WO2013133131A1 - 鋳型造型用粘結剤組成物及び鋳型の製造方法 - Google Patents

鋳型造型用粘結剤組成物及び鋳型の製造方法 Download PDF

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Publication number
WO2013133131A1
WO2013133131A1 PCT/JP2013/055505 JP2013055505W WO2013133131A1 WO 2013133131 A1 WO2013133131 A1 WO 2013133131A1 JP 2013055505 W JP2013055505 W JP 2013055505W WO 2013133131 A1 WO2013133131 A1 WO 2013133131A1
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Prior art keywords
weight
binder composition
mold
composition
acid
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PCT/JP2013/055505
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English (en)
French (fr)
Japanese (ja)
Inventor
俊樹 松尾
雅彦 渡邊
快 矢代
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花王株式会社
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Priority to IN7035DEN2014 priority Critical patent/IN2014DN07035A/en
Priority to CN201380008936.2A priority patent/CN104105558B/zh
Publication of WO2013133131A1 publication Critical patent/WO2013133131A1/ja

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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
    • 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
    • B22C1/224—Furan polymers

Definitions

  • the present invention relates to a binder composition for mold making, a composition for mold using the same, and a method for producing a mold.
  • the acid-curable self-hardening mold is prepared by adding a mold-forming binder containing an acid-curable resin and a curing agent containing organic sulfonic acid, sulfuric acid, phosphoric acid, etc. to refractory particles such as silica sand. After kneading these, the obtained kneaded sand is filled into a mold such as a wooden mold and the acid curable resin is cured.
  • Furan resin, phenol resin, etc. are used for acid curable resin.
  • Furan resin is furfuryl alcohol, furfuryl alcohol / urea formaldehyde resin, furfuryl alcohol / formaldehyde resin, furfuryl alcohol / phenol / formaldehyde. Resins and other known modified furan resins are used.
  • the obtained mold is used when casting a casting such as a machine casting part, a construction machine part, or an automobile part.
  • An improvement of the final strength of the mold is an important item when molding the above-described mold or casting a desired casting using the mold.
  • the final strength of the mold is particularly necessary when producing large molds. If the strength is insufficient, the mold may crack or core cracks may occur during casting, causing danger to the operator. There is a risk that the resulting casting will be defective.
  • Patent Document 1 there is provided an acid-curing mold binder composition obtained by mixing or reacting an acid-curing resin with a compound having one or more aldehyde groups in a molecule obtained from saccharides or starch. Disclosed is a mold with high curing speed, high mold strength and excellent surface stability.
  • Patent Document 2 At least one selected from a specific amount of 5-hydroxymethylfurfural, 2,5-furandimethylol, 2,5-furandicarboxylic acid, 2,5-diformylfuran, and polyester polyol is used.
  • the binder composition of Patent Document 2 although the odor during casting can be reduced, the final strength is not sufficient, and further improvement has been demanded.
  • the binder composition of Patent Document 1 cannot be said to have good solubility in an acid curable resin such as a furan resin, and the storage stability of the binder composition, in particular, the final strength of the mold. Since it was not enough, further improvement was required.
  • the present invention provides a binder composition for mold making that can improve the final strength of a mold, a composition for a mold using the same, and a method for producing a mold using the same.
  • the binder composition for mold making of the present invention is a binder composition for mold making containing a 5-hydroxymethylfurfural composition manufactured from Molasses and an acid-curable resin.
  • the mold composition of the present invention is a mold composition comprising a mixture of refractory particles, the mold-forming binder composition, and a furan resin curing agent for curing the mold-molding binder composition. It is a thing.
  • the method for producing a mold according to the present invention includes a step of curing a mixture containing refractory particles, the above-mentioned binder for mold molding, and a curing agent for furan resin for curing the binder composition for mold molding. This is a method for producing a mold.
  • the final strength of the mold can be improved. Further, according to the mold composition and the mold manufacturing method of the present invention, the final strength of the mold can be improved.
  • the binder composition for mold making of the present invention (hereinafter, also simply referred to as “binder composition”) is used as a binder when producing a mold, and is produced from Molasses.
  • This is a binder composition for mold making containing a 5-hydroxymethylfurfural composition and an acid curable resin.
  • the binder composition of the present invention has an effect of improving the final strength of the mold. The reason for such an effect is not clear, but is considered as follows.
  • 5-Hydroxymethylfurfural has two groups, a methylol group and an aldehyde group. The methylol group has one reactive site, the aldehyde group has two reactive sites, and 5-hydroxymethylfurfural has a total of three reactive sites.
  • the reactivity of these two functional groups is different, and it seems that there are relatively reactive sites and reactive sites. Therefore, the pot life can be secured due to the difference in reactivity between the two functional groups, and the cross-linking reaction from the linear polymer proceeds at a stroke from the three reactive sites, and the template is rapidly cured. Inferred.
  • the by-product resulting from the raw material molasses dissolves the 5-hydroxymethylfurfural composition uniformly in an acid curable resin such as furan resin. It is considered that the 5-hydroxymethylfurfural composition and the furan resin can react uniformly and efficiently. For this reason, in the binder composition containing the 5-hydroxymethylfurfural composition, the crosslinking reaction is more likely to proceed, and it is considered that the mold strength can be improved.
  • the components contained in the binder composition of the present invention will be described.
  • the binder composition of the present invention contains a 5-hydroxymethylfurfural composition manufactured from Molasses and an acid curable resin.
  • the 5-hydroxymethylfurfural composition produced from molasses of the present invention comprises a step of dehydrating molasses in a solvent to obtain a reaction mixture in the presence of an acid catalyst, and extracting the reaction mixture with an organic solvent to give 5- It is manufactured through a step of obtaining a hydroxymethylfurfural composition.
  • the 5-hydroxymethylfurfural composition produced from molasses of the present invention is composed of a polymer compound having 5-hydroxymethylfurfural as a main component and a weight average molecular weight of 1000 or more, an organic acid such as levulinic acid, fructose, glucose, mannose. , Hexose such as galactose (hexose sugar), ash, moisture and the like are included as by-products.
  • Molasses is a viscous black-brown liquid that contains components other than sugar and is produced when sugar is refined from sugar cane derived from sugarcane and sugar beet.
  • molasses ⁇ Ingredients in molasses>
  • commercially available molasses can be used, and molasses manufactured by Kaset Thai Sugar Co. can be exemplified.
  • Such molasses contains sucrose, glucose, fructose, xylose, moisture, ash, protein, a high molecular weight compound having a weight average molecular weight of 3500 or more, organic acids such as lactic acid, acetic acid, formic acid, oxalic acid and citric acid.
  • the content of sucrose in molasses is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, and preferably 50% by weight or less. , 40% by weight or less is more preferable, and 30% by weight or less is more preferable.
  • the content of glucose in molasses is preferably 1.0% by weight or more, more preferably 3.0% by weight or more, still more preferably 5.0% by weight or more, from the viewpoint of improving the final strength of the mold. Moreover, 20 weight% or less is preferable, 15 weight% or less is more preferable, and 10 weight% or less is still more preferable.
  • the content of fructose in molasses is preferably 1.0% by weight or more, more preferably 5.0% by weight or more, further preferably 7.0% by weight or more, from the viewpoint of improving the final strength of the mold. Moreover, 20 weight% or less is preferable, 18 weight% or less is more preferable, and 15 weight% or less is still more preferable.
  • the xylose content in molasses is preferably 1.0% by weight or more, more preferably 2.0% by weight or more, and preferably 20% by weight or less, from the viewpoint of improving the final strength of the mold. % By weight or less is more preferred, 10% by weight or less is more preferred, and 6.0% by weight or less is even more preferred.
  • the water content in molasses is preferably 5.0% by weight or more, more preferably 15% by weight or more, and preferably 40% by weight or less from the viewpoint of improving economy and final strength of the mold. It is more preferably 35% by weight or less, and still more preferably 30% by weight or less.
  • the content of ash in molasses is preferably 1.0% by weight or more, more preferably 3.0% by weight or more, and more preferably 20% by weight or less from the viewpoint of improving economy and final strength of the mold.
  • the protein content in molasses is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and preferably 5.0% by weight or less from the viewpoint of improving the final strength of the mold. 4.0 weight% or less is more preferable, and 3.0 weight% or less is still more preferable.
  • the content of the high molecular weight compound having a weight average molecular weight of 3500 or more in molasses is preferably 1.0% by weight or more, more preferably 2.0% by weight or more, from the viewpoint of improving the final strength of the template. 0.0% by weight or more is more preferable, 20% by weight or less is preferable, 15% by weight or less is more preferable, and 10% by weight or less is more preferable.
  • the content of organic acid such as lactic acid, acetic acid, formic acid, oxalic acid, citric acid in molasses is preferably 0.1% by weight or more, and 0.5% by weight or more from the viewpoint of improving the final strength of the mold. Is more preferably 1.0% by weight or more, more preferably 5% by weight or less, more preferably 4.5% by weight or less, and still more preferably 4% by weight or less.
  • sucrose, glucose, fructose, xylose, moisture, ash, protein, high molecular weight compound having a weight average molecular weight of 3500 or more and organic acid in molasses can be measured by the method described in the examples.
  • Step I The production method of the present invention includes a step of dehydrating molasses (waste molasses) in a solvent in the presence of an acid catalyst to obtain a reaction mixture (hereinafter sometimes simply referred to as “step I”).
  • the dehydration reaction in Step I is performed in the presence of an acid catalyst.
  • the acid catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and boric acid and salts thereof, sulfonic acids such as p-toluenesulfonic acid and xylenesulfonic acid and salts thereof, acetic acid and levulinic acid.
  • Carboxylic acids such as oxalic acid, fumaric acid, maleic acid, citric acid and their salts, cationic sulfonic acid resins represented by amberlist, amberlite, diamond ion, zeolite, alumina, silica-alumina, clay , Sulfuric acid immobilization catalysts typified by sulfated zirconia, phosphoric acid immobilization catalysts typified by phosphorylated titania, heteropoly acids, metal salts that act as Lewis acids such as aluminum chloride and chromium chloride, or these A mixture is mentioned.
  • inorganic acids or carboxylic acids are preferred from the viewpoint of improving the yield of 5-hydroxymethylfurfural composition produced from molasses and from the viewpoint of economy, and more preferred are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boron.
  • hydrochloric acid sulfuric acid, phosphoric acid, nitric acid, boron.
  • acids acetic acid, levulinic acid, oxalic acid, fumaric acid, maleic acid and citric acid, more preferably one or two selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid More than a seed.
  • the amount of the acid catalyst used in the dehydration reaction is preferably 0.1 to 50% by weight based on molasses from the viewpoint of improving the reaction rate, suppressing the production of by-products, economically and reducing waste. More preferred is 0.1 to 30% by weight, still more preferred is 0.1 to 20% by weight.
  • reaction form The reaction form of the dehydration reaction is not particularly limited, and may be a batch type, a semi-batch type, a continuous type, or a combination of both types.
  • a semi-batch reaction and a continuous reaction are preferable from the viewpoint of productivity improvement, and a batch reaction is preferable from the viewpoint of easy operation.
  • reaction temperature The reaction temperature in the dehydration reaction is preferably 50 to 250 ° C., more preferably 70 to 230 ° C., still more preferably 80 to 220 ° C., and still more preferably 100 to 200 from the viewpoint of improving the reaction rate and suppressing the production of by-products. ° C.
  • the reaction pressure in the dehydration reaction is preferably 0.1 to 40 MPa, more preferably 0.1 to 20 MPa, and still more preferably 0 from the viewpoints of improving the reaction rate, reducing the amount of by-products generated, and reducing the equipment load.
  • 0.1 to 10 MPa more preferably 0.1 to 5 MPa, still more preferably 0.1 to 2 MPa, and still more preferably 0.1 to 1 MPa.
  • reaction solvent The dehydration reaction of molasses is performed in a solvent.
  • Suitable reaction solvents are those which can at least partially dissolve the raw materials and their reaction intermediates, preferably to a significant extent, more preferably completely, and are stable under the reaction conditions.
  • HMF 5-hydroxymethylfurfural
  • a considerable extent more preferably completely dissolved.
  • water, a highly polar aprotic organic solvent, and an ionic liquid are mentioned.
  • examples of the highly polar aprotic organic solvent include dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N-methylmorpholine, N-methylpyrrolidinone, 1,3-dimethyl-2-imidazolidinone, and hexamethyl.
  • examples thereof include phosphoric acid triamide, tetramethylurea, acetonitrile, ethylene glycol dimethyl ether, tetrahydrofuran, acetone and the like.
  • the ionic liquid examples include imidazolium salts such as 1-ethyl-3-methylimidazolium chloride, Pyrrolidinium salts such as butyl-1-methylpyrrolidinium, piperidinium salts such as 1-butyl-1-methylpiperidinium bromide, pyridinium salts such as 1-butylpyridinium chloride, tetrabutylammonium Ammonium salts such as Romido, sulfonium salts such as phosphonium salts and triethyl sulfonium bis (trifluoromethylsulfonyl) imide such as methane sulfonic acid tetrabutyl phosphonium and the like.
  • imidazolium salts such as 1-ethyl-3-methylimidazolium chloride
  • Pyrrolidinium salts such as butyl-1-methylpyrrolidinium
  • piperidinium salts such as 1-butyl-1-methyl
  • a combination of two or more arbitrary solvents can also be used. From the viewpoint of reactivity and suppression of the amount of by-products produced, highly polar organic solvents and ionic liquids such as dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidinone, imidazolium salts and pyridinium salts are preferred. Water is more preferable from the viewpoint of economy. When water is selected as the main solvent, it is preferable to mix one or more organic solvents in addition to water. The solvent used in this case is low in miscibility with water from the viewpoint of reactivity and suppression of the amount of by-product produced, has physical properties such as polarity and solubility that can extract the produced HMF, and is used under the conditions used.
  • unsaturated and saturated aliphatic ketones include acyclic aliphatic ketones and cyclic aliphatic ketones
  • unsaturated and saturated aliphatic ethers as aliphatic ethers
  • unsaturated and saturated aliphatic alcohols unsaturated and saturated aliphatic esters
  • unsaturated and saturated lactones aromatic hydrocarbons
  • Saturated and saturated aliphatic alkanes unsaturated and saturated halogenated alkanes, and the like
  • unsaturated and saturated aliphatic ketones include acyclic aliphatic ketones and cyclic aliphatic ketones
  • unsaturated and saturated aliphatic ethers as aliphatic ethers
  • unsaturated and saturated aliphatic alcohols unsaturated and saturated aliphatic esters
  • unsaturated and saturated lactones aromatic hydrocarbons
  • Saturated and saturated aliphatic alkanes unsaturated and saturated halogenated alkanes, and the like
  • the mixture which combined arbitrary 2 or more types of these from polarity or a soluble viewpoint can be used.
  • the weight ratio of water to the organic solvent is preferably 1:10 to 1: 0. 01, more preferably 1: 7 to 1: 0.05, still more preferably 1: 5 to 1: 0.1.
  • the concentration of molasses used in the production method of the present invention with respect to the solvent is preferably 0.01 to 70% by weight, more preferably from the viewpoint of improving the yield of the 5-hydroxymethylfurfural composition produced from molasses. It is 0.1 to 65% by weight, more preferably 1 to 60% by weight, still more preferably 3 to 40% by weight, and still more preferably 5 to 20% by weight.
  • the acid catalyst may be neutralized after completion of Step I or after completion of Step II described below.
  • neutralization is preferably performed.
  • the neutralizing agent used for neutralization include bases such as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth gold carbonates, organic amines, calcium oxide, and magnesium oxide. Substances. From the viewpoint of economy, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates are preferable, and alkali metal hydroxides and alkaline earth metal hydroxides are more preferable. .
  • Step I solid matter may be generated during the dehydration reaction depending on the reaction temperature, catalyst type, and raw material concentration. These are the sugars and sugar condensates by intramolecular and intermolecular dehydration of molasses which is the starting material, 5-hydroxymethylfurfural polymer by condensation polymerization of 5-hydroxymethylfurfural, 5-hydroxymethylfurfural and starting materials and intermediate reaction From the overreaction product of 5-hydroxymethylfurfural, it is presumed to be a humic substance that becomes solid waste. If necessary, this solid matter may be removed by filtration, or may be carried over to the next production step such as an extraction step without filtration.
  • the production method of the present invention includes a step of obtaining 5-hydroxymethylfurfural produced from molasses by extracting the reaction mixture after the dehydration reaction in Step I with an organic solvent (hereinafter sometimes simply referred to as “Step II”). .
  • Organic solvent 5-Hydroxymethylfurfural in the reaction mixture obtained in Step I is extracted and recovered using an organic solvent.
  • organic solvent examples include unsaturated and saturated aliphatic ketones (the aliphatic ketones include acyclic aliphatic ketones and cyclic aliphatic ketones), and unsaturated and saturated aliphatic ethers.
  • Aliphatic ethers include acyclic aliphatic ethers and cyclic aliphatic ethers.
  • Unsaturated and saturated aliphatic alcohols, aromatic hydrocarbons, unsaturated and saturated halogenated alkanes, Saturated and saturated aliphatic alkanes, unsaturated and saturated aliphatic esters and the like can be used.
  • the mixture which combined two arbitrary types among these from a polar or soluble viewpoint can be used.
  • the amount of the organic solvent used for extraction is preferably 0.1 to 50 when water is 1 by weight from the viewpoint of improving the extraction efficiency of the 5-hydroxymethylfurfural composition produced from molasses. More preferably, it is 0.2 to 10, more preferably 0.3 to 5, and still more preferably 0.5 to 2.5.
  • the organic solvent is preferably used in several times (for example, three times).
  • the step of extracting and recovering 5-hydroxymethylfurfural from the reaction mixture may be performed after the dehydration reaction in Step I, during the dehydration reaction in Step I, or both. From the viewpoint of improving the productivity of the 5-hydroxymethylfurfural composition and suppressing by-products, the step of extracting and recovering from the reaction mixture is preferably both during and after the dehydration reaction.
  • the production method of the present invention may further comprise a step of concentrating the 5-hydroxymethylfurfural composition produced from molasses by distilling off the organic solvent after completion of Step II.
  • the concentration conditions are not particularly limited, but from the viewpoint of suppressing side reactions and the thermal stability of the 5-hydroxymethylfurfural composition produced from molasses, for example, vacuum concentration, methods using osmotic membranes, transpiration, lyophilization, etc. Is mentioned.
  • vacuum concentration it is preferably performed at 150 ° C. or lower under sufficient pressure reduction conditions that can distill off the solvent, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower, still more preferably 80 ° C. or lower, More preferably, it is 60 degrees C or less. At this time, it may be distilled off simply by reducing the pressure, or it may be distilled off while topping a gas such as nitrogen.
  • the 5-hydroxymethylfurfural content in the 5-hydroxymethylfurfural composition produced from the molasses of the present invention is preferably 60% by weight or more, more preferably 70% by weight, more preferably 72% by weight from the viewpoint of improving the mold strength.
  • the above is more preferable, 80% by weight or more is more preferable, 95% by weight or less is preferable, and 90% by weight or less is more preferable.
  • the 5-hydroxymethylfurfural content in the 5-hydroxymethylfurfural composition produced from molasses of the present invention is preferably 60 to 95% by weight, more preferably 70 to 90% by weight from the viewpoint of improving the mold strength.
  • it is 72 to 90% by weight, more preferably 80 to 90% by weight.
  • the content of levulinic acid in the 5-hydroxymethylfurfural composition produced from molasses of the present invention is preferably 0.1% by weight or more from the viewpoint of improving the final strength of the mold, It is preferably 5.0% by weight or less, more preferably 3.0% by weight or less, and further preferably 1.5% by weight or less.
  • the content of the high molecular weight compound having a weight average molecular weight of 1000 or more is 0.1% by weight or more from the viewpoint of improving the final strength of the mold.
  • 0.5 wt% or more is more preferable, 1.2 wt% or more is more preferable, 5.0 wt% or less is preferable, 3.0 wt% or less is more preferable, 2.0 wt% or less. Is more preferable.
  • the content of the 5-hydroxymethylfurfural composition produced from molasses of the present invention in the binder composition is preferably 1% by weight or more, more preferably 4% by weight or more from the viewpoint of improving the strength of the mold. 5% by weight or more is more preferable, 6% by weight or more is further preferable, 10% by weight or more is more preferable, 50% by weight or less is preferable, 40% by weight or less is more preferable, and 30% by weight or less is further It is preferably 20% by weight or less, more preferably 12% by weight. Further, from the same viewpoint, it is preferably 1 to 50% by weight, more preferably 4 to 40% by weight, still more preferably 5 to 30% by weight, still more preferably 6 to 20% by weight, and more preferably 10 to 12% by weight.
  • the content of 5-hydroxymethylfurfural produced from molasses of the present invention in the binder composition is preferably 1% by weight or more, more preferably 3% by weight or more from the viewpoint of improving the strength of the mold. More preferably 4% by weight or more, more preferably 5% by weight or more, more preferably 45% by weight or less, still more preferably 35% by weight or less, still more preferably 25% by weight or less, and even more preferably 15% by weight or less. preferable. From the same viewpoint, it is preferably 1 to 45% by weight, more preferably 3 to 35% by weight, still more preferably 4 to 25% by weight, still more preferably 5 to 15% by weight.
  • the content of levulinic acid in the binder composition of the present invention is preferably 0.001% by weight or more, more preferably 0.01% by weight, and 2.5%. % By weight or less is preferable, 1.5% by weight or less is more preferable, and 0.5% by weight or less is more preferable.
  • the content of the high molecular weight compound having a weight average molecular weight of 1000 or more in the binder composition of the present invention is preferably 0.001% by weight or more from the viewpoint of improving the final strength of the mold, and 0.01% by weight. % Or more is more preferable, 0.08% by weight or more is further preferable, 2.5% by weight or less is preferable, 1.0% by weight or less is more preferable, and 0.60% by weight or less is further preferable.
  • a conventionally known resin can be used, for example, a self-hardening resin such as a furan resin or a phenol resin can be used. From the viewpoint of mold productivity due to the development of mold strength and environmental aspects due to plant-derived materials.
  • Furan resin is preferred.
  • Furan resins include furfuryl alcohol, furfuryl alcohol condensate, furfuryl alcohol and aldehyde condensate, furfuryl alcohol and urea condensate, furfuryl alcohol, phenol and aldehyde condensate, furfuryl.
  • One or more selected from the group consisting of a condensate of alcohol, melamine and aldehydes, and a condensate of furfuryl alcohol, urea and aldehydes, or a cocondensate consisting of two or more selected from the above group can be used.
  • furfuryl alcohol condensate of furfuryl alcohol and aldehydes, condensate of furfuryl alcohol and urea
  • the condensate of furfuryl alcohol, urea, and aldehydes is preferably synthesized in furfuryl alcohol in the presence of urea and formaldehyde.
  • aldehydes examples include formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, and the like, and one or more of these can be used as appropriate. From the viewpoint of improving the final strength of the mold, it is preferable to use formaldehyde, and from the viewpoint of reducing the amount of formaldehyde generated during molding, it is preferable to use furfural or terephthalaldehyde.
  • urea and aldehydes In the case of producing a condensate of furfuryl alcohol, urea and aldehydes, 0.05 to 0.5 mol of urea is used with respect to 1 mol of furfuryl alcohol, and 0.1 to 1. It is preferable to use 5 mol.
  • the mixing ratio of formaldehyde and urea at the time of synthesizing the acid curable resin improves the deep curability and final strength of the mold.
  • the molar ratio of formaldehyde / urea is preferably 1.5 to 4.0, and more preferably 3.0 to 4.0. More preferred.
  • the content of the acid curable resin in the binder composition is preferably 55 to 99% by weight, more preferably 60 to 95% by weight, and still more preferably 80% from the viewpoint of sufficiently expressing the final strength. ⁇ 90% by weight.
  • the pH of the acid curable resin is preferably 2.0 to 8.5, more preferably 3.0 to 6.5 from the viewpoints of improving the deep curability and final strength of the mold and improving the storage stability. 0, and more preferably 3.5 to 5.0.
  • the acid curable resin may be adjusted by adding an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an acidic aqueous solution such as an oxalic acid aqueous solution to the acid curable resin.
  • amino groups such as urea are considered to form a cross-linking bond with the resin component, and it is presumed that this has a favorable effect on the flexibility of the resulting mold.
  • the amino group content can be estimated by the nitrogen content (% by weight). Note that the flexibility of the mold is necessary when the mold is removed from the original mold. In particular, when a mold having a complicated shape is formed, if the mold has high flexibility, it is possible to prevent mold cracks caused by stress concentration at a portion where the thickness of the mold is thin at the time of mold removal.
  • the binder composition of the present invention has a nitrogen content of 0.8 to 6.0% by weight from the viewpoint of improving the final strength and preventing cracking of the resulting mold.
  • the content of the nitrogen-containing compound in the binder composition may be adjusted.
  • the nitrogen-containing compound urea, melamine, a condensate of urea and aldehydes, a condensate of melamine and aldehydes, a urea resin, a urea-modified resin, and the like are preferable.
  • the nitrogen content in the binder composition can be quantified by the Kjeldahl method.
  • urea, urea resin, furfuryl alcohol / urea resin (urea-modified resin), and nitrogen content derived from furfuryl alcohol / urea formaldehyde resin are 13C-NMR for the carbonyl group (C ⁇ O group) derived from urea. It can also be determined by quantifying with.
  • the binder composition may further contain an additive such as a silane coupling agent.
  • a silane coupling agent is contained because the final strength can be improved.
  • silane coupling agents include N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl)- aminosilanes such as ⁇ -aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycol Epoxy silanes such as sidoxypropyltriethoxysilane, 3-glycidoxypropy
  • silane coupling agent used.
  • Amino silane, epoxy silane, and ureido silane are preferable, amino silane is more preferable, and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane is more preferable.
  • the content of the silane coupling agent in the binder composition is preferably 0.01 to 0.5% by weight, and 0.05 to 0.3% by weight from the viewpoint of improving the final strength. Is more preferable.
  • the silane coupling agent may be contained as one component of the acid curable resin.
  • the mold composition of the present invention contains refractory particles, a curing agent, and a mold forming binder composition of the present invention.
  • refractory particles conventionally known particles such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand can be used. Recycled ones can also be used.
  • Curing agents include sulfonic acid compounds such as xylene sulfonic acid (especially m-xylene sulfonic acid) and toluene sulfonic acid (especially p-toluene sulfonic acid), acidic aqueous solutions containing phosphoric acid compounds, sulfuric acid, etc.
  • sulfonic acid compounds such as xylene sulfonic acid (especially m-xylene sulfonic acid) and toluene sulfonic acid (especially p-toluene sulfonic acid), acidic aqueous solutions containing phosphoric acid compounds, sulfuric acid, etc.
  • the curing agent may contain one or more solvents selected from the group consisting of alcohols, ether alcohols and esters, and carboxylic acids. Among these, alcohols and ether alcohols are preferable, and ether alcohols are more preferable from the viewpoint of improving the deep curability of the mold and improving the final strength.
  • the said solvent and carboxylic acid are contained, since the moisture content in a hardening
  • the content of the solvent or the carboxylic acid in the curing agent is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight from the viewpoint of improving the final strength.
  • the ratio of the refractory particles, the binder composition and the curing agent in the kneaded sand can be set as appropriate, but the binder composition is 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the refractory particles.
  • the curing agent is preferably in the range of 0.07 to 1 part by weight. With such a ratio, it is easy to obtain a mold having a sufficient final strength.
  • the content of the curing agent is such that the amount of water contained in the mold is reduced as much as possible to improve the deep curability of the mold, and from the viewpoint of mixing efficiency in the mixer, the acid curability in the binder composition.
  • the amount is preferably 10 to 70 parts by weight, more preferably 15 to 60 parts by weight, and still more preferably 20 to 55 parts by weight with respect to 100 parts by weight of the resin.
  • the binder composition of the present invention is suitable for a method for producing a mold having a step of curing a mixture containing refractory particles, a binder composition for mold making, and a curing agent. That is, the method for producing a mold of the present invention is a method for producing a mold using the above-mentioned binder composition of the present invention as a binder composition for mold making.
  • the mold can be manufactured using the process of the conventional mold manufacturing method as it is.
  • the binder composition of the present invention and a curing agent for curing the binder composition to the refractory particles and kneading them with a batch mixer or a continuous mixer, the mixture (kneading) Sand.
  • the binder composition of the present invention it is preferable to add the binder composition of the present invention after adding the curing agent to the refractory particles from the viewpoint of improving the final strength.
  • composition of the present invention comprises: ⁇ 1> A binder composition for mold making containing a 5-hydroxymethylfurfural composition produced from Molasses and an acid curable resin.
  • the following composition or production method or use is further preferred.
  • ⁇ 2> The step of obtaining a reaction mixture by dehydrating molasses in a solvent in the presence of an acid catalyst in the presence of an acid catalyst, and extracting the reaction mixture with an organic solvent to form a 5-hydroxymethylfurfural composition
  • the binder composition for mold making according to the above ⁇ 1> which is produced through a step of obtaining a product.
  • ⁇ 3> The binder composition for mold making according to ⁇ 2>, wherein in the step of dehydrating molasses in the solvent, the solvent is a two-layer system of water and an organic solvent.
  • the organic solvent is unsaturated and saturated aliphatic ketones, unsaturated and saturated aliphatic ethers, unsaturated and saturated aliphatic alcohols, aromatic hydrocarbons, unsaturated and saturated halogenated alkanes
  • the binder composition for mold making according to the above ⁇ 2> or ⁇ 3> which is at least one selected from saturated and saturated aliphatic alkanes and unsaturated and saturated aliphatic esters.
  • the acid catalyst is at least one selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid.
  • the content of the 5-hydroxymethylfurfural composition in the binder composition is preferably 1% by weight or more, more preferably 4% by weight or more, still more preferably 5% by weight or more, and still more preferably 6%.
  • % By weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 20% by weight or less, and even more preferably.
  • the content of the 5-hydroxymethylfurfural in the binder composition is preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 4% by weight or more, and still more preferably 5% by weight.
  • the viscosity for mold making according to the above ⁇ 1> to ⁇ 6> which is preferably 45% by weight or less, more preferably 35% by weight or less, still more preferably 25% by weight or less, and still more preferably 15% by weight or less.
  • the content of 5-hydroxymethylfurfural in the 5-hydroxymethylfurfural composition is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 72% by weight or more, and still more preferably 80% by weight.
  • the binder composition for molding according to the above ⁇ 1> to ⁇ 7> which is not less than wt%, preferably not more than 95 wt%, more preferably not more than 90 wt%.
  • the content of levulinic acid in the binder composition is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and preferably 2.5% by weight or less, more preferably 1.
  • the binder composition for mold making according to the above ⁇ 1> to ⁇ 8> which is not more than 5% by weight, more preferably not more than 0.5% by weight.
  • the content of levulinic acid in the 5-hydroxymethylfurfural composition is preferably 0.1% by weight or more, preferably 5.0% by weight or less, more preferably 3.0% by weight or less,
  • the content of the high molecular weight compound having a weight average molecular weight of 1000 or more in the binder composition is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and further preferably 0.08% by weight.
  • the content of the high molecular weight compound having a weight average molecular weight of 1000 or more in the 5-hydroxymethylfurfural composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and further preferably 1 2 to 5% by weight, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, and still more preferably 2.0% by weight.
  • Binder composition preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and further preferably 1 2 to 5% by weight, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, and still more preferably 2.0% by weight.
  • molasses is a viscous black-brown liquid containing components other than sugar, which is generated when sugar is refined from sugar liquid derived from sugarcane or sugar beet Binder composition.
  • molasses is a viscous black-brown liquid containing components other than sugar, which is generated when sugar is refined from sugar liquid derived from sugarcane or sugar beet Binder composition.
  • the acid curable resin is furfuryl alcohol and / or a condensate of furfuryl alcohol, urea, and aldehydes.
  • a mold composition comprising refractory particles, a curing agent, and the above-mentioned ⁇ 1> to ⁇ 15> a binder composition for mold making.
  • a binder composition for mold making Use in which the binder composition for mold making according to the above ⁇ 1> to ⁇ 15> is used for mold production.
  • a method for producing a mold comprising a step of curing a mixture comprising refractory particles, a curing agent, and the above binder molding composition for molding ⁇ 1> to ⁇ 15>.
  • Molasses used in the present invention was sucrose 24.4 wt%, glucose 7.0 wt%, fructose 9.9 wt%, xylose 4.1 wt%, moisture 25.4 wt%, ash content 5.6 wt%,
  • the organic acid was 2.9% by weight
  • the protein was 1.1% by weight
  • the weight average molecular weight was 3,500 or more
  • the high molecular weight compound was 6.5% by weight.
  • the breakdown of the organic acid was 1.5% by weight of lactic acid, 0.7% by weight of acetic acid, 0.3% by weight of formic acid, 0.1% by weight of oxalic acid, and 0.3% by weight of citric acid.
  • molasses manufactured by Kaset Thai Sugar was used.
  • waste molasses is a viscous black-brown liquid containing components other than sugar, which is generated when sugar is purified from sugar liquid derived from sugarcane or sugar beet.
  • the contents were cooled while maintaining stirring until the temperature of the contents became 30 ° C or lower. After cooling, the contents are filtered to remove solids, then a sample is taken from each of the aqueous phase and the methyl isobutyl ketone solution phase, diluted with pure water, and 5-hydroxymethylfurfural in each phase. The concentration of was measured by liquid chromatography. HMF1 measures the peak area of 5-hydroxymethylfurfural in the chromatogram obtained by the RI detection method, and calculates the concentration in the sample using the 5-hydroxymethylfurfural concentration-area relation that has been prepared in advance. Calculated.
  • HMF1 was concentrated.
  • the weight of the concentrate was 3.40 g, and the weight of 5-hydroxymethylfurfural was 2.90 g.
  • HMF1 had a 5-hydroxymethylfurfural content of 85.3% by weight, a levulinic acid content of 1.1% by weight, and a high molecular weight compound having a weight average molecular weight of 1000 or more was 1.5% by weight. .
  • the reaction was carried out for 3 hours while keeping the temperature and stirring.
  • the gauge pressure during the reaction was 0.4 MPa.
  • the contents were cooled while maintaining stirring until the temperature of the contents became 30 ° C or lower.
  • the contents were filtered to remove solids, and then the filtrate was neutralized by adding 50% by weight aqueous sodium hydroxide solution while stirring the filtrate to adjust the pH of the filtrate to 7.
  • the content was filtered to remove solids, and the concentration of 5-hydroxymethylfurfural in each phase was measured in the same manner as in the production of HMF1.
  • HMF3 5-hydroxymethylfurfural composition
  • D-fructose was used as a raw material.
  • HMF was 72% based on the molar basis of fructose.
  • the weight of the concentrated liquid after extraction was 9.80 g, of which HMF was 4.90 g.
  • HMF3 had a 5-hydroxymethylfurfural content of 50.0% by weight, a levulinic acid content of 7.3% by weight, and a high molecular weight compound having a weight average molecular weight of 1000 or more was 1.1% by weight. .
  • HMF4 5-hydroxymethylfurfural composition
  • the reaction was conducted in the same manner as in Example 2 except that D-fructose was used as the starting material. As a result, the production of HMF corresponding to 66% on the basis of the fructose mole was confirmed.
  • the weight of the concentrated liquid after extraction was 8.50 g, and the weight of the internal HMF was 6.00 g.
  • HMF4 had a 5-hydroxymethylfurfural content of 70.6% by weight, a levulinic acid content of 0.4% by weight, and a high molecular weight compound having a weight average molecular weight of 1000 or more was 1.0% by weight. .
  • Unreacted furfuryl alcohol was determined by the above analytical method, and the portion excluding unreacted furfuryl alcohol was designated as condensate 1.
  • the composition of the condensate 1 was 89% by weight of urea-modified furan resin and 11% by weight of water.
  • the kneaded sand immediately after kneading is filled into a cylindrical test piece frame having a diameter of 50 mm and a height of 50 mm, and after 3 hours, the mold is removed, and after 24 hours from filling, the method described in JIS Z 2604-1976 Then, the compressive strength (MPa) was measured and defined as “compressive strength after 24 hours”. The higher the value, the higher the mold strength.
  • Table 1 As is clear from Table 1, the binder compositions of Examples 1 to 5 are superior in compressive strength to the binder compositions of Comparative Examples 1 to 3.

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  • Materials Engineering (AREA)
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CN106457362A (zh) * 2014-06-17 2017-02-22 花王株式会社 铸型造型用粘结剂组合物
CN112203784A (zh) * 2018-10-03 2021-01-08 花王株式会社 铸型造型用粘结剂组合物
US20220402018A1 (en) * 2019-11-22 2022-12-22 Kinsei Matec Co., Ltd. Casting sand and kit for sand mold
US11981770B2 (en) 2019-03-08 2024-05-14 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Formaldehyde scavenger for binder systems

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JP6062715B2 (ja) * 2012-10-31 2017-01-18 花王株式会社 鋳型造型用粘結剤組成物
CN106311960A (zh) * 2015-06-23 2017-01-11 姚伟 一种粘结剂及其制备方法
CN108717093A (zh) * 2018-04-26 2018-10-30 胡贝贞 茶叶中蔗糖的离子色谱-串联质谱联用检测方法
JP6627012B1 (ja) * 2018-08-24 2019-12-25 花王株式会社 鋳型造型用粘結剤組成物
CN109577009B (zh) * 2019-01-30 2021-01-26 山东科技大学 一种用于铸造过滤网用生物质有机材料-无机溶胶复合涂层、制备方法及应用
CN111203271B (zh) * 2020-02-26 2022-10-04 南京林业大学 一种纤维素负载型催化剂的制备方法与应用
CN119923298A (zh) * 2022-11-29 2025-05-02 花王株式会社 铸模造模用粘结剂组合物
CN118122944B (zh) * 2024-03-20 2024-10-11 苏州兴业材料科技股份有限公司 一种耐高温生物基呋喃树脂粘结剂及其制备方法

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CN106457362A (zh) * 2014-06-17 2017-02-22 花王株式会社 铸型造型用粘结剂组合物
CN106457362B (zh) * 2014-06-17 2018-11-13 花王株式会社 铸型造型用粘结剂组合物
CN112203784A (zh) * 2018-10-03 2021-01-08 花王株式会社 铸型造型用粘结剂组合物
US11981770B2 (en) 2019-03-08 2024-05-14 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Formaldehyde scavenger for binder systems
US20220402018A1 (en) * 2019-11-22 2022-12-22 Kinsei Matec Co., Ltd. Casting sand and kit for sand mold

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