CN104105558B

CN104105558B - The manufacture method of making molds adhesive composition and casting mold

Info

Publication number: CN104105558B
Application number: CN201380008936.2A
Authority: CN
Inventors: 松尾俊树; 渡边雅彦; 矢代快
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2012-03-09
Filing date: 2013-02-28
Publication date: 2016-04-06
Anticipated expiration: 2033-02-28
Also published as: JP2013212536A; CN104105558A; IN2014DN07035A; JP6026891B2; WO2013133131A1

Abstract

A kind of making molds adhesive composition, it contains the 5 hydroxymethyl furfural composition and acid setting resin that are manufactured by molasses.5 hydroxymethyl furfural composition forms preferably through following operation manufacture: in a solvent molasses carried out dehydration in the presence of acid catalyst and obtain the operation of reactant mixture and obtain the operation of 5 hydroxymethyl furfural composition with organic solvent extraction reactant mixture, the content of 5 hydroxymethyl furfural composition in adhesive composition is more than 1 % by weight, is more preferably less than 50 % by weight.

Description

The manufacture method of making molds adhesive composition and casting mold

Technical field

The present invention relates to making molds adhesive composition and employ its casting mold composition and the manufacture method of casting mold.

Background technology

Acid cure self-hardening property casting mold manufactures by the following method: in the fire resistance particles such as silica sand, add the making molds binding agent containing acid setting resin and the curing agent containing organic sulfonic acid, sulfuric acid, phosphoric acid etc., they are mixing, then the mixing sand obtained is filled in the models such as wooden die, acid setting resin is solidified.Acid setting resin uses furane resins, phenolic resins etc., and furane resins use furfuryl alcohol, furfuryl alcohol-urea-formaldehyde resin, furfuryl alcohol-formaldehyde resin, furfuryl alcohol-phenol-formaldehyde resin, other known modified furan resins etc.The casting mold of gained uses when casting foundry goods such as mechanical foundry goods parts, construction implement parts or automotive parts.

Described casting mold moulding or use casting mold desired foundry goods is cast in, as important project, the raising of the final strength of casting mold can be enumerated.About the final strength of casting mold, become be necessary especially when producing large-scale casting mold, if intensity is not enough, then veining or the internal rupture occurred when casting or bring danger to operator, the foundry goods of gained likely becomes defective work.

In patent document 1, disclose and mix the compound in molecule with one or more aldehyde radical obtained by carbohydrate or starch or the acid cure type binding agent composition for moulds making them react in acid cure type resin, obtain the casting mold accelerated curing rate, improve mould strength, have superior surface performance.

In addition, in patent document 2, disclose: containing the 5 hydroxymethyl furfural, 2 being selected from specified quantitative, 5-furyl dimethyl carbinol, 2,5-furandicarboxylic acid, 2, more than a kind of 5-Diformylfuran, PEPA and furfuryl alcohol and in fact containing the adhesive composition of phenol, formaldehyde, nitrogen (referring to the composition containing amine such as urea), by reducing harmful substance, gas and can improve operating environment.

Prior art document

Patent document

Patent document 1: Japanese Laid-Open Patent Publication 61-235034 publication

Patent document 2:US20080207796 publication

Summary of the invention

The problem that invention will solve

But although the adhesive composition of patent document 2 can reduce foul smell when casting, final strength is insufficient, is seeking further improvement.In addition, the not talkative favorable solubility to acid setting resins such as furane resins of adhesive composition of patent document 1, the final strength of storage stability, the particularly casting mold of not talkative adhesive composition is abundant, is therefore seeking further improvement.

The invention provides the manufacture method of the making molds adhesive composition that the final strength of casting mold can be made to improve, the casting mold composition employing it and the casting mold that employs it.

Solve the means of problem

Making molds adhesive composition of the present invention is the making molds adhesive composition containing the 5 hydroxymethyl furfural composition manufactured by molasses and acid setting resin.

Casting mold composition of the present invention is by fire resistance particle, described making molds adhesive composition and the casting mold composition that makes the furane resins curing agent that this making molds adhesive composition solidifies mix.

The manufacture method of casting mold of the present invention has following operation: be cured by the mixture containing fire resistance particle, described making molds adhesive composition and the furane resins curing agent that makes this making molds adhesive composition solidify.

Invention effect

Utilize making molds adhesive composition of the present invention, the final strength of casting mold can be made to improve.In addition, utilize the manufacture method of casting mold composition of the present invention and casting mold, the final strength of casting mold can be made to improve.

Detailed description of the invention

Making molds adhesive composition of the present invention is (following, also be only called " adhesive composition ") use as binding agent when manufacturing casting mold, be the making molds adhesive composition containing the 5 hydroxymethyl furfural composition manufactured by molasses and acid setting resin.Adhesive composition of the present invention plays the effect that the final strength of casting mold is improved.The reason playing such effect is still not clear, but can consider as follows.

5 hydroxymethyl furfural has both methylol and aldehyde radical.Methylol has 1 reaction site, and aldehyde radical has two reaction site, then has 3 reaction site altogether as 5 hydroxymethyl furfural.And the reactivity of this Liang Ge functional group is different, there is reactive higher reaction site and reactive lower reaction site.Therefore, the reactivity due to Liang Ge functional group is different thus become and can guarantee the up time, in addition, infers owing to having 3 reaction site, therefore can carry out the cross-linking reaction of linear polymer incessantly fast, casting mold snap cure.Think: in the 5 hydroxymethyl furfural composition manufactured by molasses of the present invention, the accessory substance resulted from as the molasses of raw material can make 5 hydroxymethyl furfural composition uniform dissolution in the acid setting resins such as furane resins, thus 5 hydroxymethyl furfural composition and furane resins can evenly and react efficiently.Therefore, think in the adhesive composition containing 5 hydroxymethyl furfural composition, cross-linking reaction becomes more to be dissolved in carries out, therefore, it is possible to improve mould strength.

Below, composition contained in adhesive composition of the present invention is described.

Adhesive composition of the present invention contains the 5 hydroxymethyl furfural composition and acid setting resin that are manufactured by molasses.

The 5 hydroxymethyl furfural composition > that < is manufactured by molasses

The 5 hydroxymethyl furfural composition manufactured by molasses of the present invention manufactures through following operation: in a solvent molasses carried out dehydration in the presence of acid catalyst and obtain the operation of reactant mixture and obtain the operation of 5 hydroxymethyl furfural composition with organic solvent extraction reactant mixture.The 5 hydroxymethyl furfural composition manufactured by molasses of the present invention take 5 hydroxymethyl furfural as main component, comprises as accessory substance the hexose such as the organic acid such as macromolecular compound, levulic acid, fructose, glucose, mannose, galactolipin (hexose), ash content, moisture etc. that weight average molecular weight is more than 1000.

< molasses >

That molasses produce when being and refining granulated sugar by the liquid glucose from sugarcane, beet, also comprise composition beyond sugar in sticky shape and the liquid of pitchy, be blackstrap.

Composition > in < molasses

In the present invention, the molasses of commercially available product can be used, the molasses of KasetThaiSugar Inc. can be exemplified.The organic acid etc. such as high-molecular weight compounds, lactic acid, acetic acid, formic acid, oxalic acid, citric acid that these molasses contain sucrose, glucose, fructose, wood sugar, moisture, ash content, protein, weight average molecular weight are more than 3500.

Improve from the viewpoint of making the final strength of casting mold, the content of the sucrose in molasses is preferably more than 10 % by weight, be more preferably more than 15 % by weight, more preferably more than 20 % by weight, in addition, be preferably less than 50 % by weight, be more preferably less than 40 % by weight, more preferably less than 30 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, the content of the glucose in molasses is preferably more than 1.0 % by weight, be more preferably more than 3.0 % by weight, more preferably more than 5.0 % by weight, in addition, be preferably less than 20 % by weight, be more preferably less than 15 % by weight, more preferably less than 10 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, the content of the fructose in molasses is preferably more than 1.0 % by weight, be more preferably more than 5.0 % by weight, more preferably more than 7.0 % by weight, in addition, be preferably less than 20 % by weight, be more preferably less than 18 % by weight, more preferably less than 15 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, the content of the wood sugar in molasses is preferably more than 1.0 % by weight, be more preferably more than 2.0 % by weight, in addition, be preferably less than 20 % by weight, be more preferably less than 15 % by weight, more preferably less than 10 % by weight, be further preferably less than 6.0 % by weight.

In addition, from the viewpoint of economy and make the final strength of casting mold improve, the content of the moisture in molasses is preferably more than 5.0 % by weight, be more preferably more than 15 % by weight, in addition, be preferably less than 40 % by weight, be more preferably less than 35 % by weight, more preferably less than 30 % by weight.

In addition, from the viewpoint of economy and make the final strength of casting mold improve, the content of the ash content in molasses is preferably more than 1.0 % by weight, be more preferably more than 3.0 % by weight, in addition, be preferably less than 20 % by weight, be more preferably less than 15 % by weight, more preferably less than 10 % by weight.

In addition, from the viewpoint of making the final strength of casting mold improve, the content of the protein in molasses is preferably more than 0.1 % by weight, be more preferably more than 0.3 % by weight, in addition, be preferably less than 5.0 % by weight, be more preferably less than 4.0 % by weight, more preferably less than 3.0 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, weight average molecular weight in molasses is that the content of the high-molecular weight compounds of more than 3500 is preferably more than 1.0 % by weight, be more preferably more than 2.0 % by weight, more preferably more than 3.0 % by weight, in addition, be preferably less than 20 % by weight, be more preferably less than 15 % by weight, more preferably less than 10 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, the organic acid content such as the lactic acid in molasses, acetic acid, formic acid, oxalic acid, citric acid are preferably more than 0.1 % by weight, be more preferably more than 0.5 % by weight, more preferably more than 1.0 % by weight, in addition, be preferably less than 5 % by weight, be more preferably less than 4.5 % by weight, more preferably less than 4 % by weight.

Sucrose in the method mensuration molasses can recorded by embodiment, glucose, fructose, wood sugar, moisture, ash content, protein, weight average molecular weight are high-molecular weight compounds and the organic acid content of more than 3500.

The manufacture method > of the 5 hydroxymethyl furfural composition that < is manufactured by molasses

[operation I]

Manufacture method of the present invention has carries out dehydration by molasses (blackstrap) in a solvent in the presence of acid catalyst and obtains the operation (hereinafter sometimes referred to simply as " operation I ") of reactant mixture.

(acid catalyst)

Carry out the dehydration in operation I in the presence of acid catalyst.As the acid catalyst used, such as, can enumerate inorganic acid and its esters such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid; The sulfonic acid such as p-methyl benzenesulfonic acid, xylene monosulfonic acid and its esters; Carboxylic acid and its esters such as acetic acid, levulic acid, oxalic acid, fumaric acid, maleic acid, citric acid; The cationic sulfonate resin class being representative with amberlyst, amberlite, Diaion etc.; Zeolite, aluminium oxide, silica-alumina, clay, with sulfated zirconia be representative sulfuric acid immobilized catalyst, have slaine as the effect of Louis or their mixture using phosphorylation titanium dioxide be representative phosphoric acid immobilized catalyst, heteropllyacids, aluminium chloride, chromium chloride etc.Wherein, the viewpoint improved from the viewpoint of the yield of the 5 hydroxymethyl furfural composition manufactured by molasses and economy, be preferably inorganic acids or carboxylic acids, be more preferably a kind or two or more of being selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, acetic acid, levulic acid, oxalic acid, fumaric acid, maleic acid and citric acid, be more preferably selected from a kind or two or more in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, boric acid.

As the consumption of the acid catalyst in dehydration, the viewpoint, economy and the discarded object that suppress from the viewpoint of the generation of the raising of reaction speed, accessory substance reduce, be preferably 0.1 ~ 50 % by weight relative to molasses, be more preferably 0.1 ~ 30 % by weight, more preferably 0.1 ~ 20 % by weight.

(reactive mode)

The reactive mode of dehydration is not particularly limited, and can be batch (-type), also can be semi continuous, can also be continous way, and can be the reactive mode both combined.Improve from the viewpoint of productivity ratio, be preferably semi continuous reaction and continuous reaction, from the viewpoint of the ease of operation, be preferably intermittent reaction.

(reaction temperature)

As the reaction temperature in dehydration, suppress from the viewpoint of the generation of the raising of reaction speed, accessory substance, be preferably 50 ~ 250 DEG C, be more preferably 70 ~ 230 DEG C, more preferably 80 ~ 220 DEG C, further preferably 100 ~ 200 DEG C.

(reaction pressure)

As the reaction pressure in dehydration, the viewpoint reduced from the viewpoint of the growing amount of the raising of reaction speed, accessory substance and machine utilization reduce, be preferably 0.1 ~ 40MPa, be more preferably 0.1 ~ 20MPa, more preferably 0.1 ~ 10MPa, further be preferably 0.1 ~ 5MPa, be further preferably 0.1 ~ 2MPa, be further preferably 0.1 ~ 1MPa.

(reaction dissolvent)

Carry out the dehydration of described molasses in a solvent.About reaction dissolvent, can by raw material or its reaction intermediate at least partially, be preferably sizable degree, more preferably dissolve completely, and solvent stable is at reaction conditions suitable.Further, make the 5 hydroxymethyl furfural of generation (hereinafter also referred to HMF.) with sizable degree soluble, be more preferably and make it dissolve completely.Such as can enumerate water, high PAO solvent, ionic liquid.Particularly, as high PAO solvent, such as dimethyl sulfoxide (DMSO) can be enumerated, sulfolane, dimethylacetylamide, dimethyl formamide, N-methylmorpholine, 1-METHYLPYRROLIDONE, 1, 3-dimethyl-2-imidazolinone, HMPA, tetramethylurea, acetonitrile, glycol dimethyl ether, oxolane, acetone etc., in addition as ionic liquid, such as can enumerate the imidazole salts such as chlorination 1-ethyl-3-methylimidazole, the pyrrolidines salts such as bromination 1-butyl-1-crassitude, the piperidines salts such as bromination 1-butyl-1-methyl piperidine, chlorination 1-butyl-pyridinium drone salt such as pyridinium such as grade, the ammonium salt classes such as Tetrabutylammonium bromide, the sulfosalt classes etc. such as the microcosmic salt classes such as methanesulfonic acid tetrabutyl phosphorus and two (trifluoromethyl sulfonyl) acid imides of triethyl group sulphur.Also two or more arbitrary solvents can be combinationally used in addition.Suppress from the viewpoint of growing amount that is reactive and accessory substance, be preferably high polar organic solvent and ionic liquid, such as dimethyl sulfoxide (DMSO), dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE, imidazole salt, pyridinium salt.From the viewpoint of economy, be more preferably water.When selecting water as main solvent, more than one organic solvent is preferably made to mix in addition to water.As the solvent now used, suppress from the viewpoint of growing amount that is reactive and accessory substance, low with water miscibility, have the physical property such as the polarity of the degree of the HMF that can extract generation, dissolubility, solvent stable is under the conditions employed suitable.Such as, unsaturated and representative examples of saturated aliphatic ketone can be used (as aliphatic ketone, Noncyclic aliphatic ketone, annular aliphatic ketone can be enumerated.), unsaturated and representative examples of saturated aliphatic ethers (as aliphatic ethers, can enumerate Noncyclic aliphatic ethers, annular aliphatic ethers.), unsaturated and representative examples of saturated aliphatic alcohols, unsaturated and representative examples of saturated aliphatic ester class, unsaturated and saturated lactone, aromatic hydrocarbon based, unsaturated and representative examples of saturated aliphatic alkanes, unsaturated and saturated alkyl halide hydro carbons etc.In addition, consider from polarity, deliquescent viewpoint, can use the two or more mixture combined arbitrarily in them.Particularly, 3-methyl-2-butanone, methyl iso-butyl ketone (MIBK), DIBK, 5-methyl-3-heptanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, isophorone, oxolane, furfural, furfuryl alcohol, butanols, amylalcohol, isoamyl alcohol, hexanol, chloromethanes, carrene, chloroform, trichloroethanes, diethyl ether, isopropyl ether, two tertiary butyl ether, toluene, dimethylbenzene, decane, decene, dodecane, laurylene, hexane, pentane, benzinum, ethyl acetate, propyl acetate, butyl acetate or their arbitrary combination can be enumerated.Wherein, improve from the viewpoint of the extraction efficiency of HMF, be preferably methyl iso-butyl ketone (MIBK), cyclohexanone, butanols, oxolane, amylalcohol, carrene, chloroform, ethyl acetate, propyl acetate, butyl acetate, toluene, be more preferably methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, butanols, carrene, chloroform.

In operation I when solvent uses water and organic solvent, suppress from the viewpoint of economy and accessory substance, the weight rate (water: organic solvent) of water and organic solvent is preferably 1:10 ~ 1:0.01, is more preferably 1:7 ~ 1:0.05, more preferably 1:5 ~ 1:0.1.

Improve from the viewpoint of the yield of the 5 hydroxymethyl furfural composition manufactured by molasses, as the concentration relative to solvent of the molasses used in manufacture method of the present invention, be preferably 0.01 ~ 70 % by weight, be more preferably 0.1 ~ 65 % by weight, more preferably 1 ~ 60 % by weight, further be preferably 3 ~ 40 % by weight, be further preferably 5 ~ 20 % by weight.

(in and operation)

As required, after operation I terminates or after aftermentioned operation II terminates, acid catalyst can be neutralized.From the viewpoint of the stability formed of the 5 hydroxymethyl furfural composition manufactured by molasses, preferably neutralize.As in and the nertralizer of middle use, such as can enumerate the alkaline matters such as alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkaline earth metal carbonate, organic amine, calcium oxide, magnesia.From the viewpoint of economy, be preferably alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkaline earth metal carbonate, more preferably alkali metal hydroxide, alkaline earth metal hydroxide.

In operation I, according to reaction temperature or catalyst type, material concentration, sometimes in dehydration, generate solid content.Infer they be in molecule as the molasses of initiation material and the anhydrousugar of intermolecular dehydration or sugared condensation body, 5 hydroxymethyl furfural each other the 5 hydroxymethyl furfural polymer of polycondensation, 5 hydroxymethyl furfural and initiation material and reaction intermediate, formed the humus of solid-state castoff by the mistake product of 5 hydroxymethyl furfural.As required, can cross and filter this solid content, also can not filter and wait until the ensuing manufacturing processes such as extraction process.

[operation II]

Manufacture method of the present invention has the operation (hereinafter sometimes referred to simply as " operation II ") obtaining the 5 hydroxymethyl furfural manufactured by molasses after the dehydration of operation I with organic solvent extraction reactant mixture.

(organic solvent)

5 hydroxymethyl furfural with an organic solvent in the reactant mixture that obtained by operation I of extraction and recovery.

As the organic solvent used, such as unsaturated and representative examples of saturated aliphatic ketone can be used (as aliphatic ketone, Noncyclic aliphatic ketone, annular aliphatic ketone can be enumerated.), unsaturated and representative examples of saturated aliphatic ethers (as aliphatic ethers, can enumerate Noncyclic aliphatic ethers, annular aliphatic ethers.), unsaturated and representative examples of saturated aliphatic alcohols, aromatic hydrocarbon based, unsaturated and saturated alkyl halide hydro carbons, unsaturated and representative examples of saturated aliphatic alkanes, unsaturated and representative examples of saturated aliphatic ester class etc.In addition, consider from polarity, deliquescent viewpoint, can use two kinds of mixtures combined arbitrary among them.Particularly, 3-methyl-2-butanone, methyl iso-butyl ketone (MIBK), DIBK, 5-methyl-3-heptanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, oxolane, furfural, furfuryl alcohol, butanols, amylalcohol, isoamyl alcohol, hexanol, chloromethanes, carrene, chloroform, trichloroethanes, diethyl ether, isopropyl ether, two tertiary butyl ether, toluene, dimethylbenzene, decane, decene, dodecane, laurylene, hexane, pentane, benzinum, ethyl acetate, propyl acetate, butyl acetate or their arbitrary combination can be enumerated.Wherein, improve from the viewpoint of the extraction efficiency of the 5 hydroxymethyl furfural composition manufactured by molasses, be preferably methyl iso-butyl ketone (MIBK), cyclohexanone, butanols, oxolane, amylalcohol, carrene, chloroform, ethyl acetate, propyl acetate, butyl acetate, toluene, be more preferably methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butanols, carrene, chloroform, more preferably methyl iso-butyl ketone (MIBK), ethyl acetate, carrene.

In operation II, improve from the viewpoint of the extraction efficiency of the 5 hydroxymethyl furfural composition manufactured by molasses, when water being set to 1 in weight rate, the organic solvent amount used in extraction is preferably 0.1 ~ 50, be more preferably 0.2 ~ 10, more preferably 0.3 ~ 5, be further preferably 0.5 ~ 2.5.It should be noted that, during extraction, organic solvent preference score time (such as 3 times) uses.

Can after the dehydration of operation I from the operation of reactant mixture extraction and recovery 5 hydroxymethyl furfural, also can in the dehydration of operation I, can also above-mentioned in both.To improve from the viewpoint of the productivity ratio of 5 hydroxymethyl furfural composition and accessory substance suppresses, from the operation of reactant mixture extraction and recovery to be preferably dehydration and after dehydration both.

(enrichment process)

Manufacture method of the present invention can be included in after operation II terminates, distillation removing organic solvent further, by operation concentrated for the 5 hydroxymethyl furfural composition that manufactured by molasses.Concentrated condition is not particularly limited, but from the viewpoint of the suppression of side reaction, the heat endurance of 5 hydroxymethyl furfural composition that manufactured by molasses, such as, can enumerate reduced pressure concentration, use the method, transpiration (evapotranspiring), freeze drying etc. of permeable membrane.When carrying out reduced pressure concentration, distilling on the basis except the sufficient reduced pressure of desolventizing, preferably carry out below 150 DEG C, more preferably below 120 DEG C, preferred below 100 DEG C further, preferred below 80 DEG C further, preferred below 60 DEG C further.Now, only can distill removing with reducing pressure, can the distillation of the gas toppings such as nitrogen (トッピ Application グ) limit be removed limit in addition.

Improve from the viewpoint of mould strength, 5 hydroxymethyl furfural content in the 5 hydroxymethyl furfural composition manufactured by molasses of the present invention is preferably more than 60 % by weight, be more preferably 70 % by weight, more preferably more than 72 % by weight, further be preferably more than 80 % by weight, in addition, be preferably less than 95 % by weight, be more preferably less than 90 % by weight.

In addition, improve from the viewpoint of mould strength, 5 hydroxymethyl furfural content in the 5 hydroxymethyl furfural composition manufactured by molasses of the present invention is preferably 60 ~ 95 % by weight, be more preferably 70 ~ 90 % by weight, more preferably 72 ~ 90 % by weight, be further preferably 80 ~ 90 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, the content of the levulic acid in the 5 hydroxymethyl furfural composition manufactured by molasses of the present invention is preferably more than 0.1 % by weight, in addition, be preferably less than 5.0 % by weight, be more preferably less than 3.0 % by weight, more preferably less than 1.5 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, in the 5 hydroxymethyl furfural composition manufactured by molasses of the present invention, weight average molecular weight is that the content of the high-molecular weight compounds of more than 1000 is preferably more than 0.1 % by weight, be more preferably more than 0.5 % by weight, more preferably more than 1.2 % by weight, in addition, be preferably less than 5.0 % by weight, be more preferably less than 3.0 % by weight, more preferably less than 2.0 % by weight.

Improve from the viewpoint of the intensity of casting mold, the content of 5 hydroxymethyl furfural composition in adhesive composition manufactured by molasses of the present invention is preferably more than 1 % by weight, be more preferably more than 4 % by weight, more preferably more than 5 % by weight, further be preferably more than 6 % by weight, further be preferably more than 10 % by weight, in addition, be preferably less than 50 % by weight, be more preferably less than 40 % by weight, more preferably less than 30 % by weight, be further preferably less than 20 % by weight, be further preferably 12 % by weight.In addition, from the same viewpoint, be preferably 1 ~ 50 % by weight, be more preferably 4 ~ 40 % by weight, more preferably 5 ~ 30 % by weight, be further preferably 6 ~ 20 % by weight, be further preferably 10 ~ 12 % by weight.In addition, improve from the viewpoint of the intensity of casting mold, the content of the 5 hydroxymethyl furfural manufactured by molasses of the present invention in adhesive composition is preferably more than 1 % by weight, is more preferably more than 3 % by weight, and more preferably more than 4 % by weight, further be preferably more than 5 % by weight, in addition, be preferably less than 45 % by weight, be more preferably less than 35 % by weight, more preferably less than 25 % by weight, be further preferably less than 15 % by weight.In addition, from the same viewpoint, be preferably 1 ~ 45 % by weight, be more preferably 3 ~ 35 % by weight, more preferably 4 ~ 25 % by weight, be further preferably 5 ~ 15 % by weight.

Improve from the viewpoint of making the final strength of casting mold, the content of the levulic acid in adhesive composition of the present invention is preferably more than 0.001 % by weight, be more preferably 0.01 % by weight, in addition, be preferably less than 2.5 % by weight, be more preferably less than 1.5 % by weight, more preferably less than 0.5 % by weight.

In addition, improve from the viewpoint of making the final strength of casting mold, weight average molecular weight in adhesive composition of the present invention is that the content of the high-molecular weight compounds of more than 1000 is preferably more than 0.001 % by weight, be more preferably more than 0.01 % by weight, more preferably more than 0.08 % by weight, in addition, be preferably less than 2.5 % by weight, be more preferably less than 1.0 % by weight, more preferably less than 0.60 % by weight.

< acid setting resin >

As acid setting resin, known resin can be used, such as, the self-hardening resin such as furane resins, phenolic resins can be used, but the environment side of the casting mold productivity ratio from the viewpoint of the performance based on mould strength and the raw material based on plant origin, preferred furane resins.As furane resins, more than a kind in the condensation product of condensation product, furfuryl alcohol and the urea being selected from furfuryl alcohol, the condensation product of furfuryl alcohol, furfuryl alcohol and aldehydes, the condensation product of furfuryl alcohol and phenols and aldehydes, furfuryl alcohol and the condensation product of melamine and aldehydes and the condensation product of furfuryl alcohol and urea and aldehydes or comprise the two or more cocondensation compound be selected from described group can be used.Wherein, from the viewpoint of making successfully to carry out with the curing reaction of foundry goods sand (cast thing sand), make deep curability and final strength improve, preferred use is selected from more than a kind and their cocondensation compound in the condensation product of furfuryl alcohol, furfuryl alcohol and aldehydes, furfuryl alcohol and the condensation product of urea and the condensation product of furfuryl alcohol and urea and aldehydes, more preferably uses the condensation product of furfuryl alcohol and/or furfuryl alcohol and urea and aldehydes.In furfuryl alcohol, under the existence of urea and formaldehyde, preferably synthesize the condensation product of furfuryl alcohol and urea and aldehydes.

As described aldehydes, formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde etc. can be enumerated, among them, can suitably use more than a kind.From the viewpoint of making the final strength of casting mold improve, preferably using formaldehyde, reducing from the viewpoint of formaldehyde generation during moulding, preferably using furfural, terephthalaldehyde.

When manufacturing the condensation product of furfuryl alcohol and urea and aldehydes, relative to furfuryl alcohol 1 mole, preferably use 0.05 ~ 0.5 mole of urea and 0.1 ~ 1.5 mole of aldehydes.

In addition, by when comprising the Material synthesis acid setting resin of urea and formaldehyde, the generation of the formaldehyde from the viewpoint of the viewpoint that the deep curability of casting mold and final strength can be made to improve and when can reduce moulding, formaldehyde during synthesis acid setting resin and the proportioning of urea are preferably formaldehyde/urea=1.5 ~ 4.0 with molar ratio computing, are more preferably 3.0 ~ 4.0.

From the viewpoint of fully showing final strength, the content of the acid setting resin in adhesive composition is preferably 55 ~ 99 % by weight, is more preferably 60 ~ 95 % by weight, and more preferably 80 ~ 90 % by weight.

Improve from the viewpoint of the viewpoint making the deep curability of casting mold and final strength improve and storage-stable, the pH of acid setting resin is preferably 2.0 ~ 8.5, is more preferably 3.0 ~ 6.0, and more preferably 3.5 ~ 5.0.In order to the pH of acid setting resin is controlled in above-mentioned scope, can regulate by adding the acidic aqueous solutions such as alkaline aqueous solution or oxalic acid aqueous solution such as sodium hydrate aqueous solution in acid setting resin.

Think in adhesive composition of the present invention, the amino of urea etc. and resinous principle form cross-bond, infer and bring preferred impact to the pliability of the casting mold obtained.Amino content can be estimated with nitrogen content (% by weight).It should be noted that, needing the pliability of casting mold when extracting casting mold from model.Particularly when the casting mold of the shape of shaping complexity, if the pliability of casting mold is high, then when can prevent from pulling out type, stress concentrates on the thin part of the wall thickness of casting mold and the veining caused.With regard to adhesive composition of the present invention, the viewpoint improved from the viewpoint of making final strength is broken with the casting mold preventing from obtaining, nitrogen content in adhesive composition is preferably 0.8 ~ 6.0 % by weight, be more preferably 1.8 ~ 6.0 % by weight, more preferably 2.2 ~ 5.0 % by weight, further be preferably 2.3 ~ 4.5 % by weight, be further preferably 2.5 ~ 4.0 % by weight.In order to be adjusted in above-mentioned scope by the nitrogen content in adhesive composition, the content of the nitrogen-containing compound in adhesive composition can be regulated.As nitrogen-containing compound, be preferably the condensation product of the condensation product of urea, melamine, urea and aldehydes, melamine and aldehydes, urea resin and urea-modified resin etc.Can come the nitrogen content in adhesive composition quantitative by Kjeldahl's method.Further, also can by quantitatively obtaining with 13C-NMR the nitrogen content being derived from urea, urea resin, furfuryl alcohol-urea resin (urea-modified resin) and furfuryl alcohol-urea-formaldehyde resin to the carbonyl (C=O yl) being derived from urea.

Other additives of < >

In addition, can further containing additives such as silane couplers in adhesive composition.If such as containing silane coupler, then final strength can be made to improve, therefore preferably.As silane coupler, N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane can be used, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-γ aminopropyltriethoxy silane, 3-TSL 8330, the amino silanes such as N-β-(amino-ethyl)-alpha-amido propyl trimethoxy silicane, or 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl diethoxy silane, the epoxy silanes such as 3-glycidoxypropyl group triethoxysilane, ureido silane, hydrosulphonyl silane, sulfidesilane, methacryloxypropyl silane, acryloxy silane etc.Be preferably amino silane, epoxy silane, ureido silane, be more preferably amino silane, more preferably N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane.Improve from the viewpoint of final strength, the content of silane coupler in adhesive composition is preferably 0.01 ~ 0.5 % by weight, is more preferably 0.05 ~ 0.3 % by weight.It should be noted that, silane coupler can be contained as of an acid setting resin composition.

Casting mold composition of the present invention contains fire resistance particle, curing agent and making molds adhesive composition of the present invention.

As fire resistance particle, the known particles such as silica sand, chromite sand, zircon sand, olivine sand, aluminum oxide sand, mullite sand, mullite synthesizing sand can be used, in addition, also can use by use after fire resistance particle reclaim and obtain particle, regeneration process after particle etc.

As curing agent, more than a kind of the known curing agent such as the acidic aqueous solution containing sulfonate-based compound, phosphoric acid based compound, sulfuric acid etc. such as xylene monosulfonic acid (particularly meta-xylene sulfonic acid) or toluenesulfonic acids (particularly p-methyl benzenesulfonic acid) can be used.Further, can containing the solvent of more than a kind that is selected from alcohols, ether alcohol class and ester class or carboxylic acids in curing agent.Among them, from the viewpoint of the raising of deep curability, the raising of final strength that realize casting mold, be preferably alcohols, ether alcohol class, be more preferably ether alcohol class.In addition, if containing above-mentioned solvent, carboxylic acids, then can reduce the amount of moisture in curing agent, therefore the deep curability of casting mold becomes good further, and final strength improves further simultaneously.Improve from the viewpoint of final strength, described solvent, the content of described carboxylic acids in curing agent are preferably 5 ~ 50 % by weight, are more preferably 10 ~ 40 % by weight.In addition, from the viewpoint of making the viscosity of curing agent reduce, preferably containing methyl alcohol, ethanol.

Suitably can set the ratio of fire resistance particle in mixing sand and adhesive composition and curing agent, but relative to fire resistance particle 100 weight portion, the scope that adhesive composition is preferably the scope of 0.5 ~ 1.5 weight portion, curing agent is preferably 0.07 ~ 1 weight portion.If such ratio, then easily obtain the sufficient casting mold of final strength.Further, from the viewpoint of the viewpoint reducing amount of moisture contained in casting mold, make the deep curability of casting mold improve and the mixing efficiency using blender as far as possible, relative to acid setting resin 100 weight portion in adhesive composition, the content of curing agent is preferably 10 ~ 70 weight portions, be more preferably 15 ~ 60 weight portions, more preferably 20 ~ 55 weight portions.

Adhesive composition of the present invention is applicable to have the manufacture method of the casting mold of the operation of the mixture solidified made containing fire resistance particle, making molds adhesive composition and curing agent.That is, the manufacture method of casting mold of the present invention uses the adhesive composition of the invention described above as the manufacture method of the casting mold of making molds adhesive composition.

In the manufacture method of casting mold of the present invention, can directly utilize the process of the manufacture method of casting mold in the past to manufacture casting mold.Such as, by the adhesive composition of the invention described above and make the curing agent that this adhesive composition solidifies add in fire resistance particle, with batch mixer, continuous mixing device etc., they are mixing, said mixture (mixing sand) can be obtained thus.In the manufacture method of casting mold of the present invention, improve from the viewpoint of final strength, after preferably adding described curing agent in fire resistance particle, add adhesive composition of the present invention.

With regard to composition of the present invention,

<1> is the making molds adhesive composition containing the 5 hydroxymethyl furfural composition manufactured by molasses and acid setting resin.

The composition that the present invention is further preferably following or manufacture method or purposes.

<2> is according to the making molds adhesive composition of described <1>, wherein, described 5 hydroxymethyl furfural composition forms through following operation manufacture: in a solvent molasses carried out dehydration in the presence of acid catalyst and obtain the operation of reactant mixture and obtain the operation of 5 hydroxymethyl furfural composition with organic solvent extraction reactant mixture.

<3> is according to the making molds adhesive composition of described <2>, wherein, carried out by molasses in described solvent in the operation of dehydration, described solvent is two coating systems of water and organic solvent.

<4> is according to the making molds adhesive composition of described <2> or <3>, wherein, described organic solvent is be selected from more than a kind in unsaturated and representative examples of saturated aliphatic ketone, unsaturated and representative examples of saturated aliphatic ethers, unsaturated and representative examples of saturated aliphatic alcohols, aromatic hydrocarbon based, unsaturated and saturated alkyl halide hydro carbons, unsaturated and representative examples of saturated aliphatic alkanes and unsaturated and representative examples of saturated aliphatic ester class.

<5> is according to the making molds adhesive composition of described <2> ~ <4>, wherein, described acid catalyst is more than a kind of being selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid.

<6> is according to the making molds adhesive composition of described <1> ~ <5>, wherein, the content of described 5 hydroxymethyl furfural composition in adhesive composition is preferably more than 1 % by weight, be more preferably more than 4 % by weight, more preferably more than 5 % by weight, further be preferably more than 6 % by weight, further be preferably more than 10 % by weight, in addition, be preferably less than 50 % by weight, be more preferably less than 40 % by weight, more preferably less than 30 % by weight, further be preferably less than 20 % by weight, further be preferably less than 12 % by weight.

<7> is according to the making molds adhesive composition of described <1> ~ <6>, wherein, the content of described 5 hydroxymethyl furfural in adhesive composition is for being preferably more than 1 % by weight, be more preferably more than 3 % by weight, more preferably more than 4 % by weight, further be preferably more than 5 % by weight, in addition, be preferably less than 45 % by weight, be more preferably less than 35 % by weight, more preferably less than 25 % by weight, further be preferably less than 15 % by weight.

<8> is according to the making molds adhesive composition of described <1> ~ <7>, wherein, the content of the 5 hydroxymethyl furfural in described 5 hydroxymethyl furfural composition is preferably more than 60 % by weight, be more preferably more than 70 % by weight, more preferably more than 72 % by weight, further be preferably more than 80 % by weight, in addition, be preferably less than 95 % by weight, be more preferably less than 90 % by weight.

<9> is according to the making molds adhesive composition of described <1> ~ <8>, wherein, the content of levulic acid in adhesive composition is preferably more than 0.001 % by weight, be more preferably more than 0.01 % by weight, in addition, be preferably less than 2.5 % by weight, be more preferably less than 1.5 % by weight, more preferably less than 0.5 % by weight.

<10> is according to the making molds adhesive composition of described <1> ~ <9>, wherein, the content of the levulic acid in described 5 hydroxymethyl furfural composition is preferably more than 0.1 % by weight, in addition, be preferably less than 5.0 % by weight, be more preferably less than 3.0 % by weight, more preferably less than 1.5 % by weight.

<11> is according to the making molds adhesive composition of described <1> ~ <10>, wherein, weight average molecular weight is that the content of high-molecular weight compounds in adhesive composition of more than 1000 is for being preferably more than 0.001 % by weight, be more preferably more than 0.01 % by weight, more preferably more than 0.08 % by weight, in addition, be preferably less than 2.5 % by weight, be more preferably less than 1.0 % by weight, more preferably less than 0.60 % by weight.

<12> is according to the making molds adhesive composition of described <1> ~ <11>, wherein, weight average molecular weight in described 5 hydroxymethyl furfural composition is that the content of the high-molecular weight compounds of more than 1000 is preferably more than 0.1 % by weight, be more preferably more than 0.5 % by weight, more preferably more than 1.2 % by weight, in addition, be preferably less than 5.0 % by weight, be more preferably less than 3.0 % by weight, more preferably 2.0 % by weight.

<13> is according to the making molds adhesive composition of described <1> ~ <12>, wherein, produce when molasses are and refine granulated sugar by the liquid glucose from sugarcane, beet, also comprise composition beyond sugar in sticky shape and the liquid of pitchy.

<14> is according to the making molds adhesive composition of described <1> ~ <13>, and wherein, molasses are blackstrap.

<15> is according to the making molds adhesive composition of described <1> ~ <14>, wherein, described acid setting resin is the condensation product of furfuryl alcohol and/or furfuryl alcohol and urea and aldehydes.

<16> casting mold composition, it contains the making molds adhesive composition of fire resistance particle, curing agent and described <1> ~ <15>.

Making molds adhesive composition described in described <1> ~ <15> is used for the purposes of Casting mold manufacturing by <17> mono-kind.

The manufacture method of a <18> casting mold, it has following operation: by the mixture solidified of the making molds adhesive composition containing fire resistance particle, curing agent and described <1> ~ <15>.

Embodiment

Below, by the embodiment etc. specifically illustrated, the present invention will be described.It should be noted that, as follows the assessment item in embodiment etc. is measured.

The content > of the levulic acid in <5-hydroxymethylfurfural composition and in adhesive composition

Content is calculated by following method by the chromatography of ions.

Device: DX-320 (Japanese Dionex Inc.)

Post: IonPacAS11HC

Eluent: 10mMKOH (0min) → 40mMKOH (25min)

Flow: 1.5mL/min

Automatic TVS (Autosuppressor): ASRS-300 (Japanese Dionex Inc.)

Detect: electrical conductivity

MS device: LCMS-2010EV (Shimadzu Seisakusho Ltd.'s system)

Flow: 1mL/min

The content > of the high-molecular weight compounds in <5-hydroxymethylfurfural composition and in adhesive composition

With gel permeation chromatography, calculate content by following method.

Detector: RI

Post: TSKgel α-M × 2 (Dong Cao Inc.)

Temperature: 40 DEG C

Eluent: DMF

Flow: 1.0mL/min

Scale merit: polystyrene

Furfuryl alcohol content > in < adhesive composition

Measure by gas chromatography.(with furfuryl alcohol production standard curve)

Condition determination:

Inner mark solution: 1,6-hexylene glycol

Post: PEG-20MChromosorbWAWDMCS60/80mesh (GLSciences Inc.)

Column temperature: 80 ~ 200 DEG C (8 DEG C/min)

Injector temperature: 210 DEG C

Detector temperature: 250 DEG C

Carrier gas: 50mL/min (He)

Moisture > in < adhesive composition

Measured by the moisture test method of the chemicals shown in JISK0068.

Nitrogen content > in < adhesive composition

Measured by the Kjeldahl's method shown in JISM8813.

Weight nitroxide % in adhesive composition is 3.00 % by weight in embodiment 1 ~ 5 and comparative example 1.

Sugared conversion ratio during <HMF manufactures and hexose content >

Measure by high performance liquid chromatography.

Detector: colonaCAD

Post: AsahipakNH2P-50

Temperature: 25 DEG C

Eluent: a) acetonitrile b) containing the water of 30% methyl alcohol

Flow: 1.0mL/min

HMF content > during <HMF manufactures

Measure by high performance liquid chromatography.

Detector: RI

Post: CARBOSepCOREGEL-87H

Temperature: 80 DEG C

Eluent: containing the water of 0.1% trifluoroacetic acid

Flow: 0.6mL/min

The content > of the high-molecular weight compounds in < molasses

With gel permeation chromatography, calculate content by following method.

Detector: RI

Post: TSKgel α-M × 2 (Dong Cao Inc.)

Temperature: 40 DEG C

Eluent: containing the water of 30% methyl alcohol

Flow: 0.6mL/min

Scale merit: polystyrene

Organic acid content > in < molasses

By the chromatography of ions, calculate content by following method.

Device: DX-320 (Japanese Dionex Inc.)

Post: IonPacAS11HC

Eluent: 10mMKOH (0min) → 40mMKOH (25min)

Flow: 1.5mL/min

Automatic TVS: ASRS-300 (Japanese Dionex Inc.)

Detect: electrical conductivity

MS device: LCMS-2010EV (Shimadzu Seisakusho Ltd.'s system)

Flow: 1mL/min

The content > of the sucrose in < molasses, glucose, fructose, wood sugar

By the chromatography of ions, calculate content by following method.

Device: DX-320 (Japanese Dionex Inc.)

Post: CarboPacPA1 (4.0mm × 250mm)

Sample concentration: 100ppm

Eluent: A100mMNaOHB100mMNaOH/CH3COONaC ultra-pure water

Flow: 1.0mL/min

Detect: electrochemical detector

Protein content > in < molasses

As analytical equipment, fully automatic high-speed amino acid analysis machine (model JLC-500/V, Inc. of NEC) is used to measure.

Ash content > in < molasses

Measured by the decrement of the chemicals shown in JISK0067 and residue (residual point) test method(s).

Moisture > in < molasses

The moisture test method of the chemicals according to JISK0068 measures.

Composition > in < molasses

The high-molecular weight compounds 6.5 % by weight that the molasses used in the present invention are sucrose 24.4 % by weight, glucose 7.0 % by weight, fructose 9.9 % by weight, wood sugar 4.1 % by weight, moisture 25.4 % by weight, ash content 5.6 % by weight, organic acid 2.9 % by weight, protein 1.1 % by weight, weight average molecular weight are more than 3500.Organic acid detailed content is lactic acid 1.5 % by weight, acetic acid 0.7 % by weight, formic acid 0.3 % by weight, oxalic acid 0.1 % by weight, citric acid 0.3 % by weight.

It should be noted that, employ the blackstrap of KasetThaiSugar Inc. as molasses.That this blackstrap produces when being and refining granulated sugar by the liquid glucose from sugarcane, beet, also containing the composition beyond sugar in sticky shape and the liquid of pitchy.

Production Example 1 (HMF1) > of <5-hydroxymethylfurfural composition

The phosphoric acid (purity 85%, Aldrich system) of the blackstrap (KasetThaiSugar Inc.) of 20.0g, the ion exchange water of 40.0g, the methyl iso-butyl ketone (MIBK) (Wako Pure Chemical Industries, Ltd.'s system) of 160g and 2.0g is added in 500mL titanium electromagnetic type autoclave (Dong high pressure Inc.).After container closure, with nitrogen, inner space is fully replaced.Back fully stir content limit and be warming up to 140 DEG C, arrive 140 DEG C of back and continue insulation, stir 3 hours limits and react.It should be noted that, gauge pressure during reaction is 0.4MPa.After reaction terminates, limit maintains stirring limit and the temperature of content is cooled to less than 30 DEG C.After cooling, content is filtered and after carrying out the removing of solid state component, gathers sample mutually respectively from water-soluble liquid phase and methyl isobutyl ketone solution, with pure water dilution, the concentration of the 5 hydroxymethyl furfural of each phase with liquid chromatography for measuring.With regard to HMF1, measure the peak area of the 5 hydroxymethyl furfural in the chromatogram obtained by RI detection method, calculate the concentration in sample by the relational expression of the concentration-area of ready-made 5 hydroxymethyl furfural.Consequently, with the blackstrap amount added for benchmark, confirm the generation of the 5 hydroxymethyl furfural of 16.0 % by weight (3.20g).With the molar basis of the sucrose in blackstrap, glucose, fructose, it is equivalent to 54%.

Then, the difference water-soluble liquid phase of separated and collected and methyl isobutyl ketone solution phase.The water-soluble liquid phase be mixed to get, is transferred to 1L separatory funnel, the aqueous solution is added to the methyl iso-butyl ketone (MIBK) of 0.5 times of weight, carries out the separatory extracting operation of the HMF1 in water-soluble liquid phase.Carry out 3 extracting operations, the methyl isobutyl ketone solution that extracting operation by water-soluble liquid phase is obtained and the mixing of the methyl isobutyl ketone solution after being terminated by the reaction of above-mentioned separated and collected, steam instrument by methyl iso-butyl ketone (MIBK) distillation removing by revolving, HMF1 is concentrated.The weight of concentrate is 3.40g, and wherein the weight of 5 hydroxymethyl furfural is 2.90g.The 5 hydroxymethyl furfural content of HMF1 is 85.3 % by weight, and levulinic acid content is 1.1 % by weight, weight average molecular weight be more than 1000 high-molecular weight compounds be 1.5 % by weight.

Production Example 2 (HMF2) > of <5-hydroxymethylfurfural composition

The phosphoric acid (purity 85%, Aldrich system) of the blackstrap (KasetThaiSugar Inc.) of 20.0g, the ion exchange water of 40.0g, the methyl iso-butyl ketone (MIBK) (Wako Pure Chemical Industries, Ltd.'s system) of 160g and 2.0g is added in 500mL titanium electromagnetic type autoclave (Dong high pressure Inc.).After container closure, with nitrogen, inner space is fully replaced.Back fully stir content limit and be warming up to 140 DEG C, arrive 140 DEG C of back and continue insulation, stir 3 hours limits and react.It should be noted that, gauge pressure during reaction is 0.4MPa.After reaction terminates, limit maintains stirring limit and the temperature of content is cooled to less than 30 DEG C.After cooling, content is filtered and after carrying out the removing of solid state component, limit is stirred filtrate limit instillation 50 % by weight sodium hydrate aqueous solutions and neutralizes, the pH of filtrate is adjusted to 7.After neutralization, content is filtered and after carrying out the removing of solid state component, with the method same with the manufacture of HMF1, determines the concentration of the 5 hydroxymethyl furfural of each phase.Consequently, confirm the generation of the 5 hydroxymethyl furfural of 11.6 % by weight (4.65g) for benchmark with the blackstrap amount added.With the molar basis of the sucrose in blackstrap, glucose, fructose, it is equivalent to 31%.

Then, carry out the operation same with the manufacture of HMF1, obtain the concentrate of HMF2.The weight of concentrate is the weight of 4.293g, wherein 5 hydroxymethyl furfural is 3.16g.The 5 hydroxymethyl furfural content of HMF2 is 73.6 % by weight, and levulinic acid content is 0.2 % by weight, weight average molecular weight be more than 1000 high-molecular weight compounds be 1.7 % by weight.

Production Example 3 (HMF3) > of <5-hydroxymethylfurfural composition

Except use raw material is set to react similarly to Example 1 except D-Fructose.Consequently, the generation of the HMF being equivalent to 72% is confirmed with the molar basis of fructose.The weight of the concentrate after extraction is 9.80g, and wherein HMF is 4.90g.The 5 hydroxymethyl furfural content of HMF3 is 50.0 % by weight, and levulinic acid content is 7.3 % by weight, weight average molecular weight be more than 1000 high-molecular weight compounds be 1.1 % by weight.

Production Example 4 (HMF4) > of <5-hydroxymethylfurfural composition

Except use raw material is set to react similarly to Example 2 except D-Fructose.Consequently, confirm the generation of the HMF being equivalent to 66% with the molar basis of fructose, the weight of the concentrate after extraction is 8.50g, and wherein the weight of HMF is 6.00g.The 5 hydroxymethyl furfural content of HMF4 is 70.6 % by weight, and levulinic acid content is 0.4 % by weight, weight average molecular weight be more than 1000 high-molecular weight compounds be 1.0 % by weight.

The manufacture > of < condensation product 1

By furfuryl alcohol 100 weight portion and paraformaldehyde 35 weight portion and the mixing of urea 13 weight portion in three-neck flask, be adjusted to pH9 with 25% sodium hydrate aqueous solution.After being warming up to 100 DEG C, after making it react 1 hour with identical temperature, being adjusted to pH4.5 with 37% hydrochloric acid, making it react 1 hour at 100 DEG C further.Afterwards, be adjusted to pH7 with 25% sodium hydrate aqueous solution, add urea 5 weight portion, make it react 30 minutes at 100 DEG C, obtain reactant 1.Obtain unreacted furfuryl alcohol by above-mentioned analytical method, will the part of unpolymerized furfuryl alcohol be eliminated as condensation product 1.Condensation product 1 consist of urea-modified furane resins 89 % by weight, water 11 % by weight.

The manufacture > of < adhesive composition

(embodiment 1 ~ 5, comparative example 1 ~ 3)

In the mode becoming the composition of table 1 by condensation product 1 with furfuryl alcohol, silane coupler, additive mix and blend, coordinate.

[table 1]

< test example (compressive strengths after 24 hours) >

25 DEG C, under the condition of 55%RH, relative to silica sand (Fremantle) 100 weight portion, add curing agent (kaoquaker Inc. カオーライトナー curing agent (US-3/C-21=40%/60%)) 0.40 weight portion, then add adhesive composition 1.00 weight portion shown in table 1, they are obtained by mixing mixing sand.Afterwards, just mixing mixing sand is filled to the columniform test piece frame of diameter 50mm, high 50mm, carried out pulling out type after 3 hours, from filling after 24 hours, be used in the method recorded in JISZ2604-1976 and measure compressive strength (MPa), as " compressive strengths after 24 hours ".Numerical value higher expression mould strength is higher.Show the result in table 1.

As from table 1 clear and definite, the adhesive composition of embodiment 1 ~ 5 is more excellent with the adhesive composition phase specific compress strength of comparative example 1 ~ 3.

Claims

1. a making molds adhesive composition, it contains the 5 hydroxymethyl furfural composition and acid setting resin that are manufactured by molasses, wherein,

Described 5 hydroxymethyl furfural composition forms through following operation manufacture:

In a solvent molasses are carried out dehydration in the presence of acid catalyst and obtain reactant mixture operation and

The operation of 5 hydroxymethyl furfural composition is obtained with organic solvent extraction reactant mixture.

2. making molds adhesive composition according to claim 1, wherein,

Describedly in a solvent molasses carried out dehydration and obtain in the operation of reactant mixture, its solvent is two coating systems of water and organic solvent.

3. making molds adhesive composition according to claim 1, wherein,

Described organic solvent is be selected from more than a kind in unsaturated and representative examples of saturated aliphatic ketone, unsaturated and representative examples of saturated aliphatic ethers, unsaturated and representative examples of saturated aliphatic alcohols, aromatic hydrocarbon based, unsaturated and saturated alkyl halide hydro carbons, unsaturated and representative examples of saturated aliphatic alkanes and unsaturated and representative examples of saturated aliphatic ester class.

4. making molds adhesive composition according to claim 2, wherein,

Obtain two coating systems that the solvent that uses in the operation of reactant mixture is water and organic solvent molasses are carried out dehydration, the organic solvent in this two coating systems is be selected from more than a kind in unsaturated and representative examples of saturated aliphatic ketone, unsaturated and representative examples of saturated aliphatic ethers, unsaturated and representative examples of saturated aliphatic alcohols, aromatic hydrocarbon based, unsaturated and saturated alkyl halide hydro carbons, unsaturated and representative examples of saturated aliphatic alkanes and unsaturated and representative examples of saturated aliphatic ester class.

5. making molds adhesive composition according to claim 1 and 2, wherein,

Described acid catalyst is more than a kind of being selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid.

6. making molds adhesive composition according to claim 1 and 2, wherein,

The content of described 5 hydroxymethyl furfural composition in adhesive composition is more than 1 % by weight and less than 50 % by weight.

7. making molds adhesive composition according to claim 1 and 2, wherein,

The content of described 5 hydroxymethyl furfural in adhesive composition is more than 1 % by weight and less than 45 % by weight.

8. making molds adhesive composition according to claim 1 and 2, wherein,

The content of the 5 hydroxymethyl furfural in described 5 hydroxymethyl furfural composition is more than 60 % by weight and less than 95 % by weight.

9. making molds adhesive composition according to claim 1 and 2, wherein,

The content of levulic acid in adhesive composition is more than 0.001 % by weight and less than 2.5 % by weight.

10. making molds adhesive composition according to claim 1 and 2, wherein,

The content of the levulic acid in described 5 hydroxymethyl furfural composition is more than 0.1 % by weight and less than 5.0 % by weight.

11. making molds adhesive compositions according to claim 1 and 2, wherein,

Weight average molecular weight be more than 1000 the content of high-molecular weight compounds in adhesive composition be more than 0.001 % by weight and less than 2.5 % by weight.

12. making molds adhesive compositions according to claim 1 and 2, wherein,

Weight average molecular weight in described 5 hydroxymethyl furfural composition is that the content of the high-molecular weight compounds of more than 1000 is more than 0.1 % by weight and less than 5.0 % by weight.

13. making molds adhesive compositions according to claim 1 and 2, wherein,

That molasses produce when being and refining granulated sugar by the liquid glucose from sugarcane, beet, also comprise composition beyond sugar in sticky shape and the liquid of pitchy.

14. making molds adhesive compositions according to claim 1 and 2, wherein,

Molasses are blackstrap.

15. making molds adhesive compositions according to claim 1 and 2, wherein,

Described acid setting resin is the condensation product of furfuryl alcohol and/or furfuryl alcohol and urea and aldehydes.

16. 1 kinds of casting mold compositions, it contains the making molds adhesive composition in fire resistance particle, curing agent and described claim 1 ~ 14 described in wantonly 1.

Making molds adhesive composition in described claim 1 ~ 15 described in wantonly 1 is used for the purposes of Casting mold manufacturing by 17. 1 kinds.

The manufacture method of 18. 1 kinds of casting molds, it has following operation:

By the mixture solidified containing the making molds adhesive composition in fire resistance particle, curing agent and described claim 1 ~ 15 described in wantonly 1.