CN112368091A - Binder composition for mold making - Google Patents
Binder composition for mold making Download PDFInfo
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- CN112368091A CN112368091A CN201880095229.4A CN201880095229A CN112368091A CN 112368091 A CN112368091 A CN 112368091A CN 201880095229 A CN201880095229 A CN 201880095229A CN 112368091 A CN112368091 A CN 112368091A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
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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
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Abstract
The binder composition for mold making of the present invention contains a furan resin, water, a saccharide and a compatible binder component. According to the binder composition for mold making of the present invention, it is possible to provide a binder composition for mold making that uses a saccharide without a modification step and can suppress economic cost and energy cost.
Description
Technical Field
The present invention relates to a binder composition for mold making.
Background
Generally, an acid-curable mold is manufactured as follows: a binder composition for mold making containing an acid-curable resin and a curing agent composition containing sulfonic acid, sulfuric acid, phosphoric acid, and the like are added to refractory particles such as silica sand, and after kneading them, the resulting kneaded sand is filled into a prototype such as a wood mold, and the acid-curable resin is cured. As the acid-curable resin, furan resin, phenol resin, or the like is used, and as the furan resin, furfuryl alcohol-urea-formaldehyde resin, furfuryl alcohol-phenol-formaldehyde resin, other known modified furan resins, or the like is used. Such a method for producing a mold is widely used for casting a casting such as a machine part, a construction machine part, or an automobile part because it enables a high-quality casting to be produced by a high-degree-of-freedom molding operation and because it has excellent thermal properties.
As described above, furfuryl alcohol is widely used as a constituent component of an acid-curable resin such as a furan resin. However, furfuryl alcohol is produced through the following steps: hydrolyzing and dehydrating a raw material comprising agricultural byproducts such as corn cobs to obtain furfural; then, the production cost of furfural becomes high in the step of hydrogenating furfural. In addition, a large amount of residue is generated as a waste in the furfural production process (chinese patent application publication No. 103113548). In recent years, furfuryl alcohol and furfural production plants have been unable to stably supply furfuryl alcohol due to reasons such as shutdown due to environmental regulations and production reduction. From the above background, an alternative raw material to furfuryl alcohol, which is inexpensive, has a low load on the environment, and has high supply stability, is required.
Examples of the inexpensive reagent having a low load on the environment and high supply stability include saccharides, and a method for producing a furan resin in which a part of furfuryl alcohol is replaced with a saccharide has been reported (specification of chinese patent application No. 102861867).
Disclosure of Invention
The binder composition for mold making of the present invention contains a furan resin, water, a saccharide, and a compatible binder component.
Detailed Description
Since the solubility of saccharides to furan resins is poor, it has been necessary to improve the solubility to furan resins by modification such as reaction with furan resins. However, this modification requires a complicated process, and requires economic and energy costs.
The invention provides a binder composition for mold making, which uses saccharides without modification process and can restrain economic cost and energy cost.
The binder composition for mold making of the present invention contains a furan resin, water, a saccharide and a compatible binder component.
According to the present invention, there can be provided a binder composition for mold making, which can suppress economic cost and energy cost by using a saccharide without requiring a modification step.
Hereinafter, one embodiment of the present invention will be described.
< Binder composition for mold formation >
The binder composition for mold making of the present embodiment (hereinafter, also simply referred to as a binder composition) contains a furan resin, water, a saccharide, and a compatible binder component.
As described above, the saccharide has poor compatibility with furan resin. However, by finding a compatible binder component that can improve the compatibility of the saccharide with the furan resin while maintaining the mold strength, it is possible to provide a binder composition that can suppress economic and energy costs while using the saccharide without a modification step.
[ Furan resin ]
Examples of the furan resin include 1 kind of substance selected from furfuryl alcohol, a condensate of furfuryl alcohol and an aldehyde, a condensate of furfuryl alcohol and urea and an aldehyde (urea-modified furan resin), a condensate of urea and ethylene urea and an aldehyde (urea-ethylene urea copolycondensation resin), a condensate of melamine and an aldehyde, and a condensate of urea and an aldehyde; a substance comprising a mixture of 2 or more selected from these. In addition, a substance containing 2 or more copolycondensates selected from these may also be used. Among them, from the viewpoint of improving the solidification rate of the mold and improving the mold strength, it is preferable to use 1 or more selected from furfuryl alcohol, a condensate of furfuryl alcohol, and a condensate of furfuryl alcohol, urea, and aldehydes, and a copolycondensate thereof. Since furfuryl alcohol can be produced from plants as non-petroleum resources, it is preferable to use a part or more of furfuryl alcohol from the viewpoint of global environment.
The monomer composition used for the synthesis of the furan resin contains furfuryl alcohol, and 1 or more monomers selected from aldehydes, urea, phenols, and melamine, for example, can be selected and used depending on the target condensate.
Examples of the aldehydes include formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, hydroxymethylfurfural, and the like, and 1 or more of these can be suitably used. From the viewpoint of improving the mold strength, formaldehyde is preferably used, and from the viewpoint of reducing the amount of formaldehyde generated during molding, furfural, terephthalaldehyde, and hydroxymethylfurfural are preferably used.
Examples of the phenols include phenol, cresol, resorcinol, bisphenol a, bisphenol C, bisphenol E, bisphenol F, and the like, and 1 or more of these can be used.
In the case of producing a condensate of furfuryl alcohol and an aldehyde, it is preferable to use 0.01 to 1 mole of the aldehyde based on 1 mole of furfuryl alcohol. In the case of producing a condensate of furfuryl alcohol with aldehydes and urea, it is preferable to use 0.05 to 3 moles of aldehydes and 0.03 to 1.5 moles of urea per 1 mole of furfuryl alcohol.
The reaction temperature in synthesizing the furan resin varies depending on the raw material used, and is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 80 to 130 ℃ from the viewpoints of viscosity of the obtained binder composition, residual aldehyde content, reduction in production time, prevention of runaway reaction of the furan resin, and prevention of evaporation of the raw material. From the same viewpoint, the reaction time in the synthesis of the furan resin is preferably 0.5 to 12 hours, more preferably 1 to 10 hours, and still more preferably 3 to 8 hours.
In the production of furan resins, furfuryl alcohol as a raw material, water contained in the raw material, water produced during the reaction, and the like may be contained and may not be removed from the viewpoint of economy. The furan resin composition contains a furan resin, furfuryl alcohol, and a component other than the furan resin, for example, water.
The content of the furan resin in the binder composition is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, from the viewpoint of improving the mold strength. The content of the furan resin in the binder composition is more preferably 98% by mass or less, and still more preferably 95% by mass or less, from the viewpoint of lowering the viscosity. The content of the furan resin in the binder composition of the present embodiment is preferably 40 to 98 mass%, more preferably 50 to 95 mass%, and still more preferably 60 to 95 mass%, from the viewpoint of improvement in mold strength and reduction in viscosity.
[ Water ]
The content of water in the adhesive composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more. However, the water content of the binder composition is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoint of maintaining the curing reaction rate. The content of water in the binder composition is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 3 to 25% by mass, from the viewpoint of adjusting the viscosity of the binder composition to a viscosity that is easy to handle and maintaining the curing reaction rate.
In the case of synthesizing various condensates such as a condensate of furfuryl alcohol and an aldehyde, since a raw material in an aqueous solution state is used or condensation water is generated, the condensate is usually obtained in the form of a mixture with water. When such a condensate is used in the binder composition, water can be removed by a distillation apparatus or the like as needed, but as long as the curing reaction rate can be maintained, it is not necessary to remove the condensate during production.
[ saccharides ]
The saccharide is not particularly limited, and monosaccharides, disaccharides, oligosaccharides, polysaccharides, and sugar derivatives are exemplified.
Examples of the monosaccharide include: pentoses (pentoses) such as ribose, lyxose, xylose, arabinose, apiose, ribulose, xylulose and the like, hexoses (heptasaccharides) such as allose, talose, gulose, glucose, altrose, mannose, idose, galactose, psicose, fructose, sorbose, tagatose and the like, and heptoses (heptasaccharides) such as magnetohepose (hexose), sedoheptulose, malachite and the like.
Examples of the disaccharide include: trehalose, isohalose, kojibiose, sophorose, nigerose, laminaribiose, maltose, cellobiose, isomaltose, gentiobiose, lactose, sucrose, melibiose, isomaltulose, agarobiose, xylobiose, lactulose, rutinose, and the like.
Examples of the low saccharide include: raffinose, gentiotriose, cellotriose, maltotriose, melezitose and other trisaccharides, stachyose and other tetrasaccharides, xylooligosaccharide, isomaltooligosaccharide, gentiooligosaccharide, fructooligosaccharide, oligochitosan, Chitin oligosaccharide (Chitin oligosaccharide), oligocellose and other oligosaccharides.
Examples of the polysaccharide include: curdlan, cyclodextrin, pectin, starch, agarose, amylose, amylopectin, arabinosan, arabinogalactan, alginic acid, inulin, galactan, xylan, chitin, chitosan, glycogen, glucomannan, keratan sulfate, polysialic acid, cellulose, dextran, pectin, pectic acid, heparan sulfate (heparin sulfate), heparin, mannan, lichenin, levan, lentinan, and the like.
The above sugar derivatives may be exemplified by: deoxysugars such as deoxyribose, fucose and rhamnose, uronic acids such as glucuronic acid, galacturonic acid, iduronic acid, mannuronic acid and guluronic acid, and amino sugars such as glucosamine, galactosamine, fucosamine and mannosamine.
From the viewpoint of compatibility with water and furan resin and the viewpoint of mold strength, the above saccharide is preferably 1 or more selected from monosaccharides and disaccharides, and more preferably 1 or more selected from glucose, fructose, mannose, ribose, lyxose, xylose, arabinose, sucrose and maltose among these.
The content of the saccharide in the binder composition is preferably 1% by mass or more, and more preferably 3% by mass or more. The content of the saccharide is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of compatibility with the furan resin and the viewpoint of mold strength. The content of the saccharide is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, from the viewpoint of economy, compatibility with the furan resin, and mold strength.
[ compatible Binder component ]
The compatible binder component is a component having an effect of improving compatibility when a furan resin is mixed with a saccharide. Specifically, from the viewpoint of improving the compatibility of the saccharide with the furan resin and water and from the viewpoint of improving the mold strength, a compound represented by the following general formula (1) is preferable.
[ chemical formula 1]
[ in the formula, X1And X2Each represents a hydrogen atom, CH3Or C2H5Any one of (1). Angle (c)
Examples of the furan compound having a plurality of hydroxymethyl groups include 2, 5-dimethylolfuran, 2, 5-dimethoxymethylfuran, 2, 5-diethoxymethylfuran, 2-hydroxymethyl-5-methoxymethylfuran, 2-hydroxymethyl-5-ethoxymethylfuran, and 2-methoxymethyl-5-ethoxymethylfuran. Among these, 2, 5-dimethylolfuran is preferable from the viewpoint of improving the compatibility of the saccharide with the furan resin and water and from the viewpoint of improving the mold strength.
The content of the compatible binder component in the binder composition is preferably 3 mass% or more, and more preferably 5 mass% or more, from the viewpoint of improving the compatibility of the saccharide with the furan resin and water and from the viewpoint of improving the mold strength. From the viewpoint of reducing the viscosity of the binder composition, the content of the compatible binder component in the binder composition is preferably 30% by mass or less, and more preferably 20% by mass or less. The content of the compatible binder component in the binder composition is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint of improving the compatibility of the saccharide with the furan resin and water and from the viewpoint of reducing the viscosity of the binder composition.
[ curing accelerators ]
The binder composition of the present embodiment may contain a curing accelerator from the viewpoint of increasing the curing speed and improving the final mold strength. The curing accelerator is preferably 1 or more selected from the group consisting of phenol derivatives, aromatic dialdehydes, furfural and tannins, from the viewpoint of improving the final mold strength.
The content of the curing accelerator in the binder composition is preferably 0.5% by mass or more, more preferably 1.8% by mass or more, even more preferably 2.5% by mass or more, and even more preferably 3.0% by mass or more, from the viewpoint of improving the final strength of the mold. The content of the curing accelerator in the binder composition is preferably 63 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less, from the viewpoint of solubility of the curing accelerator in furan resin and the viewpoint of improving the final strength of the mold.
Examples of the phenol derivative include resorcinol, cresol, hydroquinone, phloroglucinol, and methylene bisphenol. Among them, resorcinol is preferable from the viewpoint of deep curing of the mold and the viewpoint of improving the final mold strength. The content of the phenol derivative in the binder composition is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass, from the viewpoint of solubility of the phenol derivative in the furan resin and from the viewpoint of improvement of the final mold strength. Among these, when resorcinol is used, the content of resorcinol in the adhesive composition is preferably 1 to 10% by mass, more preferably 2 to 7% by mass, and even more preferably 3 to 6% by mass, from the viewpoint of solubility of resorcinol in furan resin and from the viewpoint of improvement in final mold strength.
Examples of the aromatic dialdehyde include terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, and derivatives thereof. The derivatives thereof include compounds having a substituent such as an alkyl group on the aromatic ring of an aromatic compound having 2 formyl groups as a basic skeleton. From the viewpoint of preventing mold cracking, terephthalaldehyde and derivatives of terephthalaldehyde are preferable, and terephthalaldehyde is more preferable. The content of the aromatic dialdehyde in the binder composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass, from the viewpoint of sufficiently dissolving the aromatic dialdehyde in the furan resin and from the viewpoint of suppressing the odor of the aromatic dialdehyde itself.
Examples of the furfural include furfural, 5-hydroxymethylfurfural, and 5-acetoxymethylfurfural. Among them, furfural and 5-hydroxymethylfurfural are preferable from the viewpoint of increasing the solidification rate of the mold and the viewpoint of improving the final mold strength. The content of the furan aldehydes in the binder composition is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, from the viewpoints of solubility of furan aldehydes in furan resins, improvement of curing speed, and improvement of final mold strength.
Examples of the tannins include condensed tannins and hydrolyzed tannins. Examples of the condensed tannins and the hydrolyzed tannins include tannins having a pyrogallol skeleton and a resorcinol skeleton. In addition, bark extract containing these tannins, and extract extracted from natural products such as leaves, fruits, seeds, and gall parasitizing on plants can be added.
[ other additives ]
The adhesive composition may further contain an additive such as a silane coupling agent. For example, when the binder composition contains a silane coupling agent, the final strength of the obtained mold can be further improved, which is preferable. As the silane coupling agent, aminosilanes such as N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane; epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureylsilane, mercaptosilane, sulfide silane, methacryloxysilane and acryloyloxysilane. Preferred are aminosilane, epoxysilane, ureasilane. More preferably, aminosilane or epoxysilane, and still more preferably aminosilane. Among aminosilanes, N-. beta. - (aminoethyl) - γ -aminopropylmethyldimethoxysilane is preferable. The content of the silane coupling agent in the binder composition is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more, from the viewpoint of improving the final strength of the mold. From the same viewpoint, the content of the silane coupling agent in the binder composition is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less.
From the viewpoint of cost reduction, the adhesive composition may contain 1 or more alcohols selected from methanol, ethanol, ethylene glycol, propylene glycol, and glycerin. The alcohol is preferably a polyol. The content of the alcohol is preferably 1% by mass or more, more preferably 2% by mass or more. The content of the freezing inhibitor is preferably 10% by mass or less from the viewpoint of suppressing the decrease in strength of the mold. The content of the freezing inhibitor is preferably 1 to 10% by mass, more preferably 2 to 10% by mass, from the viewpoint of preventing freezing in a low-temperature environment and from the viewpoint of suppressing a decrease in the strength of the mold.
The binder composition may contain urea from the viewpoint of improving the mold strength. The urea is urea that does not undergo a condensation reaction with formaldehyde, furfuryl alcohol, or the like, and may be a substance remaining as an unreacted component or a substance added by another route. The content of the urea in the binder composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more, from the viewpoint of improving the mold strength and reducing the formaldehyde concentration. The content of the urea in the binder composition is preferably 10% by mass or less, more preferably 6.0% by mass or less, and still more preferably 4.5% by mass or less, from the viewpoint of enhancing the curing rate and the storage stability of the binder composition.
The urea in the binder composition can be measured by the following LC/MS analysis procedure. The sample was prepared by 100-fold dilution with a mixed solution of acetone/water 50/50, and further 100-fold dilution with a mobile phase.
(LC/MS analysis conditions)
Column: unison UK-Amino HT
Mobile phase: 0.1% TFA acetonitrile/water 95/5
Flow rate: 0.2mL/min
Column temperature: 40 deg.C
MS：SIM m/z：61.0[M+H]+
[ phenol resin ]
The binder composition may contain a phenol resin compound having a weight average molecular weight of 1000 or more and 5000 or less as an acid-curable resin, from the viewpoint of improving the flexibility of the mold and the viewpoint of improving the final strength of the mold. In the present specification, the weight average molecular weight (Mw) of the phenolic resin is measured by the method described in the examples.
The weight average molecular weight of the phenol resin is preferably 1000 or more, more preferably 1400 or more, from the viewpoint of improving the flexibility of the mold and the ultimate strength of the mold. The weight average molecular weight of the phenol resin is preferably 5000 or less, more preferably 2500 or less, from the viewpoint of improving the storage stability of the binder composition, improving the flexibility of the mold, and improving the final strength of the mold. Therefore, the concentration is preferably 1000 to 5000, and more preferably 1400 to 2500.
The degree of dispersion (ratio of weight average molecular weight/number average molecular weight) of the phenolic resin is preferably 1.2 or more, more preferably 1.8 or more, from the viewpoint of improving the flexibility of the mold and the ultimate strength of the mold. The ratio of the weight average molecular weight/number average molecular weight of the phenol resin is preferably 5.0 or less, more preferably 3.5 or less, from the viewpoint of improving the storage stability of the binder composition, improving the flexibility of the mold, and improving the final strength of the mold. Therefore, it is preferably 1.2 to 5.0, more preferably 1.8 to 3.5.
As the phenol resin, conventionally known phenol resins can be used, and for example, 1 type selected from the group consisting of resol type phenol resins, novolak type phenol resins, and phenol resins having a structure as described in japanese patent application laid-open No. 2009-292862; a substance comprising a mixture of 2 or more of these.
In general, the phenols used for obtaining the resol resin include phenol, cresol, xylenol, and the like, and among these, phenol is preferable from the viewpoint of improving the flexibility of the mold and the viewpoint of improving the final strength of the mold. Examples of the aldehyde used for obtaining the resol resin include formaldehyde, glyoxal, paraformaldehyde, furfural, 5-hydroxymethylfurfural and the like, and paraformaldehyde is preferable from the viewpoint of improving the flexibility of the mold and the viewpoint of improving the final strength of the mold. Examples of the basic catalyst used for obtaining the resol resin include potassium hydroxide and sodium hydroxide.
In general, phenols and aldehydes used for obtaining a novolak-type phenol resin include those similar to resol resins.
In the production of the phenol resin composition, water contained in the raw material and water produced in the reaction are contained in addition to the phenol resin, and may not be removed from the viewpoint of economy.
Among the above phenolic resins, a resol-type phenolic resin is preferably used from the viewpoint of solubility, from the viewpoint of improving the flexibility of the mold, and from the viewpoint of improving the final strength of the mold.
The content of the phenolic resin in the binder composition is 2 to 35 mass% from the viewpoint of solubility, the viewpoint of improving the flexibility of the mold, and the viewpoint of improving the final strength of the mold.
The content of the phenolic resin in the binder composition is more preferably 8 mass% or more from the viewpoint of improving the flexibility of the mold and the viewpoint of improving the final strength of the mold. The content of the phenolic resin in the binder composition is more preferably 20 mass% or less from the viewpoint of solubility, the viewpoint of improving the flexibility of the mold, and the viewpoint of improving the final strength of the mold. Therefore, more preferably 8 to 20 mass%.
The total content of the furan resin and the phenol resin in the binder composition is preferably 50 mass% or more from the viewpoint of improving the final strength of the mold. The total content of the furan resin and the phenol resin in the binder composition is preferably 95 mass% or less from the viewpoint of improving the final strength of the mold. Therefore, it is preferably 50 to 95% by mass.
The binder composition is preferably used for molding a self-curing mold. Here, the self-setting mold is a mold in which a polymerization reaction proceeds with the passage of time and the mold is set when a binder composition and a curing agent composition are mixed with sand. The temperature of the sand used in this case is in the range of-20 to 50 ℃, preferably 0 to 40 ℃. Sand at such a temperature can be appropriately solidified by selecting an appropriate amount of a solidifying agent and adding the solidifying agent to the sand.
< composition for mold >
The binder composition may be mixed with refractory particles and a curing agent composition to prepare a molding composition. The composition for a mold of the present embodiment contains the binder composition, the refractory particles, and the curing agent composition.
[ 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 the like can be used, and refractory particles obtained by recovering used refractory particles, refractory particles subjected to regeneration treatment, and the like can be used.
[ curing agent composition ]
The curing agent composition may be used without particular limitation if it contains a curing agent for curing the adhesive composition. As the curing agent, an acid curing agent can be exemplified, and 1 or more of conventionally known acid curing agents such as a sulfonic acid compound such as xylene sulfonic acid (particularly m-xylene sulfonic acid), toluene sulfonic acid (particularly p-toluene sulfonic acid), methane sulfonic acid, a phosphoric acid compound such as phosphoric acid and acidic phosphate ester, and an acidic aqueous solution containing sulfuric acid can be used. From the viewpoint of workability, these compounds are preferably aqueous solutions. The curing agent may contain 1 or more kinds of solvents or carboxylic acids selected from alcohols, ether alcohols and esters.
The content of the curing agent in the curing agent composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass, from the viewpoint of improving the final mold strength.
The composition for a mold preferably contains 0.5 to 3.0 parts by mass of the binder composition and 0.07 to 2.0 parts by mass of the curing agent composition per 100 parts by mass of the refractory particles.
From the viewpoint of improving the mold strength, the content of the curing agent composition in the mold composition is preferably 0.1 part by mass or more, more preferably 0.14 part by mass or more, further preferably 0.2 part by mass or more, preferably 0.8 part by mass or less, more preferably 0.6 part by mass or less, and further preferably 0.4 part by mass or less, relative to 1.0 part by mass of the binder composition. From the viewpoint of improving the mold strength, the content of the curing agent composition in the mold composition is preferably 0.1 to 0.8 parts by mass, more preferably 0.14 to 0.6 parts by mass, and still more preferably 0.2 to 0.4 parts by mass, based on 1.0 part by mass of the binder composition.
< method for producing casting mold >
The mold can be produced by curing the mold composition of the present embodiment. In the method of manufacturing a mold according to the present embodiment, the mold can be manufactured by using a conventional process for manufacturing a mold as it is. A preferred method for producing a mold includes the following steps: a mixing step of mixing refractory particles, the binder composition for mold molding of the present embodiment, and a curing agent for curing the binder composition for mold molding to obtain a composition for mold; and a curing step of filling the composition for a mold into a molding box and curing the composition for a mold.
The mixing step preferably includes a 1 st mixing step of mixing the refractory granular material with a curing agent composition for mold formation containing the curing agent composition; and a 2 nd mixing step of mixing the binder composition for mold making with the obtained mixture after the 1 st mixing step.
In the mixing step, an acid-curable resin, a curing accelerator, water, an additive such as a silane coupling agent, an acidic substance, a solvent, and the like may be added to the resin composition to such an extent that the effects of the present embodiment are not impaired.
In the mixing step, as a method for mixing the respective raw materials, a known general method can be used, and examples thereof include a method for adding and kneading the respective raw materials by a batch mixer, and a method for supplying and kneading the respective raw materials to a continuous mixer.
Examples
Hereinafter, examples and the like which specifically show the present invention will be described.
< examples 1 to 11, comparative examples 1 to 5 >
[ preparation of Furan resin composition ]
100 parts by mass of furfuryl alcohol, 35 parts by mass of paraformaldehyde, and 13 parts by mass of urea were mixed in a three-necked flask and adjusted to pH9 with a 25 mass% aqueous sodium hydroxide solution. After the reaction mixture was warmed to 100 ℃, it was reacted at the same temperature for 1 hour. The pH was adjusted to 4.5 with 37 mass% hydrochloric acid, and the reaction was further carried out at 100 ℃ for 1 hour. Thereafter, the pH was adjusted to 7 with a 25 mass% aqueous solution of sodium hydroxide, 5 parts by mass of urea was added, and the mixture was reacted at 100 ℃ for 30 minutes to obtain a furan resin composition. The furan resin composition consists of: 71.7% by mass of urea-modified furan resin, 19.5% by mass of furfuryl alcohol, and 8.8% by mass of water.
[ preparation of phenol resin composition ]
100 parts by mass of phenol and 45 parts by mass of paraformaldehyde were adjusted to pH8.0 with a 48 mass% potassium hydroxide aqueous solution in a three-necked flask, and reacted at 80 ℃ for 10 hours to obtain a phenol resin composition. The composition is as follows: 89 mass% of phenol resin and 11 mass% of water. The weight average molecular weight of the phenol resin was determined to be 2940 by the following method.
[ weight average molecular weight of phenolic resin ]
The weight average molecular weight was determined by gel permeation chromatography in terms of standard polystyrene.
[ measurement conditions ]
Gel filtration chromatograph SC-8020 series-Build-up System manufactured by Tosoh corporation
Column: g2000HXL + G4000HXL
A detector: UV254nm
Carrier: tetrahydrofuran 1 mL/min
Column temperature: 38 deg.C
[ production of composition for mold ]
0.40 parts by mass of a curing agent composition (Kao Lightener C-17: manufactured by Kao-Quaker Co., Ltd.) was added to 100 parts by mass of furan reclaimed silica sand at 25 ℃ and 55% RH, and 0.8 parts by mass of a binder composition prepared by adding and mixing the components shown in Table 1 in advance was added, and these were mixed to obtain the casting composition according to example 3 and comparative example 2.
[ test example 1]
The molding composition immediately after kneading was filled in cylindrical test piece frames having a diameter of 50mm and a height of 50mm, and after 1 hour, the mold was removed and the compressive strength (MPa) was measured by the method described in JIS Z2604-1976, whereby example 3 was 0.95MPa and comparative example 2 was 0.67 MPa.
[ test example 2 ]
The mold compositions prepared in the same manner as above were filled in cylindrical test piece frames having a diameter of 50mm and a height of 50mm, and were demolded when the compressive strength was 1MPa, and the compressive strength (MPa) was measured 24 hours after the start of filling by the method described in JIS Z2604-1976, whereby example 3 was 4.86MPa and comparative example 2 was 4.36 MPa.
[ solubility of saccharides ]
The following operations 1 to 4 were sequentially performed on the glass screw pipes to which each of the binder compositions described in table 1 was added, to dissolve the binder compositions. The more the binder composition is dissolved in a numerically small operation, the higher the solubility. Here, the completion of dissolution means that the glass screw tube was visually observed after each operation, and the adhesive composition was in a uniform transparent liquid state. The results are shown in Table 1.
1: 1Hr ultrasonic treatment (37kHz) in 25 ℃ Water
2: 1Hr ultrasonic treatment (37kHz) in 50 ℃ Water
3: 2Hr ultrasonic treatment (37kHz) in 50 ℃ Water
4: 4Hr ultrasonic treatment (37kHz) in 50 ℃ Water
5: insolubility (separation of saccharides in the binder composition)
[ storage stability of adhesive composition ]
Each of the binder compositions in which the saccharide was dissolved by the above procedure was left at room temperature for 1 week, and was visually evaluated according to the following criteria.
O: uniform dissolution of saccharides in binder compositions
X: sugar phase separation in the binder composition
[ Table 1]
Claims (7)
1. A binder composition for mold making, comprising a furan resin, water, a saccharide and a compatible binder component.
2. The binder composition for mold making according to claim 1 or 2, wherein the compatible binder component is represented by the following formula (1),
in the formula, X1And X2Each represents a hydrogen atom, CH3Or C2H5Any one of (1).
3. The molding binder composition according to claim 1 or 2, wherein the compatible binder component is 2, 5-dimethylolfuran.
4. The binder composition for mold making according to any one of claims 1 to 3, wherein the saccharide is at least 1 selected from the group consisting of glucose, fructose, mannose, ribose, lyxose, xylose, arabinose, sucrose and maltose.
5. The binder composition for mold making according to any one of claims 1 to 4, which contains at least one of ethylene glycol and glycerin.
6. A composition for casting molds, comprising:
refractory particles, the binder composition for mold making according to any one of claims 1 to 5, and a curing agent composition containing a curing agent for curing the binder composition for mold making.
7. A method of making a casting mold, comprising:
a mixing step of mixing refractory particles, the binder composition for mold making according to any one of claims 1 to 5, and a curing agent composition containing a curing agent for curing the binder composition for mold making to obtain a composition for mold; and a curing step of filling the composition for a mold into a molding box and curing the composition for a mold.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2018/030391 WO2020035923A1 (en) | 2018-08-16 | 2018-08-16 | Binding agent composition for foundry molding |
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| Publication Number | Publication Date |
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| CN112368091A true CN112368091A (en) | 2021-02-12 |
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| CN201880095229.4A Pending CN112368091A (en) | 2018-08-16 | 2018-08-16 | Binder composition for mold making |
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| Country | Link |
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| JP (1) | JPWO2020035923A1 (en) |
| CN (1) | CN112368091A (en) |
| WO (1) | WO2020035923A1 (en) |
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| KR102470363B1 (en) * | 2022-09-26 | 2022-11-25 | 주식회사 아이원코퍼레이션 | Furan binder composition for sand casting containing nanocellulose and furfuryl alcohol and a method for manufacturing a binder for casting |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3209420A (en) * | 1963-07-05 | 1965-10-05 | Archer Daniels Midland Co | Mold and core binder for foundry use |
| JPS5680343A (en) * | 1979-12-01 | 1981-07-01 | Daihatsu Motor Co Ltd | Additive for molding sand for green sand mold |
| EP0057934A1 (en) * | 1981-02-11 | 1982-08-18 | Maizena Gesellschaft mbH | Furan resin binder for foundry moulding and core sand |
| JPS62104649A (en) * | 1985-07-29 | 1987-05-15 | Kaou Kueekaa Kk | Binder composition for casting mold |
| JPS63264239A (en) * | 1987-04-22 | 1988-11-01 | Sadaji Nagabori | Mold material used for molding sand mold and core necessitating no coating |
| JPH0857577A (en) * | 1994-08-19 | 1996-03-05 | Kao Corp | Binder composition for production of casting mold and production of casting mold |
| CN108299351A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
-
2018
- 2018-08-16 CN CN201880095229.4A patent/CN112368091A/en active Pending
- 2018-08-16 JP JP2020537329A patent/JPWO2020035923A1/en active Pending
- 2018-08-16 WO PCT/JP2018/030391 patent/WO2020035923A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3209420A (en) * | 1963-07-05 | 1965-10-05 | Archer Daniels Midland Co | Mold and core binder for foundry use |
| JPS5680343A (en) * | 1979-12-01 | 1981-07-01 | Daihatsu Motor Co Ltd | Additive for molding sand for green sand mold |
| EP0057934A1 (en) * | 1981-02-11 | 1982-08-18 | Maizena Gesellschaft mbH | Furan resin binder for foundry moulding and core sand |
| JPS62104649A (en) * | 1985-07-29 | 1987-05-15 | Kaou Kueekaa Kk | Binder composition for casting mold |
| JPS63264239A (en) * | 1987-04-22 | 1988-11-01 | Sadaji Nagabori | Mold material used for molding sand mold and core necessitating no coating |
| JPH0857577A (en) * | 1994-08-19 | 1996-03-05 | Kao Corp | Binder composition for production of casting mold and production of casting mold |
| CN108299351A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
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| WO2020035923A1 (en) | 2020-02-20 |
| JPWO2020035923A1 (en) | 2021-02-15 |
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