CN117858773A - Casting mould composition - Google Patents

Casting mould composition Download PDF

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Publication number
CN117858773A
CN117858773A CN202280057880.9A CN202280057880A CN117858773A CN 117858773 A CN117858773 A CN 117858773A CN 202280057880 A CN202280057880 A CN 202280057880A CN 117858773 A CN117858773 A CN 117858773A
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CN
China
Prior art keywords
mass
composition
curing agent
mold
fatty acid
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Pending
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CN202280057880.9A
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Chinese (zh)
Inventor
键谷昌彦
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Kao Corp
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Kao Corp
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Publication of CN117858773A publication Critical patent/CN117858773A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only

Abstract

The present invention provides a casting mold composition comprising refractory particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms. According to the present invention, a molding composition having excellent fluidity while suppressing deterioration of handleability during use and storage of a binder composition for molding and a curing agent composition for molding can be provided. RO- (CH) 2 CH 2 O) n-H (1) (in the general formula (1), R represents a straight chain or branched chainAlkyl or alkenyl groups having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23.

Description

Casting mould composition
Technical Field
The present invention relates to a molding composition.
Background
As the binder used in the production of the mold, various organic binders are used. Among them, alkali phenolic resins are used in a large amount as organic binders capable of improving the quality of castings and the working environment, particularly in the field of cast steel.
However, when the alkali phenolic resin is kneaded with reclaimed sand, which is specifically reclaimed sand as artificial sand, that is, reclaimed sand for reuse after casting once, and reclaimed sand for reuse many times, the fluidity of the mold composition is significantly deteriorated as compared with that of new sand, and the mold composition cannot be tightly filled. Therefore, casting defects such as sand inclusion, sand sticking, and infiltration sand sticking occur in the obtained castings, and there is a disadvantage that the quality of the castings is lowered.
In order to solve the above problems, various proposals have been made heretofore for improving the fluidity of casting sand. For example, when molding a mold by kneading a self-setting water-soluble phenolic resin with a curing agent using artificial sand as refractory particles, JP-A10-216895 discloses that a surfactant and a lubricant are contained in a binder for the purpose of improving the fluidity of a molding composition, and JP-A2009-40896 discloses that a nonionic surfactant is contained in a curing agent for an alkali phenolic resin for the purpose of improving the fluidity of kneaded sand and reducing the generation of bubbles in one liquid.
Disclosure of Invention
The present invention is a mold composition that includes,
the flame-retardant resin composition comprises flame-retardant particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H(1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
The present invention also provides a curing agent composition for mold shaping, which contains a curing agent, a compound represented by the following formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H (1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
The present invention also provides a method for producing a molding composition, which comprises a step of mixing a molding binder composition containing refractory particles and a phenolic resin, and a curing agent composition for molding.
Drawings
Fig. 1 is a cross-sectional view of a wood pattern for evaluating smoothness of a mold surface.
Fig. 2 is a photograph showing the appearance of a mold of an example manufactured for evaluating the smoothness of a surface.
Fig. 3 is a photograph showing the appearance of a comparative casting mold manufactured for evaluating the surface smoothness.
Fig. 4 is a cross-sectional view of a mold or the like in evaluation of casting quality.
Fig. 5 is a cross-sectional view of a mold or the like in evaluation of casting quality.
Fig. 6 is a cross-sectional view of a mold or the like in evaluation of casting quality.
Fig. 7 is a cross-sectional view of a mold or the like in evaluation of casting quality.
Fig. 8 is a photograph of the appearance of a casting of an example in the evaluation of the quality of the casting.
Fig. 9 is a photograph of the appearance of a casting of a comparative example in the evaluation of the quality of the casting.
Detailed Description
In Japanese patent application laid-open No. 10-216895, when a surfactant is added to a binder (alkali phenolic resin), bubbles are generated at the time of preparation, use, and the like, and the operation becomes inconvenient. In addition, when a lubricant such as a fatty acid is added to the binder, the fatty acid is neutralized and precipitated as an agglomerate, and the handling during storage becomes inconvenient. On the other hand, in japanese patent application laid-open No. 2009-40896, when a nonionic surfactant is added to a curing agent for an alkali phenolic resin, even if a certain amount or more of the nonionic surfactant is added, the fluidity improving effect has reached a top point, and it is difficult to achieve a significant fluidity improvement.
The present invention provides a molding composition which is excellent in fluidity while suppressing deterioration of handleability during use and storage of a molding adhesive composition and a molding curing agent composition, and a method for producing the same.
The present invention is a mold composition that includes,
the flame-retardant resin composition comprises flame-retardant particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H (1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
The present invention also provides a curing agent composition for mold shaping, which contains a curing agent, a compound represented by the following formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H (1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
The present invention also provides a method for producing a molding composition, which comprises a step of mixing a molding binder composition containing refractory particles and a phenolic resin, and a curing agent composition for molding.
According to the present invention, it is possible to provide a molding composition having excellent fluidity while suppressing deterioration of handleability during use and storage of a binder composition for molding and a curing agent composition for molding, and a method for producing the same.
An embodiment of the present invention will be described below.
< moulding composition >
The casting mold composition of the present embodiment contains refractory particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H (1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
The mold composition of the present embodiment is excellent in fluidity. The reason why the mold composition of the present embodiment exerts such effects is not limited, but can be considered as follows.
It is considered that when the nonionic surfactant is contained in the casting composition containing the phenolic resin, the curing agent and the refractory particles, the surface tension of the mixture of the phenolic resin and the curing agent is reduced, the sliding property between the refractory particles is improved, and the fluidity is improved. On the other hand, when the fatty acid is contained in the casting composition, it is considered that the fatty acid reacts with alkali metal in the water-soluble phenol resin to become a fatty acid salt and then precipitates, and the bearing effect is exhibited between the refractory particles, thereby improving the fluidity. That is, the fluidity-improving effect obtained by containing a nonionic surfactant is mechanically different from the fluidity-improving effect obtained by containing a fatty acid. It is considered that the fluidity improving effect is greatly improved by the combination of additives of different mechanisms.
[ refractory particles ]
As the refractory particles, conventionally known refractory particles such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, synthetic mullite sand, and alumina ball sand may be used, and regenerated sand obtained by recovering and then regenerating the used refractory particles may be used. The refractory particles may be used alone or in combination of 2 or more.
The average particle diameter of the refractory particles is preferably 50 μm or more, more preferably 100 μm or more, further preferably 150 μm or more from the viewpoint of improving the mold strength and from the viewpoint of economy, and is preferably 1000 μm or less, more preferably 800 μm or less, further preferably 600 μm or less from the viewpoint of improving the mold strength. In the present specification, the average particle diameter was measured by the method described in examples.
[ phenolic resin ]
The phenolic resin is generally a resin obtained by polycondensing a phenol compound and an aldehyde compound under alkaline conditions. Among them, as the phenol compound, 1 or a mixture of 2 or more kinds of phenol compounds including phenol, bisphenol a, bisphenol F, cresol, 3, 5-xylenol, resorcinol, catechol, nonylphenol, p-tert-butylphenol, isopropenylphenol, phenylphenol, phenols of other substituted phenols, a mixture of various phenol compounds such as cashew nut shell liquid, and the like can be used. As the aldehyde compound, 1 or a mixture of 2 or more types of formaldehyde, acetaldehyde, furfural, glyoxal, and the like can be used. These compounds may be used in the form of an aqueous solution as required. Further, a monomer capable of condensing with an aldehyde compound such as urea, melamine, or cyclohexanone, a monohydric aliphatic alcohol compound such as methanol, ethanol, isopropanol, n-propanol, or butanol, a polyacrylate of a water-soluble polymer, a cellulose derivative polymer, polyvinyl alcohol, or a lignin derivative may be mixed with these.
The alkali catalyst used for the synthesis of the phenolic resin includes alkali metal hydroxides such as LiOH, naOH, KOH, and NaOH and KOH are particularly preferable. In addition, these base catalysts may be used in combination.
The phenolic resin is preferably prepared as an aqueous solution, and is preferably 30 mass% or more, more preferably 50 mass% or more, as the mass of the solid component (the mass of the solid after drying at 105 ℃ for 3 hours) from the viewpoint of improving the mold strength. The mass of the solid content of the aqueous phenolic resin solution is preferably 85% by mass or less, more preferably 75% by mass or less, from the viewpoint of improving the mold strength and the workability. The mass of the solid content of the aqueous phenolic resin solution is preferably 30 to 80% by mass, more preferably 50 to 75% by mass, from the viewpoint of improving the mold strength and the workability.
The weight average molecular weight (Mw) of the phenolic resin is preferably 500 or more, more preferably 800 or more, and even more preferably 1200 or more from the viewpoint of improving the mold strength. The weight average molecular weight (Mw) of the phenolic resin is preferably 8000 or less, more preferably 5000 or less, and even more preferably 3000 or less from the viewpoint of improving the mold strength and workability. The weight average molecular weight (Mw) of the phenolic resin is preferably 500 to 8000, more preferably 800 to 5000, and even more preferably 1200 to 3000, from the viewpoint of improving the mold strength and workability. The weight average molecular weight of the phenolic resin was measured by the method described in examples.
From the viewpoint of improving the mold strength, the content of the phenolic resin in the mold composition is preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, based on 100 parts by mass of the refractory particles. From the viewpoint of improving workability and economy, the content of the phenolic resin in the mold composition is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the refractory particles. From the viewpoint of improving the mold strength, workability, and economy, the content of the phenolic resin in the mold composition is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 1 part by mass, relative to 100 parts by mass of the refractory particles.
[ Compounds represented by the above general formula (1) ]
The compound represented by the general formula (1) contains a compound in which R in the general formula (1) represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably contains a compound in which R represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms.
The compound represented by the general formula (1) contains a compound having 8 or more, preferably 10 or more, more preferably 12 or more carbon atoms of an alkyl group or alkenyl group represented by R in the general formula (1) from the viewpoint of improving the fluidity of the molding composition and the availability of the raw material. The compound represented by the general formula (1) contains a compound having 22 or less carbon atoms, preferably 20 or less carbon atoms, more preferably 18 or less carbon atoms, which is an alkyl group or alkenyl group represented by R in the general formula (1), from the viewpoint of improving the fluidity, the storage stability and the availability of the raw material of the molding composition. The compound represented by the general formula (1) contains a compound having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms, of an alkyl group or alkenyl group represented by R in the general formula (1), from the viewpoint of improving the fluidity, the storage stability and the availability of the raw material of the molding composition.
The compound represented by the general formula (1) contains a compound in which n in the general formula (1) is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more from the viewpoint of improving the fluidity of the molding composition and the availability of the raw material. The compound represented by the above general formula (1) contains a compound in which n in the above general formula (1) is 23 or less, preferably 18 or less, more preferably 13 or less from the viewpoint of improving the fluidity, the storage stability and the availability of the raw material of the molding composition. The compound represented by the general formula (1) contains a compound having n of 1.2 to 23, preferably 1.5 to 18, more preferably 1.8 to 13 in the general formula (1) from the viewpoint of improving the fluidity, the storage stability and the availability of the raw material of the molding composition.
From the viewpoint of improving the fluidity of the mold composition, the content of the compound represented by the general formula (1) in the mold composition is preferably 0.001 parts by mass or more, more preferably 0.003 parts by mass or more, and even more preferably 0.005 parts by mass or more, based on 100 parts by mass of the refractory particles. The content of the compound represented by the general formula (1) in the mold composition is preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and even more preferably 0.02 parts by mass or less per 100 parts by mass of the refractory particles from the viewpoint of improving the fluidity, foam suppressing property, storage stability and economical efficiency of the mold composition. The content of the compound represented by the general formula (1) in the mold composition is preferably 0.001 to 0.1 part by mass, more preferably 0.003 to 0.05 part by mass, and even more preferably 0.005 to 0.02 part by mass, based on 100 parts by mass of the refractory particles, from the viewpoint of improving the fluidity, foam suppression, storage stability, and economical efficiency of the mold composition.
From the viewpoint of improving the fluidity of the mold composition, the content of the compound represented by the general formula (1) in the mold composition is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, still more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, relative to 100 parts by mass of the total of the phenolic resin and the curing agent. The content of the compound represented by the general formula (1) in the molding composition is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less based on 100 parts by mass of the total of the phenolic resin and the curing agent, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the molding composition. The content of the compound represented by the general formula (1) in the molding composition is preferably 0.5 to 15 parts by mass, more preferably 0.75 to 15 parts by mass, even more preferably 1 to 10 parts by mass, even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total of the phenolic resin and the curing agent, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the molding composition.
[ fatty acids ]
The fatty acid contains a fatty acid having 8 or more carbon atoms, preferably 10 or more carbon atoms, more preferably 12 or more carbon atoms, from the viewpoint of improving the fluidity of the molding composition and the availability of the raw material. The fatty acid contains a fatty acid having a carbon number of 22 or less, preferably 20 or less, more preferably 18 or less from the viewpoint of storage stability, improvement of fluidity of the molding composition, and availability of the raw material. The fatty acid contains a fatty acid having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms, from the viewpoint of storage stability, improvement of fluidity of the molding composition, and availability of the raw material.
The fatty acid preferably contains a fatty acid having a melting point of 45 ℃ or less from the viewpoints of storage stability and improvement of fluidity of the molding composition.
Examples of the fatty acid include linear aliphatic carboxylic acid, branched aliphatic carboxylic acid, saturated aliphatic carboxylic acid, and unsaturated aliphatic carboxylic acid, and specifically lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, oleic acid, linoleic acid, and linolenic acid. From the viewpoint of improving fluidity of the molding composition and the availability of raw materials, the fatty acid preferably contains 1 or more selected from oleic acid, linolenic acid and lauric acid.
From the viewpoint of improving the fluidity of the mold composition, the content of the fatty acid in the mold composition is preferably 0.0005 parts by mass or more, more preferably 0.00075 parts by mass or more, and even more preferably 0.001 parts by mass or more, relative to 100 parts by mass of the refractory particles. The content of the fatty acid in the mold composition is preferably 0.05 parts by mass or less, more preferably 0.02 parts by mass or less, and even more preferably 0.01 parts by mass or less based on 100 parts by mass of the refractory particles, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the mold composition. The content of the fatty acid in the mold composition is preferably 0.0005 to 0.05 parts by mass, more preferably 0.00075 to 0.02 parts by mass, and even more preferably 0.001 to 0.01 parts by mass, based on 100 parts by mass of the refractory particles, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the mold composition.
From the viewpoint of improving the fluidity of the mold composition, the content of the fatty acid in the mold composition is preferably 0.05 parts by mass or more, more preferably 0.075 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.25 parts by mass or more, and still more preferably 0.4 parts by mass or more, relative to 100 parts by mass of the total of the phenolic resin and the curing agent. The content of the fatty acid in the mold composition is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass of the total of the phenolic resin and the curing agent, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the mold composition. From the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the mold composition, the content of the fatty acid in the mold composition is preferably 0.05 to 7 parts by mass, more preferably 0.075 to 7 parts by mass, still more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total of the phenolic resin and the curing agent.
From the viewpoint of improving the fluidity of the mold composition, the ratio of the content of the fatty acid (content of the fatty acid/(total content of the compound represented by the general formula (1)) relative to the total content of the compound represented by the general formula (1) and the fatty acid in the mold composition is preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.1 or more. The ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid in the molding composition is preferably 0.6 or less, more preferably 0.5 or less, and even more preferably 0.4 or less, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the molding composition. The ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid in the molding composition is preferably 0.05 to 0.6, more preferably 0.08 to 0.5, and even more preferably 0.1 to 0.4, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the molding composition.
From the viewpoint of improving the fluidity of the mold composition, the mass ratio of the compound represented by the general formula (1) to the fatty acid in the mold composition (mass of the compound represented by the general formula (1)/mass of the fatty acid) is preferably 0.15 or more, more preferably 0.5 or more, and still more preferably 0.9 or more. The mass ratio of the compound represented by the general formula (1) to the fatty acid in the molding composition is preferably 100 or less, more preferably 20 or less, and even more preferably 10 or less, from the viewpoint of improving the fluidity, foam suppression, storage stability, and economy of the molding composition. The mass ratio of the compound represented by the general formula (1) to the fatty acid in the molding composition is preferably 0.15 to 100, more preferably 0.5 to 20, still more preferably 0.9 to 10, from the viewpoint of improving the fluidity, foam suppressing property, storage stability and economical efficiency of the molding composition.
[ curing agent ]
The curing agent may be used without particular limitation as long as it cures the phenolic resin, but from the viewpoint of improving the mold strength, an ester compound is preferable. Examples of the ester compound include lactones, organic ester compounds derived from monohydric or polyhydric alcohols having 1 to 10 carbon atoms and organic carboxylic acids having 1 to 10 carbon atoms, carbonates, and mixtures thereof. Specifically, examples of the lactones include gamma-butyrolactone, propiolactone, and epsilon-caprolactone. Examples of the organic ester compound include ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol monoacetate, ethyl acetoacetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, triacetin, dimethyl 2-ethylsuccinate, dimethyl 2-methylglutarate, and dimethyl 2-methyladipate, and examples of the carbonate include ethylene carbonate and propylene carbonate. Among them, from the viewpoint of easy control of mold strength, availability and economy, 1 or more selected from the group consisting of gamma-butyrolactone, propiolactone, epsilon-caprolactone, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triacetin, propylene carbonate, dimethyl glutarate, dimethyl adipate, triethylene glycol diacetate, dimethyl succinate, dimethyl 2-ethylsuccinate, dimethyl 2-methylpentanedioate and dimethyl 2-methyladipate are preferable. In addition, methyl formate is preferably used in the gas-curable casting method using an ester compound.
The content of the curing agent in the mold composition is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and still more preferably 25 parts by mass or more, based on 100 parts by mass of the phenolic resin, from the viewpoint of improving the mold strength and the curing speed. The content of the curing agent in the mold composition is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less, based on 100 parts by mass of the phenolic resin, from the viewpoint of improving the mold strength, the viewpoint of improving the curing speed, and the viewpoint of economy. The content of the curing agent in the mold composition is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, still more preferably 20 to 50 parts by mass, and still more preferably 25 to 45 parts by mass, based on 100 parts by mass of the phenolic resin, from the viewpoint of improving the mold strength, the viewpoint of improving the curing speed, and the viewpoint of economy.
[ other Components ]
The above-mentioned molding composition preferably contains resorcinol from the viewpoint of improving the working environment. Resorcinol has a formaldehyde capturing effect, so that formaldehyde contained in the thermal decomposition gas during casting, after casting, and during mold removal can be reduced.
The content of resorcinol in the above-mentioned molding composition is preferably 0.001 mass% or more, more preferably 0.003 mass% or more, and still more preferably 0.005 mass% or more, from the viewpoint of reducing formaldehyde and improving the molding strength. The content of resorcinol in the above-mentioned molding composition is preferably 0.06 mass% or less, more preferably 0.04 mass% or less, and still more preferably 0.02 mass% or less from the viewpoints of formaldehyde reduction, improvement in molding strength, and economy. The content of resorcinol in the above-mentioned molding composition is preferably 0.001 to 0.06 mass%, more preferably 0.003 to 0.04 mass%, and even more preferably 0.005 to 0.02 mass%, from the viewpoint of reducing formaldehyde, improving the molding strength, and economical efficiency.
The above-mentioned molding composition may contain other components within a range that does not impair the effects of the present invention. Examples of the other component include solvents such as water, alcohols, ether alcohols, and glycols. Among them, from the viewpoint of the feel of the kneaded sand and the viewpoint of odor control, 1 or more selected from the group consisting of water, alcohols, ether alcohols and glycols is preferable, 1 or more selected from the group consisting of water, alcohols having 1 to 3 carbon atoms, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol and benzyl alcohol is more preferable, 1 or more selected from the group consisting of methanol, ethanol, diethylene glycol and triethylene glycol is more preferable, and water and triethylene glycol are still more preferable.
The content of the solvent in the mold composition is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.03 mass% or more, from the viewpoint of uniformly mixing the raw materials. The content of the solvent in the mold composition is preferably 0.9 mass% or less, more preferably 0.8 mass% or less, and even more preferably 0.7 mass% or less, from the viewpoints of uniformly mixing the raw materials, suppressing odor, and economy. The content of the solvent in the molding composition is preferably 0.01 to 0.9 mass%, more preferably 0.02 to 0.8 mass%, and even more preferably 0.03 to 0.7 mass%, from the viewpoints of uniformly mixing the raw materials, suppressing odor, and economy.
Curing agent composition for mold shaping
The mold-forming curing agent composition (hereinafter, may be simply referred to as curing agent composition) of the present embodiment includes the curing agent, the compound represented by the general formula (1), and the fatty acid. When the compound represented by the above general formula (1) and the fatty acid having 8 to 22 carbon atoms are added to the binder composition for mold molding, bubbles or aggregates are generated, but when the compound represented by the above general formula (1) and the fatty acid having 8 to 22 carbon atoms are contained in the curing agent composition, the fluidity of the mold composition can be improved while suppressing bubbles or aggregates.
The content of the compound represented by the general formula (1) in the curing agent composition is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of improving the fluidity of the mold composition. The content of the compound represented by the general formula (1) in the curing agent composition is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving the fluidity, the storage stability, the low-temperature stability, and the economical efficiency of the molding composition. The content of the compound represented by the general formula (1) in the curing agent composition is preferably 1 to 10% by mass, more preferably 1.5 to 7% by mass, and even more preferably 2 to 5% by mass, from the viewpoint of improving the fluidity, the storage stability, the low-temperature stability, and the economical efficiency of the molding composition.
The content of the fatty acid in the curing agent composition is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and still more preferably 0.3 mass% or more, from the viewpoint of improving the fluidity of the mold composition. The content of the fatty acid in the curing agent composition is preferably 6% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, from the viewpoint of improving the fluidity, the storage stability, the low-temperature stability and the economical viewpoint of the molding composition. The content of the compound represented by the general formula (1) in the curing agent composition is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, still more preferably 0.3 to 4% by mass, still more preferably 0.3 to 3% by mass, from the viewpoint of improving the fluidity, the storage stability, the low-temperature stability and the economical efficiency of the molding composition.
The content of the curing agent in the curing agent composition is preferably 60 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, and still more preferably 85 mass% or more, from the viewpoint of improving the mold strength. The content of the curing agent in the curing agent composition is preferably 99 mass% or less, more preferably 98 mass% or less, and still more preferably 97 mass% or less, from the viewpoint of improving the mold strength and economy. The content of the curing agent in the curing agent composition is preferably 60 to 99% by mass, more preferably 70 to 98% by mass, still more preferably 80 to 97% by mass, and still more preferably 85 to 97% by mass, from the viewpoint of improving the mold strength and from the viewpoint of economy.
From the viewpoint of improving the fluidity of the molding composition, the ratio of the content of the fatty acid (content of the fatty acid/(total content of the compound represented by the general formula (1)) relative to the total content of the compound represented by the general formula (1) and the fatty acid in the curing agent composition is preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.1 or more. The ratio of the content of the fatty acid in the curing agent composition to the total content of the compound represented by the general formula (1) and the fatty acid is preferably 0.6 or less, more preferably 0.5 or less, and even more preferably 0.4 or less from the viewpoint of improving the fluidity, foam suppressing property, storage stability and economical efficiency of the molding composition. The ratio of the content of the fatty acid in the curing agent composition to the total content of the compound represented by the general formula (1) and the fatty acid is preferably 0.05 to 0.6, more preferably 0.08 to 0.5, and even more preferably 0.1 to 0.4, from the viewpoint of improving the fluidity, foam suppressing property, storage stability, and economical efficiency of the molding composition.
[ other Components ]
The above-mentioned curing agent composition preferably contains resorcinol from the viewpoint of improving the working environment.
The content of resorcinol in the curing agent composition is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more, from the viewpoint of reducing formaldehyde and improving the mold strength. The content of resorcinol in the curing agent composition is preferably 20 mass% or less, more preferably 15 mass% or less, further preferably 10 mass% or less, and further preferably 5 mass% or less from the viewpoint of formaldehyde reduction, improvement in mold strength, and economy. The content of resorcinol in the curing agent composition is preferably 1 to 20% by mass, more preferably 1.5 to 15% by mass, further preferably 2 to 10% by mass, and still more preferably 2 to 5% by mass, from the viewpoint of reducing formaldehyde, improving the mold strength, and economical efficiency.
The above-mentioned curing agent composition may contain other components within a range that does not impair the effects of the present invention. Examples of the other component include solvents such as water, alcohols, ether alcohols, and glycols. Among them, from the viewpoint of compatibility of the curing agent and the phenolic resin, the touch feeling of the mold composition, and the viewpoint of odor control, 1 or more selected from alcohols, ether alcohols, and glycols are preferable, 1 or more selected from alcohols having 1 to 3 carbon atoms, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and benzyl alcohol are more preferable, and 1 or more selected from methanol, ethanol, diethylene glycol, triethylene glycol, and benzyl alcohol are more preferable, and triethylene glycol is still more preferable.
The content of the solvent in the curing agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of uniformly mixing the raw materials. The content of the solvent in the curing agent composition is preferably 30 mass% or less, more preferably 25 mass% or less, and even more preferably 20 mass% or less, from the viewpoints of uniformly mixing the raw materials, suppressing odor, and economy. The content of the solvent in the curing agent composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass, from the viewpoints of uniformly mixing the raw materials, suppressing odor, and economy.
Method for producing casting mold composition
The above-mentioned molding composition can be produced by a known method. As a method for producing the above-mentioned mold composition, there is exemplified a method for producing a mold composition comprising a mixing step of mixing a binder composition for mold molding containing the above-mentioned refractory particles, the above-mentioned phenolic resin, and the above-mentioned curing agent composition.
[ adhesive composition for mold Forming ]
The content of the water-soluble phenol resin in the binder composition for mold shaping (hereinafter, also simply referred to as the binder composition) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and still more preferably 40% by mass or more, from the viewpoint of improving the mold strength. The content of the water-soluble phenol resin in the binder composition is preferably 95 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less, and further preferably 60 mass% or less, from the viewpoint of improving the mold strength and the workability. The content of the water-soluble phenol resin in the binder composition is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and further preferably 40 to 60% by mass, from the viewpoint of improving the mold strength and the workability.
[ other Components ]
The adhesive composition may further contain additives such as water, a silane coupling agent, urea, a surfactant, and alcohols to such an extent that the effect of the present embodiment is not impaired. It is preferable that the binder composition contains a silane coupling agent because the final strength of the resulting mold can be further improved. Examples of the silane coupling agent include gamma- (2-amino) propylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, and N-. Beta. -aminoethyl) gamma-aminopropylmethyldimethoxysilane. The content of the silane coupling agent in the adhesive composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 1% by mass, from the viewpoint of improving the mold strength.
In the above mixing step, as a method for mixing the raw materials, a known general method may be used, and examples thereof include a method for kneading by adding the raw materials by a batch mixer and a method for kneading by supplying the raw materials to a continuous mixer.
Method for producing mold
In the method for manufacturing a mold according to the present embodiment, a mold can be manufactured directly by a conventional process for manufacturing a mold. A preferred method for producing a mold includes a method for producing a mold having a curing step of filling the mold composition into a mold and curing the mold composition.
With respect to the above-described embodiments, the present invention further discloses the following embodiments.
＜1＞
A casting mold composition comprising refractory particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H(1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
＜2＞
The casting composition according to < 1 >, wherein the phenolic resin is contained in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the refractory particles.
＜3＞
The casting composition according to < 1 > or < 2 >, wherein the phenolic resin is contained in an amount of 0.3 to 1 part by mass based on 100 parts by mass of the refractory particles.
＜4＞
The casting mold composition according to any one of < 1 > - < 3 >, wherein the content of the curing agent is 10 parts by mass or more and 70 parts by mass or less relative to 100 parts by mass of the phenolic resin.
＜5＞
The casting mold composition according to any one of < 1 > - < 4 >, wherein the content of the curing agent is 25 parts by mass or more and 45 parts by mass or less relative to 100 parts by mass of the phenolic resin.
＜6＞
The casting mold composition according to any one of < 1 > - < 5 >, wherein the curing agent comprises at least 1 selected from the group consisting of gamma-butyrolactone, propiolactone, epsilon-caprolactone, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triacetin, propylene carbonate, dimethyl glutarate, dimethyl adipate, dimethyl succinate, triethylene glycol diacetate, dimethyl 2-ethylsuccinate, dimethyl 2-methylpentanedioate and dimethyl 2-methyladipate.
＜7＞
The casting mold composition according to any one of < 1 > - < 6 >, wherein the content of the compound represented by the general formula (1) is 0.001 parts by mass or more and 0.1 parts by mass or less relative to 100 parts by mass of the refractory particles.
＜8＞
The casting mold composition according to any one of < 1 > - < 7 >, wherein the content of the compound represented by the general formula (1) is 0.005 parts by mass or more and 0.02 parts by mass or less relative to 100 parts by mass of the refractory particles.
＜9＞
The casting composition according to any one of < 1 > - < 8 >, wherein the content of the compound represented by the general formula (1) is 1 to 10 mass% based on 100 parts by mass of the total of the phenolic resin and the curing agent.
＜10＞
The casting composition according to any one of < 1 > - < 9 >, wherein the content of the compound represented by the general formula (1) is 1 mass% or more and 5 mass% or less based on 100 parts by mass of the total of the phenolic resin and the curing agent.
＜11＞
The casting composition according to any one of < 1 > - < 10 >, wherein the compound represented by the general formula (1) comprises a compound wherein R in the general formula (1) represents a linear alkyl or alkenyl group having 10 to 20 carbon atoms and n represents a number of 1.8 to 13 carbon atoms.
＜12＞
The casting mold composition according to any one of < 1 > - < 11 >, wherein the fatty acid is contained in an amount of 0.001 parts by mass or more and 0.01 parts by mass or less relative to 100 parts by mass of the refractory particles.
＜13＞
The casting composition according to any one of < 1 > - < 12 >, wherein the fatty acid content is 0.25 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the total of the phenolic resin and the curing agent.
＜14＞
The casting composition according to any one of < 1 > - < 13 >, wherein the fatty acid content is 0.4 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the total of the phenolic resin and the curing agent.
＜15＞
The casting mold composition according to any one of < 1 > - < 14 >, wherein the fatty acid comprises a fatty acid having a melting point of 45 ℃ or lower.
＜16＞
The casting composition according to any one of < 1 > - < 15 >, wherein the fatty acid comprises 1 or more selected from oleic acid, linolenic acid and lauric acid.
＜17＞
The casting composition according to any one of < 1 > - < 16 >, wherein the ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid is 0.05 to 0.6.
＜18＞
The casting composition according to any one of < 1 > - < 17 >, wherein the ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid is 0.1 to 0.4.
＜19＞
A curing agent composition for mold shaping, which comprises a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms.
RO-(CH 2 CH 2 O)n-H (1)
(in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and represents a number of 1.2 to 23 carbon atoms.)
＜20＞
The curing agent composition for mold molding according to < 19 >, wherein the content of the curing agent in the curing agent composition is 80% by mass or more and 97% by mass or less.
＜21＞
The curing agent composition for mold shaping according to < 19 > or < 20 >, wherein the content of the curing agent in the curing agent composition is 85 mass% or more and 97 mass% or less.
＜22＞
The curing agent composition for mold shaping according to any one of < 19 > - < 21 >, wherein the curing agent comprises at least 1 selected from the group consisting of gamma-butyrolactone, propiolactone, epsilon-caprolactone, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triacetin, propylene carbonate, dimethyl glutarate, dimethyl adipate, dimethyl succinate, triethylene glycol diacetate, dimethyl 2-ethylsuccinate, dimethyl 2-methylglutarate and dimethyl 2-methyladipate.
＜23＞
The curing agent composition for mold shaping according to any one of < 19 > - < 22 >, wherein the content of the compound represented by the general formula (1) is 1 mass% or more and 10 mass% or less.
＜24＞
The curing agent composition for mold shaping according to any one of < 19 > - < 23 >, wherein the content of the compound represented by the general formula (1) is 2% by mass or more and 5% by mass or less.
＜25＞
The curing agent composition for mold shaping according to any one of < 19 > - < 24 >, wherein the compound represented by the general formula (1) comprises a compound wherein R in the general formula (1) represents a linear alkyl or alkenyl group having 10 to 20 carbon atoms and n represents a number of 1.8 to 13.
＜26＞
The curing agent composition for mold shaping according to any one of < 19 > - < 25 >, wherein the fatty acid content is 0.1 mass% or more and 6 mass% or less.
＜27＞
The curing agent composition for mold shaping according to any one of < 19 > - < 26 >, wherein the fatty acid content is 0.3 mass% or more and 3 mass% or less.
＜28＞
The curing agent composition for mold shaping according to any one of < 19 > - < 27 >, wherein the fatty acid comprises a fatty acid having a melting point of 45 ℃ or lower.
＜29＞
The curing agent composition for mold shaping according to any one of < 19 > - < 28 >, wherein the fatty acid comprises 1 or more selected from oleic acid, linolenic acid and lauric acid.
＜30＞
The curing agent composition for mold shaping according to any one of < 19 > - < 29 >, wherein the ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid is 0.05 to 0.6.
＜31＞
The curing agent composition for mold shaping according to any one of < 19 > - < 30 >, wherein the ratio of the content of the fatty acid to the total content of the compound represented by the general formula (1) and the fatty acid is 0.1 to 0.4.
＜32＞
The curing agent composition for mold shaping according to any one of < 19 > - < 31 >, further comprising resorcinol, wherein the content of resorcinol is 2 mass% or more and 10 mass% or less.
＜33＞
The curing agent composition for mold shaping according to any one of < 19 > - < 32 >, further comprising resorcinol, wherein the content of resorcinol is 2 mass% or more and 5 mass% or less.
＜34＞
A method for producing a molding composition, comprising the step of mixing a molding binder composition comprising refractory particles and a phenolic resin, and a curing agent composition for molding as defined in any one of < 19 > - < 33 >.
Examples
Hereinafter, examples and the like of the present invention will be specifically described.
< evaluation method of raw Material >)
[ weight average molecular weight (Mw) of phenolic resin ]
(a) Sample preparation: the same weight of ion exchange water was added to the sample, and 0.1 wt% of H was added 2 SO 4 And neutralization is performed. The precipitate thus formed was separated by filtration, washed with water and dried. This was dissolved in Tetrahydrofuran (THF) to prepare a sample for GPC.
(b) Chromatographic column: 1 of the protection columns TSX (manufactured by Toyo Sedum Co., ltd.) was used, 1 of the protection columns TSK3000HXL (7.8 mm. Phi. Times.30 cm) and 1 of the protection columns TSK2500HXL (7.8 mm. Phi. Times.30 cm) were used. From the injection port side, the connection was made in the order of guard column-3000 HXL-2500 HXL.
(c) Standard substance: polystyrene (Toyo Cao industrial Co., ltd.)
(d) Eluent: THF (flow rate: 1 cm) 3 /min)
(e) Column temperature: 25 DEG C
(f) A detector: ultraviolet spectrophotometer (quantification at the wavelength of the maximum peak of ultraviolet absorption of phenol)
(g) Segmentation method for calculating molecular weight: time division (2 sec)
Method for measuring average particle diameter of refractory particles
The particle diameter of 50% by mass was measured using a sieve of 850, 600, 425, 300, 212, 150, 106, 75, 53 μm based on JIS Z2601 (1993) 'test method for foundry sand' specified in appendix 2, and the mass-cumulative particle diameter was set as the average particle diameter.
< manufacture of raw materials >
[ production of adhesive composition ]
To an aqueous solution obtained by mixing 10mol of phenol, 50 mass% aqueous potassium hydroxide solution (0.40 times mol relative to phenol) and 50 mass% aqueous sodium hydroxide solution (0.40 times mol relative to phenol), water was further added, and 92 mass% paraformaldehyde (2.00 times mol relative to phenol) was added. The polycondensation reaction was carried out at 80℃and continued until the weight average molecular weight of the phenolic resin reached 2000. Then, 0.5 parts by mass of gamma-glycidoxypropyl trimethoxysilane was added to 100 parts by mass of the reaction solution to obtain a binder composition (solid content 49.1 to 50% by mass) containing a phenolic resin (weight average molecular weight 2000).
[ production of refractory particles ]
[ production of refractory particles 1 ]
A casting mold composition was obtained by adding 0.26 mass% of a curing agent (96 mass% of gamma-butyrolactone, 4 mass% of resorcinol) and 1.3 mass% of a water-soluble phenol resin composition to 100 mass% of French man's sand (natural silica sand). Molding was performed using the mold composition, and the casting material FC250 was cast at 1400 ℃ using the resulting mold with an S/M ratio of 3.5 (so-called S/M ratio, which means a ratio of the mass of the mold to the mass of the casting). The cast sand recovered from the cast mold after casting was mixed with friemanter sand (natural silica sand) to 5 mass%, and the mixture was regenerated by using an M-type rotary crusher manufactured by japan casting. The procedure was repeated 5 times or more to obtain refractory particles 1 having an average particle diameter of 378. Mu.m.
[ production of refractory particles 2 ]
The same production method was used except that the friemann sand (natural silica sand: average particle diameter: 528 μm) added to the recovered casting sand was 10 mass% in the production of the refractory particles 1, to obtain refractory particles 2 having an average particle diameter of 407 μm.
[ production of refractory particles 3 ]
The same production method was used except that the production of the refractory particles 1 was performed without adding friemann's sand (natural silica sand) to the recovered casting sand, to obtain refractory particles 3 having an average particle diameter of 348 μm.
[ production of refractory particles 4 ]
The same production method was used except that in the production of the refractory particles 1, french Manter sand was changed to ESPEARL#40L (manufactured by mountain Co., ltd.: average particle size 406 μm), and a refractory particle 4 having an average particle size 396 μm was obtained.
[ production of refractory particles 5 ]
The same production method was used except that in the production of the refractory particles 1, the fleman sand was changed to espearl#40l (manufactured by mountain and river industries, ltd.) and the amount of espearl#40l added to the recovered foundry sand was changed to 10 mass%, whereby refractory particles 5 having an average particle diameter of 398 μm were obtained.
[ production of refractory particles 6 ]
The same production method was used except that in the production of the refractory particles 1, the fleman sand was changed to espearl#40l (manufactured by mountain and river industries, ltd.) and espearl#40l was not added to the recovered foundry sand, and the refractory particles 6 having an average particle diameter of 390 μm were obtained.
[ refractory particles 7]
Frieman's sand (natural silica sand: average particle diameter 528 μm) was used as the refractory particles 7.
[ refractory particles 8]
ESPEARL #40L (manufactured by mountain and Sichuan industries Co., ltd.) was used as the refractory particles 8.
< manufacturing of mold composition >
[ examples 1-1 to 1-13, comparative examples 1-1 to comparative examples 1-6 ]
100 parts by mass of refractory particles 1 and 0.26 part by mass of the curing agent composition shown in Table 1 were added, and the mixture was kneaded for 40 seconds using a kneader (Table mixer KM-300, manufactured by Kyowa Kagaku Co., ltd.). Thereafter, 1.3 parts by mass of the binder composition shown in table 1 was added and kneaded for 40 seconds to obtain a casting composition.
[ examples 1 to 14 ]
100 parts by mass of refractory particles 1, 0.0091 part by mass of the compound of the general formula (1) (R: lauryl, n=5), 0.0026 part by mass of oleic acid, and 0.26 part by mass of the curing agent composition shown in table 1 were added, and kneaded for 40 seconds using a kneader (table mixer KM-300, manufactured by the company, ltd.). Thereafter, 1.3 parts by mass of the binder composition shown in table 1 was added and kneaded for 40 seconds to obtain a casting composition.
[ examples 1-15 to 1-21, comparative examples 1-7 to 1-13 ]
The same procedure as in example 1-1 was repeated except that the refractory particles, binder composition and curing agent composition shown in Table 2 were used, to obtain casting mold compositions of examples 1-15 to 1-21 and comparative examples 1-7 to 1-13.
[ evaluation ]
The fluidity and filling properties of the casting compositions of examples 1-1 to 1-21 and comparative examples 1-1 to 1-13 were evaluated by the following methods. The evaluation results are shown in tables 1 and 2.
[ flowability evaluation ]
Immediately after kneading, the polyvinyl chloride pipe was filled with a columnar polyvinyl chloride composition (phi 50 mm. Times.300 mmH) and the sand was scraped off from the upper mountain portion until the mountain portion appeared on the upper face of the polyvinyl chloride pipe, and the polyvinyl chloride tube was lifted up to measure the width mm of the spread-out polyvinyl chloride composition. The larger the value, the more excellent the flowability.
[ evaluation of packing Density ]
The mass of the molding composition in the polyvinyl chloride pipe was measured, and calculated from the capacity of the polyvinyl chloride pipe. The higher the value, the higher the packing density and the more excellent the flowability.
[ evaluation of casting mold ]
Using the mold compositions of example 1-1 and comparative example 1-1, a mold was produced by the following method. The molding composition immediately after kneading was passed through a sieve having a wire mesh with a pore diameter of 3.35mm and a wire diameter of 1.27mm, and then filled into a wood pattern for evaluating the smoothness of the molding surface. A cross-sectional view of the wood pattern is shown in fig. 1. The mold composition was filled higher than the upper surface of the wooden mold, and the excess mold composition on the upper surface of the wooden mold was immediately scraped off to mold the mold. After the mold composition in the wood pattern was cured, the mold was released from the wood pattern and the surface smoothness was visually observed. The appearance of the produced mold of example 1-1 is shown in fig. 2, and the appearance of the mold of comparative example 1-1 is shown in fig. 3. The mold composition of example 1-1 has higher fluidity and packing density than those of comparative example 1-1, and therefore the mold of example 1-1 has higher surface smoothness than those of comparative example 1-1. This reduces repair of the mold and greatly improves the quality of the cast.
[ evaluation of casting quality ]
A method of evaluating the quality of castings will be described with reference to the accompanying drawings. First, a master mold was produced using the mold composition of comparative example 1-1. Fig. 4 is a schematic view showing a cross section of the master mold 1, wherein reference numeral 11 denotes an inner wall of the master mold 1, and reference numeral 12 denotes a cross section of the master mold 1. The master mold 1 was provided with a mold 2 of example 1-1 or comparative example 1-1, which was prepared for mold evaluation. Fig. 5 is a schematic diagram showing a cross section of the master mold 1 in a state where the mold 2 is provided. Then, as shown in FIG. 6, 17kg of molten metal material FC200 was poured at 1400℃into the master mold 1 provided with the mold 2, to thereby prepare a casting 3. Fig. 7 is a schematic view showing a cross section 3 of the casting 3 and an inner wall (surface contacting the casting 2) 31 of the casting 3 in a state where the main mold 1 and the casting 2 are removed from among the main mold 1, the casting 2, and the casting 3 shown in fig. 6. The photograph of the appearance of the inner wall 11 of the casting 3 of example 1-1 produced is shown in FIG. 8, and the photograph of the appearance of the inner wall 11 of the casting 3 of comparative example 1-1 is shown in FIG. 9. The casting composition of example 1-1 has higher fluidity, higher packing density and higher smoothness of the casting than those of comparative example 1-1, and therefore the surface of the inner wall 11 of the casting 3 of example 1-1 has higher smoothness than that of the inner wall 11 of the casting 3 of comparative example 1-1. Therefore, the repairing of the casting can be reduced, and the quality of the casting is greatly improved.
TABLE 1
TABLE 2
The mold composition of the example was superior to the mold composition of the comparative example in fluidity and packing density. In particular, as shown in comparative examples 1-1 and 1-2, comparative examples 1-3 and comparative examples 1-4, even if the content of the compound of the above general formula (1) or the above fatty acid is increased, the fluidity and the packing density are not improved, but as shown in examples 1-1 to 1-14, the fluidity and the packing density are improved by using the compound of the above general formula (1) together with the above fatty acid.
[ examples 2-1 to 2-12, comparative examples 2-1 ]
Foaming and storage stability were evaluated using the curing agent compositions used in examples 1-1 to 1-12 and the adhesive compositions used in examples 1-13 as shown in Table 3.
[ foaming evaluation ]
The binder composition or the curing agent composition described in the table was put into a 50ml transparent glass container, and stirred for 10 seconds by shaking with a touch stirrer MT-31 manufactured by YAMATO scientific Co., ltd. After 1 minute, the presence or absence of bubbles was visually confirmed.
[ storage stability ]
After storage at 25℃for 3 days, liquid separation was performed, and the presence or absence of insoluble matter and turbidity was visually confirmed. The evaluation results are shown in table 3.
TABLE 3
Air bubble Storage stability
Example 2-1 Curing agent composition used in example 1-1 Without any means for Without any means for
Example 2-2 Curing agent composition used in examples 1-2 Without any means for Without any means for
Examples 2 to 3 Curing agent composition used in examples 1 to 3 Without any means for Without any means for
Examples 2 to 4 Curing agent compositions used in examples 1 to 4 Without any means for Without any means for
Examples 2 to 5 Curing agent compositions used in examples 1 to 5 Without any means for Without any means for
Examples 2 to 6 Curing agent compositions used in examples 1 to 6 Without any means for Without any means for
Examples 2 to 7 Curing agent compositions used in examples 1 to 7 Without any means for Without any means for
Examples 2 to 8 Curing agent compositions used in examples 1 to 8 Without any means for Without any means for
Examples 2 to 9 Curing agent compositions used in examples 1 to 9 Without any means for Without any means for
Examples 2 to 10 Curing agent compositions used in examples 1 to 10 Without any means for Without any means for
Examples 2 to 11 Curing agent compositions used in examples 1 to 11 Without any means for Without any means for
Examples 2 to 12 Curing agent compositions used in examples 1 to 12 Without any means for Without any means for
Comparative example 2-1 Adhesive compositions used in examples 1 to 13 Has the following components Has the following components
The curing agent compositions of examples 2-1 to 2-12 in which the compound of formula (1) and the fatty acid were blended in the curing agent composition showed no generation of bubbles and excellent storage stability as compared with the adhesive composition of comparative example 2-1 in which the compound of formula (1) and the fatty acid were blended in the adhesive composition.

Claims (16)

1. A composition for a casting mold, comprising a base material,
the flame-retardant resin composition comprises flame-retardant particles, a phenolic resin, a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms;
RO-(CH 2 CH 2 O)n-H(1)
in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and 1.2 to 23 carbon atoms.
2. The molding composition of claim 1, wherein,
the phenolic resin content is 0.1 to 5 parts by mass based on 100 parts by mass of the refractory particles.
3. The molding composition according to claim 1 or 2, wherein,
the content of the compound represented by the general formula (1) is 0.001 parts by mass or more and 0.1 parts by mass or less relative to 100 parts by mass of the refractory particles.
4. The molding composition according to any one of claim 1 to 3, wherein,
the compound represented by the general formula (1) includes compounds in which R in the general formula (1) represents a linear alkyl or alkenyl group having 10 to 20 carbon atoms and n represents a number of 1.8 to 13 carbon atoms.
5. The molding composition according to any one of claim 1 to 4, wherein,
the content of the fatty acid is 0.0005 parts by mass or more and 0.05 parts by mass or less relative to 100 parts by mass of the refractory particles.
6. The molding composition according to any one of claims 1 to 5, wherein,
the ratio of the content of the fatty acid relative to the total content of the compound represented by the general formula (1) and the fatty acid is 0.05 to 0.6.
7. A curing agent composition for molding a mold,
the composition comprises a curing agent, a compound represented by the following general formula (1), and a fatty acid having 8 to 22 carbon atoms;
RO-(CH 2 CH 2 O)n-H(1)
in the general formula (1), R represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, n represents an average molar number of addition, and 1.2 to 23 carbon atoms.
8. The curing agent composition for mold shaping according to claim 7, wherein,
the content of the fatty acid is 0.1% by mass or more and 6% by mass or less.
9. The curing agent composition for mold shaping according to claim 7 or 8, wherein,
the fatty acid comprises a fatty acid having a melting point of 45 ℃ or less.
10. The curing agent composition for mold shaping according to any one of claim 7 to 9, wherein,
the fatty acid contains more than 1 selected from oleic acid, linolenic acid and lauric acid.
11. The curing agent composition for mold shaping according to any one of claims 7 to 10, wherein,
The content of the compound represented by the general formula (1) is 1% by mass or more and 10% by mass or less.
12. The curing agent composition for mold shaping according to any one of claims 7 to 11, wherein,
the ratio of the content of the fatty acid relative to the total content of the compound represented by the general formula (1) and the fatty acid is 0.05 to 0.6.
13. A method for producing a molding composition, comprising the step of mixing a binder composition for molding comprising refractory particles and a phenolic resin with the curing agent composition for molding according to any one of claims 7 to 12.
14. The method for producing a molding composition according to claim 13, wherein,
the compound represented by the general formula (1) includes compounds in which R in the general formula (1) represents a linear alkyl or alkenyl group having 10 to 20 carbon atoms and n represents a number of 1.8 to 13 carbon atoms.
15. The method for producing a molding composition according to claim 13 or 14, wherein,
the fatty acid comprises a fatty acid having a melting point of 45 ℃ or less.
16. The method for producing a molding composition according to any one of claims 13 to 15, wherein,
The fatty acid contains more than 1 selected from oleic acid, linolenic acid and lauric acid.
CN202280057880.9A 2021-09-29 2022-09-28 Casting mould composition Pending CN117858773A (en)

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JP3492134B2 (en) * 1997-02-06 2004-02-03 花王株式会社 Binder composition for mold
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