WO2011078117A1 - 鋳型の製造方法 - Google Patents
鋳型の製造方法 Download PDFInfo
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- WO2011078117A1 WO2011078117A1 PCT/JP2010/072889 JP2010072889W WO2011078117A1 WO 2011078117 A1 WO2011078117 A1 WO 2011078117A1 JP 2010072889 W JP2010072889 W JP 2010072889W WO 2011078117 A1 WO2011078117 A1 WO 2011078117A1
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- WIPO (PCT)
- Prior art keywords
- sand
- mold
- curing agent
- agent composition
- weight
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Classifications
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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
- 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
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
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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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- 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
- 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
Definitions
- the present invention relates to a curing agent composition used in producing a mold using refractory particles containing regenerated sand made of artificial sand produced by a melting method, and a water-soluble phenolic resin, and the same
- the present invention relates to a mold composition and a method for producing a mold.
- a self-hardening mold molding method is known as a molding method for producing molds such as a main mold and a core using a binder.
- a mold forming method is known in which a water-soluble phenolic resin as a binder is cured with an ester-based curing agent.
- the present invention provides a curing agent composition capable of preventing the drying of the kneading sand even if the working time for molding is prolonged, and a mold composition and a method for producing the mold using the same.
- the method for producing a mold according to the present invention comprises the steps of: kneading refractory particles, a water-soluble phenolic resin, and a curing agent composition containing an ester compound to obtain a kneading sand;
- the composition for a mold according to the present invention is a hardener containing refractory particles containing regenerated sand consisting of artificial sand produced by a melting method at a content of 70% by weight or more, a water-soluble phenolic resin, and an ester compound.
- a composition for a template comprising: a composition comprising: one or more selected from triethylene glycol diacetate, triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol is there.
- the hardener composition of the present invention is used to manufacture a mold using refractory particles containing regenerated sand consisting of artificial sand produced by a melting method at a content of 70% by weight or more and a water-soluble phenolic resin
- a curing agent composition containing an ester compound, which is used for the curing which comprises one or more selected from triethylene glycol diacetate, triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol Agent composition.
- the drying of the kneading sand can be prevented even if the working time for forming is long. Moreover, according to the composition for a mold of the present invention and the method for manufacturing a mold, molding workability can be improved and a reduction in mold strength can be prevented.
- the hardener composition of the present invention is used to manufacture a mold using refractory particles containing regenerated sand consisting of artificial sand produced by a melting method at a content of 70% by weight or more and a water-soluble phenolic resin
- the curing agent composition used in hereinafter, the components of the curing agent composition of the present invention will be described.
- ⁇ Component to prevent the drying of the kneading sand> one component selected from triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol as a component for preventing drying of the kneaded sand (hereinafter referred to as a drying preventing component)
- a drying preventing component a component for preventing drying of the kneaded sand
- the content is 2% by weight or more from the viewpoint of preventing the drying of the kneading sand. Is preferably 4% by weight or more, and more preferably 8% by weight or more. Also, in view of mold strength, the content of one or more selected from triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol is preferably 50% by weight or less, and is 40% by weight or less Is more preferable, and 30% by weight or less is even more preferable.
- the content of one or more selected from triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol is preferably 2 to 50% by weight, and is 4 to 40% by weight. Is more preferably 8 to 30% by weight.
- the curing agent composition of the present invention contains an ester compound as a component for curing the water-soluble phenolic resin.
- ester compounds conventionally known ester compounds that can be used as curing agents for water-soluble phenol resins can be used, but from the viewpoint of the curability of water-soluble phenol resins, ester compounds having 1 to 5 ester bonds in the molecule are preferable.
- organic esters derived from lactones or monohydric or polyhydric alcohols having 1 to 10 carbon atoms and organic carboxylic acids having 1 to 10 carbon atoms, and inorganic esters such as ethylene carbonate and propylene carbonate can be mentioned. Among them, organic esters are preferable from the viewpoint of mold strength.
- the carboxylic acid-derived moiety may be linear or branched, and the branching is preferably branched at the ⁇ -position.
- the organic ester include ⁇ -butyrolactone, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate, triethylene glycol diacetate, triacetin, ethyl acetoacetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, 2 -Dimethyl ethyl succinate, Dimethyl 2-methyl glutarate, Dimethyl 2-methyl adipate, Methyl 2-ethyl hexanoate, Ethyl 2-ethyl hexanoate, Dimethyl 2-methyl sebacate, Dimethyl 2-ethyl azelate, 2-ethyl Diethyl glutarate, dimethyl 2- (n-propyl) glutarate, diethyl 2- (n-butyl) succinate, dimethyl 2- (n-butyl
- triethylene glycol diacetate When the temperature or sand temperature is not high or low, or when the working time is neither long nor short, triethylene glycol diacetate, triacetin and ethylene glycol diacetate are preferred. In the present invention, these ester compounds can be used alone or in combination of two or more. In addition, when using triethylene glycol diacetate as an ester compound, since triethylene glycol diacetate has the effect
- the content of the ester compound in the curing agent composition is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 70% by weight or more .
- the content of the ester compound in the curing agent composition is preferably 98 wt% or less, 96 wt% It is more preferable that it is the following, and it is still more preferable that it is 94 weight% or less.
- the content of the ester compound in the curing agent composition is preferably 50 to 98% by weight, more preferably 60 to 96% by weight, and 70 to 94% by weight. Is more preferred.
- triethylene glycol diacetate When triethylene glycol diacetate is used as the ester compound, its content is preferably 1 to 20% by weight from the viewpoint of mold strength when the air temperature or sand temperature is low or when the working time is short, and the air temperature and sand When the temperature is high or the working time is long, 30 to 98% by weight is preferable.
- the curing agent composition of the present invention is essential to contain at least one selected from triethylene glycol diacetate, triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol from the viewpoint of prevention of drying. .
- a preferred combination of the anti-drying component and the ester compound is one or more selected from triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol from the viewpoint of the compressive strength after 24 hours of molding immediately after kneading,
- a preferred combination is triethylene glycol diacetate, and one or more selected from triethylene glycol and benzyl alcohol and triethylene glycol diacetate.
- the weight ratio of one or more selected from triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol to one or more selected from ester compounds triethylene glycol diacetate, triacetin and ethylene glycol diacetate is From the viewpoint of compressive strength after 24 hours of molding immediately after kneading, 4/96 to 30/70 is preferable, and 10/90 to 25/75 is more preferable. Furthermore, the weight ratio of one or more selected from triethylene glycol and benzyl alcohol to one or more selected from ester compounds triethylene glycol diacetate, triacetin and ethylene glycol diacetate was incorporated immediately after kneading. From the viewpoint of compressive strength after 24 hours, 4/96 to 30/70 is preferable, and 10/90 to 25/75 is more preferable.
- the curing agent composition of the present invention may contain a phenol compound monomer, and an additive such as a fragrance and a surfactant to an extent not inhibiting the effect of the present invention.
- the curing agent composition of the present invention may contain a phenol compound monomer. This is because the pot life can be extended without reducing the final strength of the mold even when the outside air temperature is high (for example, 40 ° C. or higher).
- phenol compound monomer examples include phenol, cresol, xylenol, cumylphenol, nonylphenol, butylphenol, phenylphenol, ethylphenol, octylphenol, amylphenol, naphthol, resorcinol, bisphenol A, bisphenol F, bisphenol C, catechol, hydroquinone , Pyrogallol, fluoroglycine, mixtures thereof and the like. Furthermore, resorcinol residue, bisphenol A residue, chlorophenol, dichlorophenol and the like, and other substituted phenols and the like can also be used. In the present invention, these phenol compound monomers can be used alone or in combination of two or more. Among them, preferably, when containing resorcin and bisphenol A, more preferably resorcin, the pot life can be further extended without reducing the final strength of the template.
- the content of the above-mentioned phenol compound monomer is preferably 1% by weight or more, and 2% by weight or more in the curing agent composition, from the viewpoint of extending the pot life. Is more preferred.
- the content of the above-mentioned phenol compound monomer is preferably 30% by weight or less, and more preferably 20% by weight or less in the curing agent composition. Taking the above viewpoints into consideration, the content of the above-mentioned phenol compound monomer is preferably 1 to 30% by weight, and more preferably 2 to 20% by weight in the curing agent composition.
- the curing agent composition of the present invention may contain a surfactant to such an extent that the effects of the present invention are not impaired.
- a nonionic surfactant such as polyoxyethylene (5) lauryl ether
- the addition amount of these additives is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of the ester compound.
- the composition for a mold according to the present invention contains fire-resistant particles containing regenerated sand consisting of artificial sand produced by a melting method at a content of 70% by weight or more, a water-soluble phenol resin, and an ester compound.
- a composition for a template containing a curing agent composition comprising: one or more selected from triethylene glycol diacetate, triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol It is a thing.
- One or more selected from triethylene glycol diacetate, triethylene glycol, 3-phenylpropan-1-ol and benzyl alcohol in the composition for a mold of the present invention may be contained as one component of a curing agent composition They may be contained as one component of the water-soluble phenolic resin, or may be separately added when mixing the refractory particles, the water-soluble phenolic resin and the curing agent composition.
- the timing of the addition of the anti-drying component and triethylene glycol diacetate at that time is not particularly limited.
- the other components that can be contained in the above-described curing agent composition of the present invention can be obtained similarly to the above even if they are separately added without being included in the curing agent composition. That is, a phenolic compound monomer such as resorcin, or an additive such as a fragrance or a surfactant may be contained as one component of the curing agent composition, or may be contained as one component of the water-soluble phenolic resin In mixing the refractory particles, the water-soluble phenolic resin and the curing agent composition, they may be separately added.
- composition for template (kneaded sand) after preparation contains a phenolic compound monomer such as resorcin or an additive such as a fragrance or a surfactant. Just do it.
- the method for producing a mold of the present invention produces a mold from a composition for mold (kneaded sand) obtained by adding the above-mentioned curing agent composition of the present invention and a water-soluble phenolic resin to refractory particles.
- a step of kneading refractory particles, a water-soluble phenol resin and the curing agent composition of the present invention to obtain kneading sand, and a step of molding the kneading sand for molding A method for producing a mold having the above, wherein the refractory particles contain regenerated sand consisting of artificial sand produced by a melting method at a content of 70% by weight or more.
- the phenol compound monomer especially resorcinol
- the phenol compound monomer be contained in the kneading sand as the other components described above, but it is more preferable that it be contained in the curing agent composition preferable.
- template of this invention is demonstrated.
- refractory particles containing regenerated sand composed of artificial sand produced by a melting method at a content of 70% by weight or more are used.
- silica sand, zircon sand, chromite sand, olivine sand, cement sand, etc. may be contained as refractory particles other than the regenerated sand which consists of the artificial sand manufactured by the melting method.
- the artificial sand manufactured by the sintering method may be contained.
- the refractory particles used in the present invention have a content of the above-mentioned recycled sand of about 100% by weight. It is preferable to contain, and "containing the above-mentioned reclaimed sand at a content of about 100% by weight" means that even if it is a refractory particle other than the above-mentioned reclaimed sand, if it is unavoidably included, its content If the ratio is 2% by weight or less, it means that it may be contained.
- the artificial sand produced by the melting method refers to, for example, an artificial sand obtained by melting and granulating using heat and the like, using a starting material containing alumina and silica.
- alumina sand containing 40 wt% or more of alumina is preferable, alumina sand containing 55 to 90 wt% of alumina is more preferable, and alumina sand containing 67 to 90 wt% of alumina is more preferable. Is more preferred.
- a method of granulating the melt of the starting material a method of spraying the melt, a method of blowing air to the melt, and the like can be mentioned. That is, the melt is air-crushed in the molten state to particles of a predetermined particle size distribution in air, and after air-crushing, the surface tension of the molten particles themselves becomes cast sand (refractory particles) of a predetermined surface area.
- the melting method is not particularly limited, and melting may be performed by an arc furnace, a crucible furnace, an induction electric furnace (high frequency furnace, low frequency furnace, etc.), a resistance type electric furnace, a reflection furnace, a rotary furnace, a vacuum melting furnace, a cupola furnace, etc. it can.
- a method of melting and spheroidizing the starting material in a flame may be used.
- the starting material of the artificial sand can be selected, for example, from mineral materials and synthetic materials having fire resistance.
- mineral materials and synthetic materials having fire resistance for example, as an alumina source, bauxite, van earth shale, aluminum oxide, aluminum hydroxide and the like can be mentioned.
- silica source silica stone, silica sand, quartz, cristobalite, amorphous silica, feldspar, pyrophyllite, etc. can be mentioned.
- alumina source and a silica source kaolin, van soil shale, bauxite, mica, sillimanite, andalusite, mullite, zeolite, montmorillonite, hylosite and the like can be mentioned. These starting materials can be used alone or in combination of two or more.
- the reclaimed sand that can be used in the present invention is produced by casting a cast from a water-soluble phenolic resin and then releasing it, and the loose sand is reclaimed one or more times by a general reclaiming method (wet, dry, thermal, etc.) Sand, which is regenerated by a dry method (in particular, a wear type), has a high yield and is economically excellent and preferable. Also, these reproduction methods may be combined and reproduced.
- the reclaimed sand that can be used in the present invention preferably has a loss on ignition (LOI) of 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, and further preferably, from the viewpoint of improving the strength of the mold. It is preferably 0.2 to 5% by weight, more preferably 0.2 to 2.0% by weight.
- LOI refers to the weight loss rate when heated in air at 500 ° C. for 2 hours.
- the water-soluble phenolic resin that can be used in the method for producing a mold of the present invention is a resin curable with an ester compound, and is generally obtained by polycondensation of a phenolic compound and an aldehyde compound under alkaline conditions .
- phenol compounds include phenol, bisphenol A, bisphenol F, cresol, 3,5-xylenol, resorcine, catechol, nonylphenol, p-tert-butylphenol, isopropenylphenol, phenylphenol and other substituted phenols.
- mixtures of various phenolic compounds such as cashew nut shell liquid are used.
- aldehyde compound formaldehyde, furfural, glyoxal etc. can be used 1 type or in mixture of 2 or more types.
- aldehyde compound formaldehyde, furfural, glyoxal etc.
- aldehyde compound formaldehyde, furfural, glyoxal etc.
- monomers capable of condensation with aldehyde compounds such as urea, melamine and cyclohexanone, and monovalent aliphatic alcohol compounds such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol and butyl alcohol, and water-soluble polymers
- cellulose derivative polymers, polyvinyl alcohol, lignin derivatives and the like may be mixed.
- alkali catalyst used for the synthesis of the water-soluble phenolic resin examples include hydroxides of alkali metals such as LiOH, NaOH and KOH, but NaOH and KOH are particularly preferable. Moreover, you may mix and use these alkali catalysts.
- the molar ratio of the aldehyde compound to the phenolic compound is preferably 1.0 to 6.0 moles, more preferably 1.1 to 5.5 moles.
- the molar ratio of the alkali catalyst to the phenolic compound is preferably 0.2 to 5.0 moles, more preferably 0.5 to 4.0 moles.
- the solid content weight (solid weight after drying for 3 hours at 105 ° C.) in the water-soluble phenolic resin is preferably 25 to 90% by weight, more preferably 30 to 85% by weight from the viewpoint of mold strength. is there.
- the weight average molecular weight (Mw) of the water-soluble phenolic resin is preferably 500 to 8000, more preferably 800 to 5000, from the viewpoint of mold strength.
- the weight average molecular weight (Mw) of the water-soluble phenolic resin can be measured by GPC (gel permeation chromatography) under the following conditions.
- the mold can be manufactured using the process of the conventional self-hardening mold making method as it is.
- the temperature of the kneading sand at the time of molding is usually about -10 to 50 ° C, but from the viewpoint of securing the pot life, -5 to 40 ° C is preferable, and 0 to 35 ° C is more preferable.
- the working time from the end of kneading to the end of molding of the kneading sand is usually about 1 to 9 minutes, but when the above operation time is 10 minutes or more, the artificially produced by the conventional melting method
- a mold is produced by a self-hardening mold making method using a reclaimed sand consisting of sand, the drying of the kneading sand proceeds remarkably and the workability is deteriorated.
- drying of the kneading sand can be prevented even if the working time is 10 minutes or more.
- the working time is preferably 10 minutes or more, more preferably 12 minutes or more, further preferably 15 minutes or more, The effects of the present invention are more significantly exhibited. Moreover, from a viewpoint of productivity, 60 minutes or less are preferable and, as for the said working time, 30 minutes or less are more preferable.
- the content of the curing agent composition in the kneading sand is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the refractory particles.
- the content of the water-soluble phenolic resin in the kneading sand is 0.1 to 10 with respect to 100 parts by weight of the refractory particles as the content of the solid content from the viewpoint of mold strength, workability, odor and cost.
- the parts by weight are preferable, and 0.5 to 5 parts by weight are more preferable.
- mixing sand the method of adding and mixing each component with a batch mixer, and the method of supplying and mixing each component to a continuous mixer are mentioned.
- silane coupling agents include ⁇ - (2-amino) propylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, N- ⁇ (Aminoethyl) ⁇ -aminopropylmethyldimethoxysilane and the like.
- the compounding amount of the silane coupling agent is preferably 0.001 to 10 parts by weight, more preferably 0.02 to 1 parts by weight with respect to 100 parts by weight of the water-soluble phenol resin (in terms of solid content).
- the mold production method of the present invention is suitable for molding non-ferrous alloy castings such as aluminum castings and casting molds for producing cast steel castings or cast iron castings, but the application for casting is particularly limited. It is not a thing.
- the recovered sand was placed in a crusher and regenerated using a M-type rotary reclaimer manufactured by Nippon Casting Co., Ltd.
- the regenerated sand (LOI: 0.6% by weight) obtained by repeating the above steps 10 times was used for the evaluation shown below.
- Example 4 and Comparative Example 2 the said reproduction
- regeneration sand: new sand 70: 30.
- the state in which the surface of the kneading sand is dried means that the wettability of the kneading sand is lost and the sand particles are in a fixed state.
- mixing it evaluated by the following references
- the compressive strength is described by the method (compression rate 5 mm / sec) described in JIS Z 2604-1976.
- the compressive strength was a value obtained by dividing the applied load by the cross-sectional area of the test piece.
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Abstract
Description
本発明の硬化剤組成物には、混練砂の乾燥を防止するための成分(以下、乾燥防止成分という)として、トリエチレングリコール、3-フェニルプロパン-1-オール及びベンジルアルコールから選ばれる1種以上を含有することができる。なかでも、混練砂の乾燥防止の観点から、トリエチレングリコール及びベンジルアルコールから選ばれる1種以上を含有することが好ましい。
本発明の硬化剤組成物には、水溶性フェノール樹脂を硬化させる成分として、エステル化合物が含有される。エステル化合物としては、水溶性フェノール樹脂の硬化剤として使用できる従来公知のエステル化合物が使用できるが、水溶性フェノール樹脂の硬化性の観点から、分子内にエステル結合を1~5個有するエステル化合物が好ましい。例えば、ラクトン類、又は炭素数1~10の一価若しくは多価アルコールと炭素数1~10の有機カルボン酸とから導かれる有機エステルや、炭酸エチレン、炭酸プロピレン等の無機エステルが挙げられる。なかでも、鋳型強度の観点から有機エステルが好ましい。有機エステルはカルボン酸由来部分が直鎖であっても、分岐であってもよく、分岐はα-位の分岐が好ましい。有機エステルの具体例としては、γ-ブチロラクトン、ギ酸エチル、エチレングリコールジアセテート、エチレングリコールモノアセテート、トリエチレングリコールジアセテート、トリアセチン、アセト酢酸エチル、コハク酸ジメチル、グルタル酸ジメチル、アジピン酸ジメチル、2-エチルコハク酸ジメチル、2-メチルグルタル酸ジメチル、2-メチルアジピン酸ジメチル、2-エチルヘキサン酸メチル、2-エチルヘキサン酸エチル、2-メチルセバシン酸ジメチル、2-エチルアゼライン酸ジメチル、2-エチルグルタル酸ジエチル、2-(n-プロピル)グルタル酸ジメチル、2-(n-ブチル)コハク酸ジエチル、2-(n-ブチル)コハク酸ジメチル、2-メチルピメリン酸ジエチル、2-メチルスベリン酸ジメチル等が挙げられ、鋳型強度の観点から、気温や砂の温度が低い場合あるいは作業時間が短い場合はγ-ブチロラクトン、ギ酸エチルが好ましく、気温や砂の温度が高い場合あるいは作業時間が長い場合はアセト酢酸エチル、コハク酸ジメチル、グルタル酸ジメチル、アジピン酸ジメチル、2-エチルコハク酸ジメチル、2-メチルグルタル酸ジメチル、2-メチルアジピン酸ジメチルが好ましい。気温や砂温度が高くも低くもない場合、あるいは作業時間が長くも短くもない場合には、トリエチレングリコールジアセテート、トリアセチン、エチレングリコールジアセテートが好ましい。本発明では、これらのエステル化合物を単独で、又は2種以上を混合して使用できる。なお、エステル化合物として、トリエチレングリコールジアセテートを使用する場合は、トリエチレングリコールジアセテートは乾燥防止の作用を有するので、乾燥防止成分は含有されなくても良い。
本発明の硬化剤組成物には、フェノール化合物単量体や、本発明の効果を阻害しない程度に香料や界面活性剤等の添加剤が含有されてもよい。
本発明の硬化剤組成物には、フェノール化合物単量体が含有されてもよい。外気温度が高い場合(例えば40℃以上の場合)においても、鋳型の最終強度を低下させることなく、可使時間を延長できるからである。
本発明の硬化剤組成物には、本発明の効果を阻害しない程度に界面活性剤が含有されてもよい。なかでも、ポリオキシエチレン(5)ラウリルエーテルのような非イオン性界面活性剤が含有されると、混練砂から発せられる臭気を低減することができるため好ましい。これら添加剤の添加量は、エステル化合物100重量部に対して、0.001~20重量部が好ましい。
本発明では、溶融法で製造された人工砂からなる再生砂を70重量%以上の含有率で含有する耐火性粒子を使用する。なお、溶融法で製造された人工砂からなる再生砂以外の耐火性粒子として、珪砂、ジルコン砂、クロマイト砂、オリビン砂、セメント砂等が含有されてもよい。また、焼結法で製造された人工砂が含有されてもよい。
本発明の鋳型の製造方法で使用可能な水溶性フェノール樹脂は、エステル化合物で硬化可能な樹脂であり、一般にはアルカリ条件下でフェノール化合物とアルデヒド化合物とを重縮合させることによって得られるものである。このうちフェノール化合物としては、フェノール、ビスフェノールA、ビスフェノールF、クレゾール、3,5-キシレノール、レゾルシン、カテコール、ノニルフェノール、p-tert-ブチルフェノール、イソプロペニルフェノール、フェニルフェノール、その他の置換フェノールを含めたフェノール類や、カシューナット殻液のような各種のフェノール化合物の混合物等が用いられる。製造時には、これらを1種又は2種以上混合して使用することができる。また、アルデヒド化合物としては、ホルムアルデヒド、フルフラール、グリオキザール等を1種又は2種以上混合して使用することができる。これらの化合物は必要に応じて水溶液として用いることができる。また、これらに、尿素、メラミン、シクロヘキサノン等のアルデヒド化合物と縮合が可能なモノマーや、メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、ブチルアルコール等の1価の脂肪族アルコール化合物や、水溶性高分子のポリアクリル酸塩や、セルロース誘導体高分子、ポリビニルアルコール、リグニン誘導体などを混合しても差し支えない。
(a)サンプル調製:試料に同重量のイオン交換水を加え、0.1重量%のH2SO4を加えて中和する。生成した沈殿を濾過分離し、水洗し、乾燥する。これをテトラヒドロフラン(THF)に溶解し、GPC用のサンプルを調製する。
(b)カラム:ガードカラムTSX(東洋曹達工業社製)HXL(6.5mmφ×4cm)1本と、TSK3000HXL(7.8mmφ×30cm)1本と、TSK2500HXL(7.8mmφ×30cm)1本を使用する。注入口側よりガードカラム-3000HXL-2500HXLの順に接続する。
(c)標準物質:ポリスチレン(東洋曹達工業社製)
(d)溶出液:THF(流速:1cm3/min)
(e)カラム温度:25℃
(f)検出器:紫外分光光度計(フェノールの紫外吸収の最大ピークの波長において定量)
(g)分子量計算の為の分割法:時間分割(2sec)
溶融法で製造された人工アルミナ砂(エスパール#40L、山川産業社製)の新砂100重量部に対し、水溶性フェノール樹脂(カオーステップ SH-8010、花王クエーカー社製)1.2重量部と、水溶性フェノール樹脂の硬化剤としてトリアセチン0.3重量部とを添加し、これらを混練して得られた混練砂を用いて鋳型を造型した。得られた鋳型を用いて、鋳物材質FC-250(S/M=4、ここでS/Mとは鋳型の重量(S)と鋳造物の重量(M)の比を表す)を鋳造し、回収した砂をクラッシャーにかけ、日本鋳造社製M型ロータリーリクレーマーを用いて再生した。以上の工程を10回繰り返して得られた再生砂(LOI:0.6重量%)を以下に示す評価に用いた。なお、実施例4及び比較例2については、上記再生砂と、エスパール#40Lの新砂とを、再生砂:新砂=70:30の重量比で混合して用いた。また、参考例1については、上記再生砂と、エスパール#40Lの新砂とを、再生砂:新砂=60:40の重量比で混合して用いた。
表1に示すアルミナ砂100重量部に対し、水溶性フェノール樹脂(カオーステップ SH-8010、花王クエーカー社製)1.2重量部と、表1に示す硬化剤組成物0.3重量部とを添加し、これらを混練して得られた混練砂を外気に曝される開放状態で放置し、混練終了直後から1分毎に混練砂の表面の乾燥状態を指触にて確認し、乾燥するまでの時間を測定した。なお、「混練砂の表面が乾燥した状態」とは、混練砂の湿潤性が無くなり、砂粒子同士が固着した状態であることをいう。また、混練終了直後から10分後の混練砂の表面の乾燥状態について、指触にて以下の基準で評価した。
A:砂粒子同士が固着しておらず、混練直後の砂と同レベルの湿潤性がある。
B:砂粒子同士は固着してないが、混練直後の砂と同レベルの湿潤性はない。
C:砂粒子同士が固着している。
表1に示すアルミナ砂100重量部に対し、水溶性フェノール樹脂(カオーステップ SH-8010、花王クエーカー社製)1.2重量部と、表1に示す硬化剤組成物0.3重量部とを添加し、これらを混練して混練砂を得た。得られた混練砂を型込めし、テストピース(50mm×50mmφ)を成型した。型込めには、混練直後の混練砂と、混練した後で10分放置(雰囲気温度は型込め時と同じ温度)した混練砂の2種類を用いた。そして、25℃(55%RH)の条件下で成型から24時間経過した後のテストピースについて、JIS Z 2604-1976に記載された方法(圧縮速度5mm/sec)で、圧縮強度(鋳型強度)を測定した。なお、圧縮強度は、負荷した荷重をテストピースの断面積で除した値とした。
Claims (10)
- 耐火性粒子と、水溶性フェノール樹脂と、エステル化合物を含有する硬化剤組成物とを混練して、混練砂を得る工程、及び前記混練砂を型込めして造型する工程を有する鋳型の製造方法であって、
前記耐火性粒子が、溶融法で製造された人工砂からなる再生砂を70重量%以上の含有率で含有し、
前記硬化剤組成物が、トリエチレングリコールジアセテート、トリエチレングリコール、3-フェニルプロパン-1-オール及びベンジルアルコールから選ばれる1種以上を含有する、鋳型の製造方法。 - 前記混練砂が、更にレゾルシンを含有する請求項1記載の鋳型の製造方法。
- 前記硬化剤組成物が、更にレゾルシンを含有する請求項1記載の鋳型の製造方法。
- 前記人工砂が、アルミナ砂である請求項1~3の何れか1項記載の鋳型の製造方法。
- 前記混練終了直後から型込め終了までの作業時間が、10分以上である請求項1~4の何れか1項記載の鋳型の製造方法。
- 溶融法で製造された人工砂からなる再生砂を70重量%以上の含有率で含有する耐火性粒子と、水溶性フェノール樹脂と、エステル化合物を含有する硬化剤組成物とを含有する鋳型用組成物であって、
トリエチレングリコールジアセテート、トリエチレングリコール、3-フェニルプロパン-1-オール及びベンジルアルコールから選ばれる1種以上を含有する、鋳型用組成物。 - 更にレゾルシンを含有する請求項6記載の鋳型用組成物。
- 前記鋳型用組成物の混練終了直後から型込め終了までの作業時間が10分以上である鋳型の製造に用いられる請求項6又は7記載の鋳型用組成物。
- 溶融法で製造された人工砂からなる再生砂を70重量%以上の含有率で含有する耐火性粒子と、水溶性フェノール樹脂とを用いて鋳型を製造する際に使用される、エステル化合物を含有する硬化剤組成物であって、
トリエチレングリコールジアセテート、トリエチレングリコール、3-フェニルプロパン-1-オール及びベンジルアルコールから選ばれる1種以上を含有する、硬化剤組成物。 - 更にレゾルシンを含有する請求項9記載の硬化剤組成物。
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EP10839347.1A EP2581148B1 (en) | 2009-12-24 | 2010-12-20 | Process for production of molds |
CN201080058535.4A CN102665961B (zh) | 2009-12-24 | 2010-12-20 | 铸型的制造方法 |
US13/518,745 US20120261087A1 (en) | 2009-12-24 | 2010-12-20 | Process for producing a mold |
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CN104117625A (zh) * | 2014-06-26 | 2014-10-29 | 芜湖市鸿坤汽车零部件有限公司 | 一种废保温砖醇基铸造涂料及其制作方法 |
CN104525837A (zh) * | 2014-12-01 | 2015-04-22 | 繁昌县恒鑫汽车零部件有限公司 | 一种灰铸铁大件用手工型砂及其制备方法 |
CN104525834A (zh) * | 2014-12-01 | 2015-04-22 | 繁昌县恒鑫汽车零部件有限公司 | 一种高压造型面砂及其制备方法 |
CN104525836A (zh) * | 2014-12-01 | 2015-04-22 | 繁昌县恒鑫汽车零部件有限公司 | 一种可回收粘土型砂及其制备方法 |
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