CN113891771A - Binder composition for mold making - Google Patents

Binder composition for mold making Download PDF

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Publication number
CN113891771A
CN113891771A CN202080038660.2A CN202080038660A CN113891771A CN 113891771 A CN113891771 A CN 113891771A CN 202080038660 A CN202080038660 A CN 202080038660A CN 113891771 A CN113891771 A CN 113891771A
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mass
mold
parts
binder composition
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CN113891771B (en
Inventor
神泽智史
石山翔午
山谷满喜人
中畑优
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Kao Corp
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Kao Corp
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—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
    • 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
    • B22C1/2233—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 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

The present invention is a binder composition for mold molding, which contains a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms. According to the present invention, a binder composition for mold making is provided which can improve the disintegration of a mold (i.e., reduce the compressive strength of a residual mold) and improve the productivity of a mold removal operation after casting.

Description

Binder composition for mold making
Technical Field
The present invention relates to a binder composition for mold making.
Background
There is known a mold molding method in which a phenol resin is used as a binder and the phenol resin is cured with an organic ester and carbon dioxide having excellent safety.
While the mold is required to have strength to withstand handling and casting with molten metal, high disintegration is required to facilitate taking out of the cast after casting and to shorten the time for removing the mold.
The organic binder is considered to have a good disintegrability because the binder is thermally decomposed by heat at the time of casting, but the phenol resin is cured so-called 2 times by heating at about 100 to 300 ℃, so that the mold strength is increased, and thus the disintegrability of the portion heated in this range at the time of casting is lowered.
In order to solve the above problems, methods of adding a metal salt compound and the like are proposed in Japanese patent application laid-open Nos. 7-148546, 10-193033 and 9-57391.
Disclosure of Invention
The binder composition for mold making of the present invention contains a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
The method for manufacturing a mold of the present invention comprises: a mixing step of mixing refractory particles and the binder composition for mold molding to obtain a composition for mold molding; and a curing step of charging the composition for mold formation into a mold and curing the composition for mold formation.
The composition for mold making of the present invention contains the binder composition for mold making and refractory particles.
The additive for mold making of the present invention contains a cyclic ketal compound having a hydroxyl group and 5 or more carbon atoms.
Detailed Description
The conventional binder composition for mold molding is insufficient in the mold disintegratability, and there is room for improvement.
The invention provides a binder composition for mold molding, a composition for mold molding, an additive for mold molding, and a method for manufacturing a mold, which can improve the disintegration of the mold (i.e., reduce the residual strength) without reducing the mold strength during mold molding and improve the productivity of the mold removal operation after casting.
The binder composition for mold making of the present invention contains a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
The method for manufacturing a mold of the present invention comprises: a mixing step of mixing refractory particles and the binder composition for mold molding to obtain a composition for mold molding; and a curing step of charging the composition for mold formation into a mold and curing the composition for mold formation.
The composition for mold making of the present invention contains the binder composition for mold making and refractory particles.
The additive for mold making of the present invention contains a cyclic ketal compound having a hydroxyl group and 5 or more carbon atoms.
According to the present invention, there can be provided a binder composition for mold molding, a composition for mold molding, an additive for mold molding, and a method for producing a mold, which can improve the disintegration of a mold and improve the productivity of a demold operation after casting without lowering the mold strength at the time of mold molding.
Hereinafter, one embodiment of the present invention will be described.
< Binder composition for mold formation >
The binder composition for mold molding (hereinafter, also referred to as a binder composition) of the present embodiment is a binder composition for mold molding containing a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms (hereinafter, also referred to as a cyclic ketal compound). According to the binder composition of the present embodiment, the increase in the residual mold compressive strength of the mold after casting can be suppressed without lowering the mold strength at the time of mold molding, so that the disintegration property of the mold is improved, and the productivity of the mold removal work of the mold after casting can be improved. Since the disintegration property of the mold is improved, agglomerates which are generated during the casting sand crushing treatment and cannot be crushed into individual sand particles are reduced, and the amount of waste is reduced. In addition, since the residual resin in the regeneration of the casting sand is easily removed, LOI (loss on ignition) of the regenerated sand is reduced, and the strength of the mold using the regenerated sand is improved. Further, it is considered that since there is almost no 2-time solidification by heating, in the field of cast steels having large solidification shrinkage, the mold can follow the solidification shrinkage of the cast after casting, and therefore cracking defects at the time of shrinkage of the cast are also reduced. The reason for exhibiting such an effect is not determined, but is considered as follows.
When a phenol resin is contained in a composition for a mold, the phenol resin is usually cured 2 times when the mold is heated by casting or the like, and the compression strength of the mold is increased, so that the mold is not easily disintegrated. However, it is considered that the cyclic ketal compound having a hydroxyl group and 5 or more carbon atoms contained in the binder composition of the present embodiment is appropriately compatible with the phenol resin because of appropriate hydrophobicity, and appropriately coordinates to the phenolic hydroxyl group or the like which is a reaction site of the phenol resin to suppress 2-time curing of the phenol resin, thereby suppressing an increase in the compression strength of the residual mold and improving the disintegration property of the mold.
[ phenol resin ]
The above-mentioned phenol resin is generally a product obtained by polycondensation of a phenol compound with an aldehyde compound under alkaline conditions. The phenol compound may be a mixture of 1 or more than 2 kinds of phenol compounds including phenol, bisphenol a, bisphenol F, cresol, 3, 5-xylenol, resorcinol, catechol, nonylphenol, p-tert-butylphenol, isopropenylphenol, phenylphenol, phenols including other substituted phenols, cashew nut shell liquid, and the like. Further, as the aldehyde compound, 1 or a mixture of 2 or more 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. In addition, these may be mixed with a monomer capable of condensing with an aldehyde compound, such as urea, melamine, cyclohexanone; 1-membered aliphatic alcohol compounds such as methanol, ethanol, isopropanol, n-propanol and butanol; a water-soluble high-molecular polyacrylate; cellulose derivative polymers, polyvinyl alcohol, lignin derivatives, and the like.
The alkali catalyst used for the synthesis of the phenol resin includes hydroxides of alkali metals such as LiOH, NaOH, and KOH, and NaOH and KOH are particularly preferable. Further, these base catalysts may be used in combination.
The phenol resin is preferably prepared as an aqueous solution, and the mass of the solid content (mass of solid after drying at 105 ℃ for 3 hours) is preferably 30 mass% or more, and more preferably 50 mass% or more, from the viewpoint of improving the mold strength. The mass of the solid content of the phenol resin aqueous solution is preferably 85 mass% or less, and more preferably 75 mass% or less, from the viewpoint of improving the mold strength and improving the workability. The mass of the solid content of the phenol resin aqueous solution is preferably 30 to 80 mass%, more preferably 50 to 75 mass%, from the viewpoint of improving the mold strength and improving the workability.
From the viewpoint of improving the mold strength, the weight average molecular weight (Mw) of the phenol resin is preferably 500 or more, more preferably 800 or more, and still more preferably 1200 or more. From the viewpoint of improving the mold strength and the workability, the weight average molecular weight (Mw) of the phenol resin is preferably 8000 or less, more preferably 5000 or less, and still more preferably 3000 or less. The weight average molecular weight (Mw) of the phenol resin is preferably 500 to 8000, more preferably 800 to 5000, and still more preferably 1200 to 3000, from the viewpoint of improving the mold strength and improving the workability. The weight average molecular weight of the phenol resin was measured by the method described in examples.
The content of the phenol resin in the binder composition is preferably 10% by mass or more, more preferably 25% by mass or more, and still more preferably 40% by mass or more, from the viewpoint of improving the mold strength. From the viewpoint of improving the mold strength and the workability, the content of the phenol resin in the binder composition is preferably 95% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less. The content of the phenol resin in the binder composition is preferably 10 to 95% by mass, more preferably 25 to 80% by mass, even more preferably 25 to 70% by mass, and even more preferably 40 to 60% by mass, from the viewpoint of improving the mold strength and improving the workability.
[ Cyclic ketal compound having hydroxyl group and having 5 or more carbon atoms ]
The cyclic ketal compound has 5 or more carbon atoms, preferably 6 or more carbon atoms, from the viewpoint of improving the disintegrability of the mold after casting. From the same viewpoint, the carbon number of the cyclic ketal compound is preferably 20 or less, more preferably 14 or less, still more preferably 10 or less, and still more preferably 8 or less.
From the viewpoint of improving the disintegrability of the cast mold, the molecular weight of the cyclic ketal compound is preferably 110 or more, more preferably 115 or more, and still more preferably 130 or more. From the same viewpoint, the molecular weight of the cyclic ketal compound is preferably 200 or less, more preferably 170 or less, still more preferably 150 or less, and still more preferably 140 or less.
From the viewpoint of improving the disintegrability of the cast mold, the number of cyclic ketal structures in 1 molecule of the cyclic ketal compound is preferably 2 or less, and more preferably 1.
From the viewpoint of improving the disintegrability of the cast mold, the number of hydroxyl groups in 1 molecule of the cyclic ketal compound is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1.
In addition, from the viewpoint of improving the disintegrability of the cast mold, the cyclic ketal compound is preferably a compound having 1 cyclic ketal structure and 2 hydroxyl groups and a compound having 1 cyclic ketal structure and 1 hydroxyl group, and more preferably a compound having 1 cyclic ketal structure and 1 hydroxyl group.
The cyclic ketal compound can be obtained by reacting a 3-or more-membered polyol with 1 or more kinds selected from aldehydes and ketones.
From the viewpoint of improving the disintegratability and the acquisition of the cast mold, the number of the polyol is preferably 3 or more, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.
Examples of the 3-or more-membered polyol include: glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, xylitol, sorbitol, mannitol, dipentaerythritol, and the like.
From the viewpoint of improving the disintegratability and the acquisition of the cast mold, the carbon number of the aldehyde and ketone is preferably 1 or more, more preferably 2 or more, and from the same viewpoint, preferably 25 or less, more preferably 10 or less, further preferably 5 or less, further preferably 4 or less, and further preferably 3 or less.
Examples of aldehydes and ketones are: formaldehyde, acetaldehyde, acetone, propionaldehyde, methyl ethyl ketone, butyraldehyde, valeraldehyde, diethyl ketone, and the like.
The cyclic ketal compound is preferably a compound represented by the following general formula (1) from the viewpoint of improving the disintegrability of a cast mold.
[ chemical formula 1]
Figure BDA0003371761640000061
(in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2And (4) OH groups. However, R3 and R4 are not both hydrogen. )
The cyclic ketal compound is more preferably a compound represented by the following general formula (2) from the viewpoint of improving the disintegrability of the mold after casting.
[ chemical formula 2]
Figure BDA0003371761640000062
(in the general formula (2), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; however, R1 and R2 are not hydrogen at the same time.)
The hydrocarbyl group of R1 and R2 in the general formulae (1) and (2) is preferably an alkyl group from the viewpoint of improving the disintegratability and the acquisition property of the cast mold.
From the viewpoint of improving the disintegratability and the acquisition of the cast mold, the carbon number of R1 and R2 in the general formulae (1) and (2) is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2, and even more preferably 2.
The hydrocarbon group of R1 and R2 in the general formulae (1) and (2) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group, from the viewpoint of improving the disintegratability and the acquisition property of the cast mold.
From the viewpoint of improving the disintegratability and the acquisition of the cast mold, at least one of R1 and R2 in the general formulae (1) and (2) is preferably an alkyl group, and more preferably both are alkyl groups.
With respect to R1 and R2 in the above general formulae (1) and (2), from the viewpoint of improving the disintegratability and the acquisition property of the cast mold, it is preferable that R1 is methyl and R2 is methyl, R1 is methyl and R2 is ethyl, R1 is methyl and R2 is hydrogen, R1 is ethyl and R2 is ethyl, more preferable that R1 is methyl and R2 is methyl, R1 is methyl and R2 is ethyl, R1 is methyl and R2 is hydrogen, further preferable that R1 is methyl and R2 is methyl, R1 is methyl and R2 is hydrogen, and still more preferable that R1 is methyl and R2 is methyl.
With respect to R3 and R4 in the above general formula (2), from the viewpoint of improving the disintegration property and the acquisition property of the cast mold, it is preferable that R1 is hydrogen and R2 is — CH2And (4) OH groups. That is, the compound represented by the above general formula (1) is preferably a compound represented by the above general formula (2).
From the viewpoint of improving the disintegratability and the acquisition of the cast mold, the content of the compound represented by the general formula (1) or the general formula (2) in the cyclic ketal compound is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass.
From the viewpoint of improving the disintegrability of the mold after casting and the strength of the mold, the content of the cyclic ketal compound in the binder composition is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 4% by mass or more, further preferably 8% by mass or more, and from the same viewpoint, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. The content of the cyclic ketal compound in the binder composition is preferably 0.2 to 30% by mass, more preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, even more preferably 1 to 20% by mass, even more preferably 2 to 20% by mass, even more preferably 4 to 20% by mass, and even more preferably 8 to 20% by mass, from the viewpoint of improving the disintegratability of a cast mold after casting and the strength of the cast mold.
From the viewpoint of improving the disintegrability of the mold after casting and the strength of the mold, the content of the cyclic ketal compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, further preferably 4 parts by mass or more, further preferably 8 parts by mass or more, further preferably 16 parts by mass or more, with respect to 100 parts by mass of the phenol resin, and from the same viewpoint, preferably 65 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less. The content of the cyclic ketal compound is preferably 0.5 to 65 parts by mass, more preferably 0.5 to 50 parts by mass, even more preferably 0.5 to 40 parts by mass, even more preferably 1 to 40 parts by mass, even more preferably 2 to 40 parts by mass, even more preferably 4 to 40 parts by mass, even more preferably 8 to 40 parts by mass, and even more preferably 16 to 40 parts by mass, based on 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegratability of the cast mold and the strength of the cast mold.
[ other Components ]
The binder composition may further contain additives such as water, alcohol, a silane coupling agent, an oxyanion compound, and a surfactant to such an extent that the effects of the present embodiment are not impaired.
[ alcohol ]
The binder composition preferably contains an alcohol from the viewpoint of improving the mold strength. The alcohol is preferably 1 or more selected from the group consisting of a polyol, a glycol ether, an alicyclic diol compound, and an aromatic alcohol. Examples of the alcohol include: polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-dimethyl-1, 3-propanediol, and glycerin; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether and dipropylene glycol monomethyl ether; alicyclic diol compounds such as cyclohexanediol and cyclohexanedimethanol; phenoxy alcohols such as 2-phenoxyethanol, 2-phenoxypropanol and 1-phenoxy-2-propanol, and aromatic alcohols such as benzyl alcohol. When carbon dioxide is used as the curing agent, from the viewpoint of improving the mold strength, 1 or more selected from glycol ethers and aromatic alcohols is preferable, and 1 or more selected from triethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and 2-phenoxyethanol is more preferable.
From the viewpoint of improving the disintegratability of the cast mold, the content of 1 or more selected from the group consisting of the polyhydric alcohol, the glycol ether, the alicyclic diol compound, and the aromatic compound alcohol in the alcohol is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass.
The content of the alcohol in the binder composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and even more preferably 4% by mass or more from the viewpoint of improving the mold strength, and is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, even more preferably 9% by mass or less, even more preferably 7% by mass or less, and even more preferably 6% by mass or less from the viewpoint of improving the disintegratability of the mold after casting and from the viewpoint of improving the mold strength. The content of the alcohol in the binder composition is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, even more preferably 2 to 10% by mass, even more preferably 2 to 9% by mass, even more preferably 2 to 7% by mass, even more preferably 4 to 6% by mass, from the viewpoint of improving the disintegratability of the cast mold after casting and from the viewpoint of improving the strength of the cast mold.
The content of the alcohol is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 4 parts by mass or more, and further preferably 8 parts by mass or more with respect to 100 parts by mass of the phenol resin, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, further preferably 20 parts by mass or less, further preferably 18 parts by mass or less, and further preferably 13 parts by mass or less from the viewpoint of improving the disintegratability of the mold after casting and the strength of the mold. The content of the alcohol is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, even more preferably 4 to 20 parts by mass, even more preferably 4 to 18 parts by mass, even more preferably 4 to 13 parts by mass, and even more preferably 8 to 13 parts by mass, based on 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegratability of the cast mold and the strength of the cast mold.
From the viewpoint of improving the disintegrability of the mold after casting and the strength of the mold, the content of the cyclic ketal compound in the binder composition containing the alcohol is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 4% by mass or more, and from the same viewpoint, preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably 7% by mass or less. The content of the cyclic ketal compound in the binder composition is preferably 0.2 to 18% by mass, more preferably 0.2 to 15% by mass, even more preferably 0.2 to 10% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 10% by mass, even more preferably 4 to 10% by mass, and even more preferably 4 to 7% by mass, from the viewpoint of improving the disintegratability of a cast mold and the strength of the cast mold.
In the binder composition containing the alcohol, the content of the cyclic ketal compound is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, further preferably 4 parts by mass or more, and further preferably 8 parts by mass or more, per 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegrability of a mold after casting and from the viewpoint of improving the mold strength, and from the same viewpoint, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 18 parts by mass or less, and further preferably 14 parts by mass or less. In the binder composition containing the alcohol, the content of the cyclic ketal compound is preferably 0.5 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 0.5 to 20 parts by mass, even more preferably 2 to 20 parts by mass, even more preferably 4 to 20 parts by mass, even more preferably 8 to 18 parts by mass, and even more preferably 8 to 14 parts by mass, per 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegrability of a cast mold after casting and the viewpoint of improving the strength of the cast mold.
The total content of the cyclic ketal compound and the alcohol in the binder composition is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 4 mass% or more, and further preferably 8 mass% or more from the viewpoint of improving the disintegrability of the mold after casting and the strength of the mold, and is preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 12 mass% or less from the viewpoint of improving the disintegrability of the mold after casting and the strength of the mold. The total content of the cyclic ketal compound and the alcohol in the binder composition is preferably 1 to 20% by mass, more preferably 2 to 20% by mass, even more preferably 4 to 15% by mass, and even more preferably 8 to 12% by mass, from the viewpoint of improving the disintegratability of a cast mold after casting and from the viewpoint of improving the mold strength.
The total content of the cyclic ketal compound and the alcohol is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, further preferably 8 parts by mass or more, and further preferably 16 parts by mass or more per 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegratability of the mold after casting and the strength of the mold, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and further preferably 25 parts by mass or less. From the viewpoint of improving the disintegrability of the cast mold and the strength of the cast mold, the total content of the cyclic ketal compound and the alcohol is preferably 2 to 40 parts by mass, more preferably 4 to 40 parts by mass, even more preferably 4 to 35 parts by mass, even more preferably 8 to 35 parts by mass, and even more preferably 16 to 25 parts by mass, based on 100 parts by mass of the phenol resin.
The ratio of the content of the cyclic ketal compound to the total content of the alcohol and the cyclic ketal compound is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, and further preferably 0.4 or more from the viewpoint of improving the disintegration of the mold after casting, and is preferably 0.8 or less, more preferably 0.7 or less, and further preferably 0.6 or less from the viewpoint of improving the mold strength. From the viewpoint of achieving both improvement in the disintegration property of the cast mold and improvement in the mold strength, the ratio of the content of the cyclic ketal compound to the total content of the alcohol and the cyclic ketal compound is preferably 0.1 to 0.8, more preferably 0.2 to 0.8, even more preferably 0.4 to 0.6, from the viewpoint of improvement in the disintegration property of the cast mold is preferably 0.4 to 0.8, and from the viewpoint of improvement in the mold strength is preferably 0.2 to 0.7, even more preferably 0.2 to 0.6.
[ silane coupling agent ]
The binder composition preferably contains a silane coupling agent from the viewpoint of improving the mold strength. Examples of the silane coupling agent include: gamma- (2-amino) propylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, N-beta- (aminoethyl) gamma-aminopropylmethyldimethoxysilane, etc. The content of the silane coupling agent in the binder composition is preferably 0.1 to 5% by mass, and more preferably 0.3 to 1% by mass, from the viewpoint of improving the mold strength.
[ oxyanion Compound ]
When the binder composition is cured with carbon dioxide, it is preferable to contain an oxyanion compound from the viewpoint of improving the strength of the mold and the curing rate of the mold. This is because it is considered that the oxyanion compound forms an ionomer after absorbing carbon dioxide, and thus the water-soluble phenol resin is polymerized. Examples of the oxyanion compound include: boric acid and borates, aluminates, stannates, and the like. Examples of the borate include: sodium tetraborate 10 hydrate (borax), potassium tetraborate 10 hydrate, sodium metaborate, sodium pentaborate, potassium pentaborate, and the like. As the aluminate, sodium aluminate can be cited. The content of the oxyanion compound in the binder composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 12% by mass, and still more preferably 1 to 8% by mass, from the viewpoint of enhancing the strength of the mold and from the viewpoint of enhancing the curing rate of the mold.
< method for producing casting mold >
In the method for manufacturing a mold according to the present embodiment, a mold can be manufactured by using a conventional mold manufacturing process as it is. A preferable method for producing a mold includes at least the following steps: a mixing step of mixing refractory particles and the binder composition to obtain a composition for mold molding; and a curing step of charging the composition for mold formation into a mold and curing the composition for mold formation.
[ mixing procedure ]
[ refractory particles ]
As the refractory particles that can be used in the method for manufacturing a mold according to the present embodiment, conventionally known materials 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 further, reclaimed sand obtained by recovering and regenerating 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 greater than 50 μm, more preferably 70 μm or greater, even more preferably 120 μm or greater, and even more preferably 150 μm or greater, and from the same viewpoint, is preferably 600 μm or less, more preferably 400 μm or less, even more preferably 300 μm or less, and even more preferably 250 μm or less. In the present specification, the average particle diameter is measured by the method described in examples.
In the mixing step, as a method for mixing the raw materials, a known general method can be used, and examples thereof include: a method of adding and kneading the respective raw materials by a batch mixer, and a method of supplying and kneading the respective raw materials to a continuous mixer.
The ratio of the refractory particles to the binder composition may be appropriately set, and the content of the binder composition is preferably 10 parts by mass or more, and preferably 100 parts by mass or less, per 1000 parts by mass of the refractory particles, from the viewpoint of improving the mold strength and from the viewpoint of economy. The phenol resin is preferably 5 parts by mass or more, and preferably 80 parts by mass or less, per 1000 parts by mass of the fire-resistant particles.
In the mixing step, the cyclic ketal compound may be further mixed in addition to the binder composition when obtaining the composition for mold making. In this case, the content of the cyclic ketal compound in the composition for mold molding is preferably in a range of 100 parts by mass of the phenolic resin relative to the content of the cyclic ketal compound.
Alternatively, a binder composition containing fire-resistant particles and a phenol resin but not containing a cyclic ketal compound and the cyclic ketal compound may be mixed to obtain a composition for mold formation. The amount of the cyclic ketal compound in this case is the same as the content described in the above adhesive composition.
Further, the refractory particles, the phenol resin, the cyclic ketal compound, and other components used in the binder composition may be mixed to obtain a composition for mold molding. In this case, the content of the phenol resin is preferably 5 parts by mass or more, and preferably 80 parts by mass or less, with respect to 1000 parts by mass of the fire-resistant particles. The amounts of the cyclic ketal compound and other components used in the adhesive composition are the same as the contents described in the adhesive composition.
When the cyclic ketal compound is mixed in addition to the binder composition as described above, the cyclic ketal compound is an additive for mold making. The additive for mold making of the present embodiment contains a cyclic ketal compound having a hydroxyl group and 5 or more carbon atoms. The additive for mold molding can reduce the residual strength of a cast mold after casting, improve the disintegration of the cast mold, and improve the productivity of the mold removal operation after casting. The preferable mode of the cyclic ketal compound in the additive for mold making of the present invention is the same as the preferable mode of the cyclic ketal compound in the binder composition for mold making.
[ curing Process ]
In the curing step, the composition for mold formation is charged into a mold and cured. As a method for curing the composition for mold making, a known and usual method can be used. As a method for curing the composition for mold making, a method of curing with a curing agent can be mentioned. Examples of the curing agent include: organic ester compounds, carbon dioxide, and the like.
The organic ester compound may be a lactone having 3 to 10 carbon atoms, an organic ester produced by a 1-membered alcohol or a polyhydric alcohol having 1 to 10 carbon atoms and an organic carboxylic acid having 1 to 10 carbon atoms, or an alkylene carbonate having 1 to 8 carbon atoms, which may be used alone or in combination. In the self-hardening mold forming method, γ -butyrolactone, propiolactone, ∈ -caprolactone, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triacetin, ethylene carbonate, propylene carbonate, and the like are preferably used, and in the gas-hardening mold forming method using an organic ester, methyl formate is preferably used.
In the case where an organic ester is used as the curing agent, the amount of the organic ester is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 35 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of the binder composition, from the viewpoints of improvement in mold strength, improvement in curing speed, and economy.
In the case where an organic ester is used as the curing agent, the amount of the organic ester is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 70 parts by mass or less, and more preferably 60 parts by mass or less, per 100 parts by mass of the phenol resin, from the viewpoint of improving the mold strength, the curing rate, and the economical viewpoint.
When carbon dioxide is used as the curing agent, the curing agent is added to the casting mold per 100cm to improve the mold strength3The flow rate of carbon dioxide is preferably 0.2L/min or more, more preferably 1L/min or more, and from the viewpoint of economy, per 100cm3The mold (3) is preferably 30L/min or less, more preferably 15L/min or less, still more preferably 7L/min or less, and yet more preferably 4L/min or less. The flow time of carbon dioxide is preferably 10 seconds or more, more preferably 20 seconds or more, and even more preferably 30 seconds or more from the viewpoint of improving the mold strength, and is preferably 90 seconds or less, more preferably 70 seconds or less, and even more preferably 50 seconds or less from the viewpoint of economy. Temperature at the time of curing from the viewpoint of improving mold strengthPreferably-5 ℃ or higher, more preferably 5 ℃ or higher, and still more preferably 10 ℃ or higher, and from the viewpoint of economy, preferably 45 ℃ or lower, more preferably 40 ℃ or lower, and still more preferably 35 ℃ or lower.
In the case where carbon dioxide is used as the curing agent, the amount of carbon dioxide is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 100 parts by mass or less, more preferably 75 parts by mass or less, per 100 parts by mass of the binder composition, from the viewpoint of improving the mold strength, the curing rate, and the economical viewpoint.
In the case of using carbon dioxide as the curing agent, the amount of carbon dioxide is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 150 parts by mass or less, per 100 parts by mass of the phenol resin, from the viewpoint of improving the mold strength, the curing rate, and the economical viewpoint.
< composition for mold formation >
The composition for mold making of the present embodiment contains refractory particles and the binder composition. That is, the composition for mold molding of the present embodiment contains refractory particles, a phenol resin, and the cyclic ketal compound.
The content of the binder composition with respect to the refractory particles is as described in the mixing step of the method for producing a mold.
The content of the phenol resin with respect to the refractory particles is as described in the mixing step of the above-described method for producing a mold. The content of the cyclic ketal compound relative to the phenol resin is as described in the binder composition.
[ inorganic particles ]
The composition for mold molding of the present embodiment preferably contains inorganic particles from the viewpoint of improving the disintegration property of a mold after casting. It is considered that the inorganic particles are present in the cured binder composition, and it is considered that the thermal expansion coefficient of the inorganic particles is different from that of the cured binder composition, and therefore, the decrease in residual strength after heating is promoted.
As the inorganic particles, there can be mentioned: silica, mullite, kaolin, fly ash. The inorganic particles may be amorphous or crystalline.
The shape of the inorganic particles may be any of spherical, massive, amorphous, and the like, but spherical particles are preferable from the viewpoint of improving the disintegrability of the mold after casting and the viewpoint of improving the strength of the mold.
From the viewpoint of improving the disintegratability of the cast mold, the average particle diameter of the inorganic particles is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 1 μm or more, and even more preferably 2 μm or more, and from the same viewpoint, preferably 50 μm or less, more preferably 25 μm or less, and even more preferably 18 μm or less.
From the viewpoint of improving the disintegratability of the cast mold and the mold strength, the content of the inorganic particles is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, further preferably 12 parts by mass or more, and further preferably 15 parts by mass or more, with respect to 100 parts by mass of the phenol resin, and from the same viewpoint, preferably 50 parts by mass or less, more preferably 35 parts by mass or less, further preferably 30 parts by mass or less, and further preferably 25 parts by mass or less. The content of the inorganic particles is preferably 5 to 50 parts by mass, more preferably 7 to 35 parts by mass, even more preferably 12 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, per 100 parts by mass of the phenol resin, from the viewpoint of improving the disintegratability of the cast mold and the strength of the cast mold.
The present invention further discloses the following embodiments with respect to the above embodiments.
< 1 > an adhesive composition for mold making, which comprises a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
< 2 > the binder composition for mold making according to < 1 >, wherein the cyclic ketal has 20 or less carbon atoms.
< 3 > the binder composition for mold making according to < 1 > or < 2 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1).
[ chemical formula 3]
Figure BDA0003371761640000161
(in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2And (4) OH groups. However, R3 and R4 are not both hydrogen. )
< 4 > the binder composition for mold making according to < 1 > or < 2 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (2).
[ chemical formula 4]
Figure BDA0003371761640000171
(in the general formula (2), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; however, R1 and R2 are not hydrogen at the same time.)
< 5 > the binder composition for mold making according to < 3 > or < 4 >, wherein in the general formulae (1) and (2), R1 and R2 are at least 1 kind selected from the group consisting of R1 being methyl and R2 being methyl, R1 being methyl and R2 being ethyl, R1 being methyl and R2 being hydrogen, R1 being ethyl and R2 being ethyl.
< 6 > the binder composition for mold making according to any one of < 3 > to < 5 >, wherein the content of the compound represented by the general formula (1) or the general formula (2) in the cyclic ketal is 80% by mass or more.
< 7 > the binder composition for mold making according to any one of < 1 > to < 6 >, wherein a content of the cyclic ketal compound is 0.2 mass% or more and 20 mass% or less in the binder composition for mold making.
< 8 > the binder composition for mold making according to any one of < 1 > to < 7 >, wherein the content of the cyclic ketal compound is 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the phenol resin.
< 9 > A binder composition for mold making, which comprises a phenol resin, a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms, and an alcohol containing 1 or more selected from a polyhydric alcohol, a glycol ether, an alicyclic diol compound and an aromatic alcohol.
< 10 > the binder composition for mold making according to < 9 >, wherein the cyclic ketal has 20 or less carbon atoms.
< 11 > the binder composition for mold making according to < 9 > or < 10 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1).
[ chemical formula 5]
Figure BDA0003371761640000181
(in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2And (4) OH groups. However, R3 and R4 are not both hydrogen. )
< 12 > the binder composition for mold making according to < 9 > or < 10 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (2).
[ chemical formula 6]
Figure BDA0003371761640000182
(in the general formula (2), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; however, R1 and R2 are not hydrogen at the same time.)
< 13 > the binder composition for mold making according to < 11 > or < 12 >, wherein in the general formulae (1) and (2), R1 and R2 are at least 1 kind selected from the group consisting of R1 being methyl and R2 being methyl, R1 being methyl and R2 being ethyl, R1 being methyl and R2 being hydrogen, R1 being ethyl and R2 being ethyl.
< 14 > the binder composition for mold making according to any one of < 11 > to < 13 >, wherein the content of the compound represented by the general formula (1) or the general formula (2) in the cyclic ketal is 80% by mass or more.
< 15 > the binder composition for mold making according to any one of < 9 > to < 14 >, wherein the content of 1 or more selected from the group consisting of polyhydric alcohols, glycol ethers, alicyclic diol compounds and aromatic compound alcohols in the above-mentioned alcohols is 80% by mass or more.
< 16 > the binder composition for mold making according to any one of < 9 > to < 15 >, wherein a content of the cyclic ketal compound is 0.2 mass% or more and 10 mass% or less in the binder composition for mold making.
< 17 > the binder composition for mold making according to any one of < 9 > to < 16 >, wherein the content of the alcohol is 0.5 mass% or more and 15 mass% or less in the binder composition for mold making.
< 18 > the binder composition for mold making according to any one of < 9 > to < 17 >, wherein the content of the cyclic ketal compound is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the phenol resin.
< 19 > the binder composition for mold making according to any one of < 9 > to < 18 >, wherein the alcohol is contained in an amount of 2 parts by mass or more and 35 parts by mass or less based on 100 parts by mass of the phenol resin.
< 20 > the binder composition for mold making according to any one of < 9 > to < 19 >, wherein a total content of the cyclic ketal compound and the alcohol is 1% by mass or more and 20% by mass or less in the binder composition for mold making.
< 21 > the binder composition for mold making according to any one of < 9 > to < 20 >, wherein a total content of the cyclic ketal compound and the alcohol is 4 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the phenol resin.
< 22 > the binder composition for mold making according to any one of < 9 > to < 21 >, wherein a ratio of a content of the cyclic ketal compound to a total content of the alcohol and the cyclic ketal compound is 0.1 or more and 0.8 or less.
< 23 > a method for producing a mold, comprising: a mixing step of mixing the refractory particles and the binder composition for mold molding of any one of < 1 > -22 > to obtain a composition for mold molding; and a curing step of charging the composition for mold formation into a mold and curing the composition for mold formation.
< 24 > the process for producing a mold according to < 23 >, wherein the curing agent for curing the composition for mold formation in the curing step is an organic ester compound or carbon dioxide.
< 25 > a molding composition comprising the binder composition for molding a mold as defined in any one of < 1 > -to < 22 > and refractory particles.
< 26 > the composition for mold molding < 25 >, wherein the binder composition is contained in an amount of 10 parts by mass or more and 100 parts by mass or less based on 1000 parts by mass of the refractory particles.
< 27 > a composition for mold making, which comprises a phenol resin, a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms, and a flame-resistant particle.
< 28 > the composition for mold making according to < 27 >, wherein the cyclic ketal has 20 or less carbon atoms.
< 29 > the composition for mold making according to < 27 > or < 28 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1).
[ chemical formula 7]
Figure BDA0003371761640000201
(in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2And (4) OH groups. However, R3 and R4 are not both hydrogen. )
< 30 > the composition for mold making according to < 27 > or < 28 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (2).
[ chemical formula 8]
Figure BDA0003371761640000202
(in the general formula (2), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; however, R1 and R2 are not hydrogen at the same time.)
< 31 > the composition for mold making according to < 29 > or < 30 >, wherein in the general formulae (1) and (2), R1 and R2 are selected from 1 or more of R1 is methyl and R2 is methyl, R1 is methyl and R2 is ethyl, R1 is methyl and R2 is hydrogen, R1 is ethyl and R2 is ethyl.
< 32 > the composition for mold molding according to any one of < 29 > to < 31 >, wherein the content of the compound represented by the general formula (1) or the general formula (2) in the cyclic ketal is 80% by mass or more.
< 33 > the composition for mold molding according to any one of < 25 > to < 32 >, wherein the content of the phenol resin is 5 parts by mass or more and 80 parts by mass or less with respect to 1000 parts by mass of the refractory particles.
< 34 > the composition for mold molding according to any one of < 25 > to < 33 >, wherein the content of the cyclic ketal compound is 0.5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the phenol resin.
< 35 > the composition for mold making according to any one of < 25 > to < 34 >, which further contains inorganic particles having an average particle diameter of 0.1 to 50 μm.
< 36 > the composition for mold making < 35 > wherein the content of the inorganic particles is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the phenol resin.
< 37 > an additive for mold making, which contains a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
< 38 > the additive for mold making according to < 37 > wherein the cyclic ketal has 20 or less carbon atoms.
< 39 > the additive for mold making according to < 37 > or < 38 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1).
[ chemical formula 9]
Figure BDA0003371761640000211
(in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2And (4) OH groups. However, R3 and R4 are not both hydrogen. )
< 40 > the additive for mold making according to < 37 > or < 38 >, wherein the cyclic ketal compound comprises a compound represented by the following general formula (2).
[ solution 10]
Figure BDA0003371761640000221
(in the general formula (2), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; however, R1 and R2 are not hydrogen at the same time.)
< 41 > the additive for mold making according to < 39 > or < 40 >, wherein in the general formulae (1) and (2), R1 and R2 are 1 or more selected from the group consisting of R1 being methyl and R2 being methyl, R1 being methyl and R2 being ethyl, R1 being methyl and R2 being hydrogen, R1 being ethyl and R2 being ethyl.
< 42 > the additive for mold making according to any one of < 39 > -41 > wherein the cyclic ketal is contained in an amount of 80% by mass or more of the compound represented by the general formula (1) or the general formula (2).
Examples
Hereinafter, examples and the like specifically illustrating the present invention will be described.
< evaluation method of raw Material >
[ weight average molecular weight (Mw) of Water-soluble phenol resin ]
The weight average molecular weight (Mw) of the water-soluble phenol resin was measured by GPC (gel permeation chromatography) under the following conditions.
(a) Sample preparation: the same weight of ion-exchanged water was added to the sample, and 0.1 mass% of H2SO4 was added to neutralize the sample. The precipitate was separated by filtration, washed with water and dried. This was dissolved in tetrahydrofuran to prepare a sample for GPC.
(b) Column: a guard column TSX (manufactured by Toyo Caoda industries, Ltd.) was used, wherein 1 column of HXL (6.5 mm. phi. times.4 cm), 1 column of TSK3000HXL (7.8 mm. phi. times.30 cm) and 1 column of TSK2500HXL (7.8 mm. phi. times.30 cm) were used. The ligation was performed from the injection port side in the order of protection column-3000 HXL-2500 HXL.
(c) Standard substance: monodisperse polystyrene having a known weight average molecular weight (manufactured by Toyo Cauda industries Co., Ltd.)
(d) Eluent: THF (flow rate: 1 cm)3Minute/minute)
(e) Column temperature: 25 deg.C
(f) A detector: ultraviolet spectrophotometer (quantification at wavelength of maximum peak of ultraviolet absorption of phenol)
(g) Segmentation method for molecular weight calculation: time division (2 seconds)
[ average particle diameter ]
(in the case of particles having a particle size of 53 μm or more)
The particle size at 50% mass accumulation was determined as the average particle size by the method specified in JIS Z2601(1993) "test method for foundry sand" appendix 2 using 850, 600, 425, 300, 212, 150, 106, 75, 53 μm sieves.
(case of particles smaller than 53 μm)
The average particle diameter is an average particle diameter of 50% cumulative volume as measured by a laser diffraction particle size distribution measuring apparatus (LA-920, horiba, Ltd.). The analysis conditions are as follows.
The measurement method: flow (flow) method
Dispersion medium: ion exchange water
Dispersion method: stirring and built-in ultrasonic wave for 3 minutes
Sample concentration: 2mg/100cc
< preparation of an aqueous solution of a phenol resin >
In a 2 liter glass vessel equipped with a thermometer and a stirrer, 380g of phenol, 670g of a 48 mass% potassium hydroxide aqueous solution, 165g of water, and 265g of 92 mass% paraformaldehyde were mixed and reacted at 85 ℃ to obtain a phenol resin aqueous solution. The solid content concentration of the phenol resin aqueous solution was 63.9 mass%. The weight average molecular weight (Mw) of the water-soluble phenol resin was 1820.
< examples 1 to 16, comparative examples 1 to 14 >
[ preparation of Binder composition ]
The binder composition was obtained by mixing 74 parts by mass of the above phenol resin aqueous solution (47.3 parts by mass of phenol resin), 3 parts by mass of sodium aluminate, 6 parts by mass of sodium tetraborate 10 hydrate (borax), 1 part by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by shin-shich chemical industries, inc.) and the respective compounds listed in table 1 in predetermined amounts, and then mixing water so as to obtain 100 parts by mass.
[ refractory particles ]
Silica sand ("Sanhe silica sand No. 6", manufactured by Sanhe silica Kaisha) was used as the refractory particles. The average particle size was 181. mu.m.
[ preparation of sample for evaluation of residual mold compression Strength ]
In a kitchen mixer ("KENMIX. AICOH. CHEF", manufactured by Aikoku Co., Ltd.) having an aluminum mixer stirring blade, 30 parts by mass of the above adhesive composition was charged to 1000 parts by mass of refractory particles, mixed at a rotation speed of 300rpm for 2 minutes, and then filled in a wooden mold for a test piece of 50 mm. times.50 mm. phi. Thereafter, carbon dioxide was introduced at 25 ℃ and a flow rate of 2.5L/min for 30 seconds to obtain a test piece for evaluation. The test piece was left to stand at 25 ℃ for 24 hours, and then an aluminum foil ("manufactured by Myfoil" UACJ) was wound so as to cover the entire surface, and then heated in an electric furnace heated to 200 ℃ for 1 hour. Thereafter, the mixture was allowed to stand at 25 ℃ for 1 hour. Thereafter, the aluminum foil was removed to obtain a sample for evaluation of residual mold compressive strength.
[ method of evaluating compression Strength of residual mold ]
The residual mold compressive strength evaluation sample was evaluated at a rate of 5 mm/sec using a compressive strength evaluation tester ("SDW 2000SH model", manufactured by Okamura corporation), and the residual mold compressive strength was calculated from the load at the time of fracture. Further, the mold compression strength of the test piece after standing at 25 ℃ for 24 hours was also measured. The results are shown in tables 1 and 2. The smaller the difference between the residual mold compressive strength (a) and the mold compressive strength (B), the more the improvement in the residual mold compressive strength is suppressed, and the more excellent the mold disintegratability is.
[ Table 1]
Figure BDA0003371761640000251
[ Table 2]
Figure BDA0003371761640000261
As is clear from table 1, the binder compositions of examples 1 to 5 have a smaller difference between the residual mold compressive strength (a) and the mold compressive strength (B) than the binder compositions of comparative example 2 and comparative examples 4 to 14, and thus the improvement of the residual mold compressive strength is suppressed, and the mold disintegration property is excellent. In addition, the binder compositions of comparative examples 1 and 3 had a small difference between the residual mold compressive strength (a) and the mold compressive strength (B), but the mold compressive strength after standing at 25 ℃ for 24 hours was low and was not practical.
As is clear from Table 2, the binder compositions of examples 6 to 16 containing an alcohol improved the mold compressive strength, and the difference between the residual mold compressive strength (A) and the mold compressive strength (B) was small.
< examples 17 to 21 >
In a kitchen mixer ("KENMIX. AICOH. CHEF", manufactured by Aikoku corporation) equipped with an aluminum mixer stirring blade, 30 parts by mass of the binder composition of example 10 and 3 parts by mass of the inorganic particles shown in Table 4 were charged to 1000 parts by mass of the refractory particles, and mixed at a rotation speed of 300rpm for 2 minutes, and then the mixture was filled in a wooden mold for test pieces of 50 mm. times.50 mm. phi. Thereafter, carbon dioxide was introduced at 25 ℃ and a flow rate of 2.5L/min for 30 seconds to obtain a test piece for evaluation. The obtained test piece for evaluation was used to perform the same evaluation as in example 10. The results are shown in Table 3. The properties of the inorganic particles used are shown in table 4.
[ Table 3]
Figure BDA0003371761640000271
[ Table 4]
Figure BDA0003371761640000281
From the above results, it is found that by containing inorganic particles in the mold composition, the difference between the residual mold compressive strength (a) and the mold compressive strength (B) is smaller, the increase in the residual mold compressive strength is suppressed, and the mold is excellent in the disintegration property.

Claims (29)

1. A binder composition for mold making, which contains a phenol resin and a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
2. The binder composition for mold making according to claim 1, wherein a content of the cyclic ketal compound is 0.2 mass% or more and 30 mass% or less in the binder composition for mold making.
3. The binder composition for mold making according to claim 1 or 2, wherein the content of the cyclic ketal compound is 0.5 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the phenol resin.
4. The binder composition for mold making according to any one of claims 1 to 3, wherein the cyclic ketal compound has 20 or less carbon atoms.
5. The binder composition for mold making according to any one of claims 1 to 4, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1),
Figure FDA0003371761630000011
in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2OH, however, R3 and R4 are not both hydrogen.
6. The binder composition for mold making according to claim 5, wherein in the general formula (1), R1 and R2 are at least 1 selected from the group consisting of R1 being methyl and R2 being methyl, R1 being methyl and R2 being ethyl, R1 being methyl and R2 being hydrogen, R1 being ethyl and R2 being ethyl.
7. The binder composition for mold making according to claim 5 or 6, wherein a content of the compound represented by the general formula (1) in the cyclic ketal is 80% by mass or more.
8. The binder composition for mold making according to any one of claims 1 to 7, further comprising an alcohol containing 1 or more selected from the group consisting of a polyol, a glycol ether, an alicyclic glycol compound and an aromatic alcohol.
9. The binder composition for mold making according to claim 8, wherein the content of 1 or more selected from the group consisting of a polyol, a glycol ether, an alicyclic glycol compound and an aromatic compound alcohol in the alcohol is 80% by mass or more.
10. The binder composition for mold making according to claim 8 or 9, wherein a content of the cyclic ketal compound is 0.2 mass% or more and 18 mass% or less in the binder composition for mold making.
11. The binder composition for mold making according to any one of claims 8 to 10, wherein the content of the alcohol in the binder composition for mold making is 0.5 mass% or more and 15 mass% or less.
12. The binder composition for mold making according to any one of claims 8 to 11, wherein a content of the cyclic ketal compound is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the phenol resin.
13. The binder composition for mold making according to any one of claims 8 to 12, wherein the content of the alcohol is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the phenol resin.
14. The binder composition for mold making according to any one of claims 8 to 13, wherein a total content of the cyclic ketal compound and the alcohol is 1 mass% or more and 20 mass% or less in the binder composition for mold making.
15. The binder composition for mold making according to any one of claims 8 to 14, wherein a total content of the cyclic ketal compound and the alcohol is 2 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the phenol resin.
16. The binder composition for mold making according to any one of claims 8 to 15, wherein a ratio of a content of the cyclic ketal compound to a total content of the alcohol and the cyclic ketal compound is 0.1 or more and 0.8 or less.
17. A method for manufacturing a mold, comprising: a mixing step of mixing the refractory particles and the binder composition for mold molding according to any one of claims 1 to 16 to obtain a composition for mold molding; and a curing step of charging the composition for mold molding into a mold and curing the composition for mold molding.
18. The method for producing a mold according to claim 17, wherein the curing agent for curing the mold-making composition in the curing step is an organic ester compound or carbon dioxide.
19. A composition for mold making, which comprises the binder composition for mold making according to any one of claims 1 to 16 and refractory particles.
20. The composition for mold making according to claim 19, wherein the binder composition is contained in an amount of 10 parts by mass or more and 100 parts by mass or less with respect to 1000 parts by mass of the refractory particles.
21. A composition for mold molding, which contains a phenol resin, a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms, and flame-resistant particles.
22. A mold-molding composition according to any one of claims 19 to 21, wherein the phenol resin is contained in an amount of 5 parts by mass or more and 80 parts by mass or less with respect to 1000 parts by mass of the refractory particles.
23. The mold making composition according to any one of claims 19 to 22, wherein a content of the cyclic ketal compound is 0.5 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the phenol resin.
24. The composition for mold making according to any one of claims 19 to 23, further comprising inorganic particles having an average particle diameter of 0.1 to 50 μm.
25. The composition for mold making according to claim 24, wherein a content of the inorganic particles is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the phenol resin.
26. An additive for mold making, which contains a cyclic ketal compound having a hydroxyl group and having 5 or more carbon atoms.
27. The additive for foundry molding according to claim 26, wherein the cyclic ketal has 20 or less carbon atoms.
28. The additive for foundry molding according to claim 26 or 27, wherein the cyclic ketal compound comprises a compound represented by the following general formula (1),
Figure FDA0003371761630000041
in the general formula (1), R1 and R2 each represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R3 and R4 each represent hydrogen or-CH2OH, however, R3 and R4 are not both hydrogen.
29. The additive for mold making according to claim 28, wherein a content of the compound represented by the general formula (1) in the cyclic ketal is 80% by mass or more.
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