ⁺ ,
K ⁺ , Cs ⁺ , Cu ⁺ , Cu ²⁺ , Mg ²⁺ , Ca ²⁺ , Ba
²⁺ , Zn ²⁺ , Al ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , C
Inorganic cations such as o ²⁺ , Ni ²⁺ and NH ₄ ⁺ are formed in the form of neutralizing charges. Examples thereof include potassium acetate, sodium acetate, magnesium acetate, calcium acetate, zinc acetate, barium acetate, magnesium acrylate, calcium acrylate, zinc acrylate, aluminum acrylate, sodium benzoate and the like.

Further, the liquid organic compound to be added when molding the sand core prototype is a phthalic acid ester, a trimellitic acid ester, an aliphatic monobasic acid ester, an aliphatic dibasic acid ester, a phosphoric acid ester, an epoxy fatty acid. ester,
It is selected from polyester, dihydric alcohol ester, and oxyacid ester, and examples thereof include dibutyl phthalate, di2-ethylhexyl phthalate, di2-ethylhexyl adipate, and di2-ethylhexyl sebacate.
Further, when a sand core prototype containing the above liquid organic compound is formed, sand, furan resin, and a curing agent for heat curing of the resin are mixed with, for example, calcium acetate and dibutyl phthalate or a solvent diluent thereof. Later, for example,
It is blown with compressed air into a mold for sand core prototype molding which is heated to 90 to 240 ° C., dried, and cured by heating.

[0010]

In the present invention, first, sand, furan resin,
An interfacial tension with a curing agent for heat curing of the resin, an organic acid salt, and a slurry-like coating agent composed of a neutral water dispersion containing a powdery refractory as a main component is at least 2.0 mN / m.
As described above, the sand core prototype is molded using the liquid organic compound that does not dissolve in each other and has a boiling point higher than the molding temperature. Next, the surface of the sand core prototype thus obtained is coated with a slurry-like coating agent composed of a neutral water dispersion containing a powdery refractory as a main component.

A sand-core prototype obtained by blending such an organic acid salt and a liquid organic compound is coated with a slurry-like coating agent composed of a neutral water dispersion containing powdery refractory as a main component. For example, the liquid organic compound attached to the surface of the sand core prototype does not allow the coating agent to penetrate into the sand core prototype, and the added organic acid salt has the effect of instantaneously coagulating the coating agent. Therefore, the sand core prototype surface can be thickly coated. Then, it is dried to form a uniform coating layer having a desired thickness.

By using the liquid organic compound and the organic acid salt in combination, the coating agent does not penetrate into the sand core mold even if the amount of the organic acid salt compounded at the time of molding is small. . By doing so, the sand core prototype can be solidified by the warm box method, and the surface of the sand core prototype can be coated with the coating agent in a desired state with certainty and ease. When the coated sand core obtained by the present invention is used, the molten core is not damaged or cracked when the molten core is cast under high pressure like high pressure die casting, and the molten core is There is no intrusion.

[0013]

[Examples] When manufacturing the sand core mold according to the claims, first, a furan resin, a curing agent for heat curing the same resin and an organic acid salt are added to a sand core aggregate such as core sand. Mix the organic compounds. As sand core aggregate, silica sand, zircon sand, chromite sand, cera beads, etc. are used, and as furan resin, furfuryl alcohol / formaldehyde resin, furfuryl alcohol / urea / formaldehyde resin, furfuryl alcohol / phenol / formaldehyde. Resin, furfur-based resin for so-called warm box such as furfuryl alcohol, phenol, urea, formaldehyde resin is used. As the curing agent for heat curing of the resin, at least one of benzene sulfonic acid, phenol sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, and lower alkyl sulfonic acid, and at least aluminum, copper, zinc, iron, or ammonium. 1
The one consisting of a salt with the seed is used. Further, a small amount of copper chloride, zinc chloride, iron chloride or the like may be used together as a curing accelerator.

Liquid organic compounds such as phthalic acid esters and aliphatic monobasic acid esters include dibutyl phthalate, di-2-ethylhexyl phthalate, isononyl phthalate, butyl oleate, dibutyl adipate, dibutyl sebacate, Tricresyl phosphate, epoxidized soybean oil,
Diethylene glycol dibenzoate, butylphthalyl butyl glycolate, etc. are used. The liquid organic compound is mixed in an amount of 0.05 to 0.5 parts by weight with respect to 100 parts by weight of sand. If the amount is less than 0.05 parts by weight, a thick coating layer will not be formed on the surface of the sand core prototype. On the other hand, if the blending amount is more than 0.5 parts by weight, the coating agent is repelled on the surface of the sand core mold, and a thick coating layer is not formed.

The above liquid organic compound may be blended as it is as a stock solution, or may be blended by dissolving it in an appropriate low boiling point solvent. The solvent used in the latter case is appropriately selected as long as it does not impair the storage stability and heat curability (molding property) of the composition comprising the sand core aggregate, the furan resin, and the curing agent for heat curing. . Therefore, the concentration and blending amount of the above liquid organic compound solution is 0.05 to 0.5 with respect to 100 parts by weight of sand in terms of liquid organic compound only.
Appropriately selected so that it will be a weight part.

Examples of the organic acid salts include organic acid salts such as calcium acetate, zinc acetate and aluminum acrylate. These organic acid salts are at least 0.
Add 1 part by weight or more. If the blending amount is less than 0.1 part by weight, a thick coating layer will not be formed on the sand core prototype surface. However, by using these liquid organic compounds and organic acid salts in combination, these organic acid salts may be blended in an amount of 0.05 parts by weight or more based on 100 parts by weight of sand. It should be noted that these organic acid salts can be blended in a larger amount in excess of 0.1 parts by weight or more with respect to 100 parts of sand as long as it does not hinder the molding of the sand core prototype.

The above-mentioned organic acid salt may be added as a solid such as powder, or may be added in the form of a solution such as an aqueous solution or a dispersion in an appropriate dispersant. The solvent or dispersant used in the latter case does not impair the storage stability and heat-curability (molding property) of the composition comprising the sand core aggregate, furan resin, and curing agent for heat curing of the resin. Is appropriately selected. Therefore, the concentration and blending amount of the above-mentioned organic acid salt solution or dispersion are at least 0.
The amount is appropriately selected so that the amount is not less than 05 parts by weight.

A mixture of these components is blown into a mold having a predetermined sand core-shaped cavity together with pressurized air, and, for example, a sand core mold is produced by a method called a warm box method. Was molded. In this case, the heating temperature of the core molding die is, for example, 90 to 240 ° C., preferably about 90 to 200 ° C., and the sand core mold is cured to a predetermined strength by heating for about 2 minutes. . For example, transverse strength 2
A sand core prototype of 0 to 50 kg was obtained.

Next, the surface of the sand core master formed as described above is coated with a coating agent. In this case, the sand core master may be dipped in the coating agent, or the surface of the sand core master may be brushed or sprayed with the coating agent. The coating agent was a slurry having a solid content of 50 to 90% by weight containing fine powder silica and fine powder alumina as main components and a small amount of colloidal silica. When the solid content is 50% by weight or less, the thickness of the coating layer becomes thin, and when it is 90% by weight or more, it becomes extremely difficult to stir the slurry. If the pH of this coating agent is not maintained at 7.0 ± 1.0, precipitation and solidification may occur even under stirring.

Other coating agents may be used as the coating agent. For example, about 30 to 80% by weight of an inorganic refractory material such as graphite, mica, fused silica, alumina, magnesia, carbon black and zircon powder, and about 1% of an inorganic binder such as colloidal silica, alumina sol, clay and amine-treated bentonite. It is also possible to use water consisting of ˜25% by weight. In this case, more preferred are fused silica and colloidal silica. Incidentally, about 10% by volume of methanol and kaolin may be added thereto.

In the coating agent, the interfacial tension between the organic acid salt and the coating agent is at least 2.0 mN.
The sand core prototype mixed with the liquid organic compound having a density of / m or more is dipped for several seconds, and then heated and dried. The drying conditions are 120 ° C. and about 10 minutes. The coating thickness is
When the above-mentioned organic acid salt and liquid organic compound are not blended, it is almost 0 mm when it is almost immersed in the sand core prototype, while it is sufficiently thick and has little penetration into the sand core prototype.
Moreover, the coating film is solid.

The coating layer may be one layer, but two layers are more preferable in order to improve the releasability between the product and the coating layer. As a coating agent for forming the second coating layer, for example, 1 liter of a 3% aqueous phenol resin solution, 500 g of mica powder,
Sodium dodecylbenzene sulfonate as a wetting agent 1
It is possible to use, for example, a mixture of 0 g and 1 g of octyl alcohol as an antifoaming agent with good stirring and mixing. This coating is carried out by immersing the sand core prototype that has been subjected to the first layer coating in the second layer coating agent, or brushing or spraying the second layer coating agent on the surface of the sand core template. , Dry to form.

As a more detailed example, an experimental example will be shown below. (Experimental Example 1) 100 parts by weight of flat sand as an aggregate, 1.5 parts by weight of a furan resin, and a commercially available curing agent mainly containing paratoluenesulfonate as a curing agent for the furan resin (FC-100, Kao Quaker product, 0.6 parts by weight of main component paratoluenesulfonic acid copper salt, and a commercially available additive (K-20, Kao Quaker product, main component silane compound).
06 parts by weight, 0.07 parts by weight of calcium acetate and 0.17 parts by weight of dibutyl phthalate (DBP) were mixed, and a sand core prototype for an engine block having a weight of about 2 kg was formed by the warm box method. The interfacial tension between DBP and the following coating agent was 6.8 mN / m. The molding conditions were a mold temperature of 120 ° C., a blowing pressure of 4.5 kg / cm ² , and a heating time of 90 seconds. The transverse rupture strength of the sand core prototype after standing for 1 day was 32 kg.

The sand core prototype was dipped in a slurry-like coating agent composed of a neutral water dispersion containing a powdery refractory as a main component for 1 to 2 seconds, and then 10 seconds in a circulating heating furnace at 120 ° C.
Min dried. The composition of the coating agent is finely divided silica 5
It was prepared by suspending 3 parts of colloidal silica in 0 part and 30 parts of finely powdered alumina in 20 parts of water, and the pH was adjusted to 7.0.

After finishing the above-mentioned first layer coating, a second layer coating was carried out next. As the coating agent for the second layer, 500 g of mica powder, 10 g of sodium dodecylbenzenesulfonate as a wetting agent, and 1 g of octyl alcohol as a defoaming agent were mixed well with 1 liter of a 3% aqueous phenol resin solution. I used one. That is, the sand core prototype that has been subjected to the first layer coating is added to the second layer coating agent in an amount of 1 to 2
After soaking for 2 seconds, it was dried for 10 minutes in a circulating hot air heating oven at 120 ° C.

The sand core obtained as described above is set in a mold and the aluminum alloy ADC10 is cast at a pressure of 600 k.
g / cm ² , spout speed 200 mm / sec, pouring temperature 7
High pressure casting was performed under the condition of 60 ° C. When sand was removed using a normal core knockout machine after casting, the core sand was completely removed, and an excellent cast product was obtained. The results are shown in Table 1.
Shown in.

[0027]

[Table 1]

(Comparative Example 1) 100 flat sand as an aggregate
Part, 1.5 parts of furan resin, 0.6 part of commercially available hardener containing para-toluene sulfonate as a hardener for furan resin (Kao Quaker FC-100, main component para-toluene sulfonic acid copper salt) , And commercially available additives (Kao Quaker product J-20, main component silane compound)
0.06 parts were mixed, and a sand core prototype for an engine block having a weight of about 2 kg was formed by the warm box method. Molding conditions are a mold temperature of 120 ° C., a blowing pressure of 4.5 kg / cm ² ,
The heating time was 90 seconds. The transverse rupture strength of the sand core prototype after standing for 1 day was 30 kg. Using this sand core prototype, the same treatment and operation as in Experimental Example 1 were performed. After removing the sand with a normal core knockout machine after casting,
The molten metal was inserted into the sand core mold and removal of the core sand was poor. The results are shown in Table 1.

COMPARATIVE EXAMPLE 2 The composition of Comparative Example 1 was mixed with calcium acetate in an amount of 0.07 part by weight with respect to sand to give a weight of about 2
A kg sand core prototype for an engine block was molded by the warm box method. The molding conditions were a mold temperature of 120 ° C., a blowing pressure of 4.5 kg / cm ² , and a heating time of 90 seconds. The transverse rupture strength of the sand core prototype after standing for 1 day was 27 kg.
Using this sand core prototype, the same treatment and operation as in Experimental Example 1 were performed. When sand was removed using a normal core knockout machine after casting, the molten metal was inserted into the sand core prototype and removal of core sand was poor. The results are shown in Table 1.

(Experimental Example 2) Di-2-ethylhexyl phthalate (DOP) was used in place of dibutyl phthalate in Experimental Example 1, and other treatments and operations were carried out in the same manner as in the case of dibutyl phthalate. Excellent results were obtained.
The results are shown in Table 1.

(Experimental Example 3) When aluminum acrylate was used in place of calcium acetate in Experimental Example 1 and the same treatment and operation were carried out in the same manner except for that, excellent results were obtained as in the case of calcium acetate. . The results are shown in Table 1.

(Experimental Example 4) When di2-ethylhexyl phthalate was used instead of dibutyl phthalate in Experimental Example 3 and the other treatments and operations were carried out in the same manner, it was as excellent as dibutyl phthalate. Results were obtained. The results are shown in Table 1.

[0033]

As described above, according to the present invention, sand, furan-based resin, curing agent for heat curing of the resin, organic acid salt, and neutral water dispersion containing powdery refractory as a main component are used. Forming a sand core mold using a liquid organic compound having an interfacial tension with a slurry-like coating agent of at least 2.0 mN / m or more, which does not dissolve each other and has a boiling point higher than the molding temperature, and this sand The coated sand core is manufactured by the steps of coating the core mold surface with the above-mentioned coating agent and drying the sand core mold obtained by the coating. At this time, the coating agent forms a uniform and appropriate thickness coating layer without penetrating into the sand core mold. Therefore, the sand core is
It can withstand a high casting pressure during casting.

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[Procedure amendment]

[Submission date] May 12, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sand having excellent pressure resistance and excellent coating property for use in high pressure die casting of a casting having an undercut portion, such as a closed deck type automobile engine. The present invention relates to a method for manufacturing a core prototype. More specifically, by blending a liquid organic compound having an interfacial tension with an organic acid salt and a coating agent of at least 2.0 mN / m at the time of molding by the warm box method, the sand core prototype surface is made uniform. Co-
Thick coating can be applied only once, and
The present invention relates to a method for producing a sand core suitable for high pressure casting.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013]

[Examples] When manufacturing the sand core prototype according to the claims, first, a sand core aggregate such as core sand, a furan resin, a curing agent for heat curing of the resin and an inorganic salt, and the liquid organic material are used. Compounds are mixed. As the sand core aggregate, silica sand, zircon sand, chromite sand, ceravise, etc. are used, and as the furan-based resin, furfuryl alcohol-formaldehyde resin, furfuryl alcohol-urea-formaldehyde resin, full-furyl alcohol. Furyl alcohol phenol formaldehyde resin, full frill alcohol phenol phenol
A furan resin for so-called warm mox such as urea / formaldehyde resin is used. Further, as the curing agent for heating and curing the resin, benzenesulfonic acid, phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid,
A salt of at least one of lower alkyl sulfonic acid and at least one of aluminum, copper, zinc, iron and ammonium is used. Also, as a curing accelerator,
A small amount of copper chloride, zinc chloride, iron chloride or the like may be used together.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Examples of the organic acid salts include organic acid salts such as calcium acetate, zinc acetate and aluminum acrylate. These organic acid salts are used in the system in which the liquid organic compound is not mixed, at least 0.
Add 1 part by weight or more. If the blending amount is less than 0.1 part by weight, a thick coating layer is not formed on the sand core prototype surface. However, by using these liquid organic compounds and organic acid salts in combination, these organic acid salts may be mixed in an amount of 0.05 parts by weight or more based on 100 parts by weight of sand. It should be noted that these organic acid salts can be further mixed in a large amount in excess of 0.05 parts by weight or more with respect to 100 parts by weight of sand as long as it does not hinder the molding of the sand core prototype.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Kawanishi Kenji Kawanishi 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Ltd. Hirakata Research Laboratory (72) Inventor Hideyuki Iitani 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Hirakata Research Institute Co., Ltd.

Claims (1)

[Claims] 1. Interfacial tension between sand, furan resin, a curing agent for heat curing of the resin, an organic acid salt, and a slurry-like coating agent comprising a neutral water dispersion containing powdery refractory as a main component. Of at least 2.0 mN / m or more, which do not dissolve in each other, and which have a boiling point higher than the molding temperature, are used to mold a sand core mold, and the surface of the sand core mold is coated with the above coating agent. A method for producing a sand core, comprising a coating step and a step of drying the sand core obtained by the coating.