CN104105558A - Binder composition for producing template, and method for producing template - Google Patents
Binder composition for producing template, and method for producing template Download PDFInfo
- Publication number
- CN104105558A CN104105558A CN201380008936.2A CN201380008936A CN104105558A CN 104105558 A CN104105558 A CN 104105558A CN 201380008936 A CN201380008936 A CN 201380008936A CN 104105558 A CN104105558 A CN 104105558A
- Authority
- CN
- China
- Prior art keywords
- weight
- adhesive composition
- acid
- making molds
- wantonly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 239000011230 binding agent Substances 0.000 title abstract description 6
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- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical class O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- QMKUAAAZHQCMKH-UHFFFAOYSA-N 2-(furan-2-yl)propan-2-ol Chemical compound CC(C)(O)C1=CC=CO1 QMKUAAAZHQCMKH-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- UNIYDALVXFPINL-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylsilicon Chemical compound CC(=C)C(=O)OCCC[Si] UNIYDALVXFPINL-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- GSZSNOPBWKTLNG-UHFFFAOYSA-N CS(=O)(=O)O.C(CCC)[P](CCCC)(CCCC)CCCC Chemical compound CS(=O)(=O)O.C(CCC)[P](CCCC)(CCCC)CCCC GSZSNOPBWKTLNG-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 241001634576 Colona Species 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A binder composition for producing a template, which comprises a 5-hydroxymethylfurfural composition produced from molasses and an acid-curable resin. It is preferred that the 5-hydroxymethylfurfural composition is produced through a step of subjecting molasses to a dehydration reaction in a solvent in the presence of an acid catalyst to produce a reaction mixture and a step of extracting the reaction mixture with an organic solvent to produce the 5-hydroxymethylfurfural composition, and it is more preferred that the content ratio of the 5-hydroxymethylfurfural composition in the binder composition is 1 to 50 wt% inclusive.
Description
Technical field
The present invention relates to making molds with adhesive composition and used the manufacture method of composition and casting mold for its casting mold.
Background technology
Acid cure self-hardening property casting mold is manufactured by the following method: in the fire resistance particles such as silica sand, add binding agent and the curing agent that contains organic sulfonic acid, sulfuric acid, phosphoric acid etc. for the making molds contain acid setting resin, they are mixing, then the mixing sand obtaining is filled in the models such as wooden die, acid setting resin is solidified.Acid setting resin is used furane resins, phenolic resins etc., and furane resins are used 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 is used when the foundry goods such as mechanical foundry goods parts, construction implement parts or automotive part are cast.
In the moulding of described casting mold or use that casting mold casts desirable foundry goods aspect, as important project, can enumerate the raising of the final strength of casting mold.About the final strength of casting mold, when producing large-scale casting mold, become and be necessary especially, if undercapacity, veining or the internal rupture while there is casting or bring danger to operator, the foundry goods of gained likely becomes defective work.
In patent documentation 1, the acid cure type binding agent composition for moulds that discloses the compound of the aldehyde radical in molecule with one or more that mixing is obtained by carbohydrate or starch in acid cure type resin or their reactions are formed, has obtained the casting mold of accelerating curing rate, improving mould strength, have superior surface performance.
In addition, in patent documentation 2, disclose: contain the 5 hydroxymethyl furfural, 2 that is selected from specified quantitative, 5-furyl dimethyl carbinol, 2,5-furandicarboxylic acid, 2,5-bis-formyl furans, PEPA a kind above and furfuryl alcohol and in fact containing phenol, formaldehyde, the nitrogen adhesive composition of (referring to that urea etc. is containing the composition of amine), can improve operating environment by reducing harmful substance, gas.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-235034 communique
Patent documentation 2:US20080207796 communique
Summary of the invention
The problem that invention will solve
Yet foul smell when although the adhesive composition of patent documentation 2 can reduce 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 the adhesive composition of patent documentation 1, the final strength of the storage stability of talkative adhesive composition, particularly casting mold is inabundant, is therefore seeking further improvement.
Composition and the manufacture method of having used its casting mold for the casting mold that the invention provides the adhesive composition for making molds that can make that the final strength of casting mold improves, has used it.
Solve the means of problem
Making molds adhesive composition of the present invention is to contain the 5 hydroxymethyl furfural composition manufactured by molasses and the making molds adhesive composition of acid setting resin.
Casting mold composition of the present invention is by adhesive composition and casting mold composition that this making molds is mixed with curing agent with the curing furane resins of adhesive composition for fire resistance particle, described making molds.
The manufacture method of casting mold of the present invention has following operation: by containing fire resistance particle, described making molds is with adhesive composition and this making molds is cured with the mixture of curing agent with the curing furane resins of adhesive composition.
Invention effect
Utilize making molds adhesive composition of the present invention, can make the final strength of casting mold improve.In addition, utilize the manufacture method of composition and casting mold for casting mold of the present invention, can make the final strength of casting mold improve.
The specific embodiment
Adhesive composition for making molds of the present invention is (following, also being only called " adhesive composition ") binding agent when manufacturing casting mold uses, is to contain the 5 hydroxymethyl furfural composition manufactured by molasses and the making molds adhesive composition of acid setting resin.The effect that adhesive composition performance of the present invention improves the final strength of casting mold.The reason of bringing into play such effect is still not clear, but can consider as follows.
5 hydroxymethyl furfural have methylol and aldehyde radical the two.Methylol has 1 reaction site, and aldehyde radical has two reaction site, as 5 hydroxymethyl furfural, has 3 reaction site altogether.And the reactivity of Zhe Liangge functional group is different, there is reactive higher reaction site and reactive lower reaction site.Therefore, thereby because the reactivity difference of Liang Ge functional group becomes and can guarantee the up time, in addition, infer owing to thering are 3 reaction site, therefore can carry out fast incessantly the cross-linking reaction of linear polymer, casting mold snap cure.Think: in the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention, the accessory substance resulting from as the molasses of raw material can make 5 hydroxymethyl furfural composition uniform dissolution in the acid setting resins such as furane resins, thereby 5 hydroxymethyl furfural composition can evenly and efficiently react with furane resins.Therefore, think in the adhesive composition that contains 5 hydroxymethyl furfural composition, cross-linking reaction becomes to be more dissolved in and carries out, and therefore can improve mould strength.
Below, composition contained in adhesive composition of the present invention is described.
Adhesive composition of the present invention contains 5 hydroxymethyl furfural composition and the acid setting resin of being manufactured by molasses.
The 5 hydroxymethyl furfural composition > that < is manufactured by molasses
The 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention is manufactured through following operation: under the existence of acid catalyst, in solvent, molasses are carried out to dehydration and obtain the operation of reactant mixture and the operation that obtains 5 hydroxymethyl furfural composition with organic solvent extraction reactant mixture.The 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention be take 5 hydroxymethyl furfural as main component, and as accessory substance, comprising weight average molecular weight is the hexoses such as organic acid, fructose, glucose, mannose, galactolipin (hexose), ash content, the moisture etc. such as more than 1000 macromolecular compound, levulic acid.
< molasses >
Molasses are the liquid that glues shape and pitchy that is producing while refining granulated sugar by the liquid glucose from sugarcane, beet, also comprise sugar composition in addition, are blackstrap.
Composition > in < molasses
In the present invention, the molasses of commercially available product can be used, the molasses of Kaset Thai Sugar company system can be exemplified.It is organic acids such as more than 3500 high-molecular weight compounds, lactic acid, acetic acid, formic acid, oxalic acid, citric acid etc. that these molasses contain sucrose, glucose, fructose, wood sugar, moisture, ash content, protein, weight average molecular weight.
From the viewpoint that the final strength of casting mold is improved, consider, more than the content of the sucrose in molasses is preferably 10 % by weight, more preferably more than 15 % by weight, more preferably more than 20 % by weight, in addition, be preferably below 50 % by weight, more preferably below 40 % by weight, more preferably below 30 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the content of the glucose in molasses is preferably 1.0 % by weight, more preferably more than 3.0 % by weight, more preferably more than 5.0 % by weight, in addition, be preferably below 20 % by weight, more preferably below 15 % by weight, more preferably below 10 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the content of the fructose in molasses is preferably 1.0 % by weight, more preferably more than 5.0 % by weight, more preferably more than 7.0 % by weight, in addition, be preferably below 20 % by weight, more preferably below 18 % by weight, more preferably below 15 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the content of the wood sugar in molasses is preferably 1.0 % by weight, more preferably more than 2.0 % by weight, in addition, be preferably below 20 % by weight, more preferably below 15 % by weight, more preferably, below 10 % by weight, be further preferably below 6.0 % by weight.
In addition, from economy and the viewpoint that the final strength that makes casting mold improves, consider, more than the content of the moisture in molasses is preferably 5.0 % by weight, more preferably more than 15 % by weight, in addition, be preferably below 40 % by weight, more preferably below 35 % by weight, more preferably below 30 % by weight.
In addition, from economy and the viewpoint that the final strength that makes casting mold improves, consider, more than the content of the ash content in molasses is preferably 1.0 % by weight, more preferably more than 3.0 % by weight, in addition, be preferably below 20 % by weight, more preferably below 15 % by weight, more preferably below 10 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the content of the protein in molasses is preferably 0.1 % by weight, more preferably more than 0.3 % by weight, in addition, be preferably below 5.0 % by weight, more preferably below 4.0 % by weight, more preferably below 3.0 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, weight average molecular weight in molasses is more than the content of more than 3500 high-molecular weight compounds is preferably 1.0 % by weight, more preferably more than 2.0 % by weight, more preferably more than 3.0 % by weight, in addition, be preferably below 20 % by weight, more preferably below 15 % by weight, more preferably below 10 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the organic acid content such as the lactic acid in molasses, acetic acid, formic acid, oxalic acid, citric acid are preferably 0.1 % by weight, more preferably more than 0.5 % by weight, more preferably more than 1.0 % by weight, in addition, be preferably below 5 % by weight, more preferably below 4.5 % by weight, more preferably below 4 % by weight.
Sucrose, glucose, fructose, wood sugar, moisture, ash content, protein, weight average molecular weight that the method that can record by embodiment is measured in molasses are more than 3500 high-molecular weight compounds and organic acid content.
The manufacture method > of the 5 hydroxymethyl furfural composition that < is manufactured by molasses
[operation I]
Manufacture method of the present invention has the operation (following, to be sometimes only called " operation I ") of in solvent, molasses (blackstrap) being carried out to dehydration and obtaining reactant mixture under the existence of acid catalyst.
(acid catalyst)
Under the existence of acid catalyst, carry out the dehydration in operation I.As the acid catalyst using, such as enumerating 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; Take the cationic sulfonate resin class that amberlyst, amberlite, Diaion etc. are representative; The phosphoric acid immobilized catalyst that the sulfuric acid immobilized catalyst that zeolite, aluminium oxide, silica-alumina, clay, the sulfated zirconia of take are representative, the phosphorylation titanium dioxide of usining are representative, heteropllyacids, aluminium chloride, chromium chloride etc. have as the slaine of Louis's effect or their mixture.Wherein, the viewpoint improving from the yield of the 5 hydroxymethyl furfural composition manufactured by molasses and the viewpoint of economy are considered, be preferably inorganic acids or carboxylic acids, more preferably be 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 a kind or two or more, be more preferably selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, boric acid a kind or two or more.
Consumption as the acid catalyst in dehydration, from the raising of reaction speed, the viewpoint that the viewpoint that the generation of accessory substance suppresses, economy and discarded object reduce consider, with respect to molasses, be preferably 0.1～50 % by weight, 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), can be also semi continuous, can also be continous way, and can be the reactive mode that both are combined.The viewpoint improving from productivity ratio is considered, is preferably semi continuous reaction and continuous reaction, from the viewpoint of the simple and easy degree of operation, considers, is preferably intermittent reaction.
(reaction temperature)
As the reaction temperature in dehydration, from the raising of reaction speed,, the viewpoint that the generation of accessory substance suppresses consideration is preferably 50～250 ℃, more preferably 70～230 ℃, more preferably 80～220 ℃, be further preferably 100～200 ℃.
(reaction pressure)
As the reaction pressure in dehydration, from the raising of reaction speed, the viewpoint that the viewpoint that the growing amount of accessory substance reduces and machine utilization reduce consider, be preferably 0.1～40MPa, 0.1～20MPa more preferably, 0.1～10MPa more preferably, further be preferably 0.1～5MPa, be further preferably 0.1～2MPa, be further preferably 0.1～1MPa.
(reaction dissolvent)
In solvent, carry out the dehydration of described molasses.About reaction dissolvent, can be by least a portion of raw material or its reaction intermediate, be preferably sizable degree, more preferably dissolve completely, and also under reaction condition, stable solvent is suitable.And, make the 5 hydroxymethyl furfural generating (below also referred to as HMF.) with sizable degree, dissolve, more preferably make it dissolve completely.For example can enumerate water, high aprotic, polar organic solvent, ionic liquid.Particularly, as high aprotic, polar organic solvent, for example can enumerate dimethyl sulfoxide (DMSO), 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 enumerating 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 such as two (trifluoromethyl sulfonyl) acid imides of the microcosmic salt classes such as methanesulfonic acid tetrabutyl phosphorus and triethyl group sulphur etc.Also two or more solvents arbitrarily can be used in combination in addition.The viewpoint suppressing from the growing amount of reactivity and accessory substance is considered, is preferably high polar organic solvent and ionic liquid, for example dimethyl sulfoxide (DMSO), dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE, imidazole salt, pyridinium salt.From the viewpoint of economy, consider, more preferably water.While selecting water as main solvent, except water, preferably make more than one organic solvent mix.As the solvent now using, the viewpoint suppressing from the growing amount of reactivity and accessory substance considers, low with water miscibility, has the physical property such as polarity, dissolubility of the degree of the HMF that can extract generation, and under the condition of using, stable solvent is suitable.For example, can use unsaturated and representative examples of saturated aliphatic ketone (as aliphatic ketone, can enumerate non-annularity aliphatic ketone, annular aliphatic ketone.), unsaturated and representative examples of saturated aliphatic ethers (as aliphatic ethers, can enumerate non-annularity 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, from polarity, deliquescent viewpoint, consider, can use any two or more mixtures that combine in them.Particularly, can enumerate 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 combination arbitrarily.Wherein, the viewpoint improving from the extraction efficiency of HMF is considered, be preferably methyl iso-butyl ketone (MIBK), cyclohexanone, butanols, oxolane, amylalcohol, carrene, chloroform, ethyl acetate, propyl acetate, butyl acetate, toluene, more preferably methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, butanols, carrene, chloroform.
In operation I when solvent makes water and organic solvent, from the viewpoint of economy and accessory substance inhibition, consider, the weight rate of water and organic solvent (water: organic solvent) be preferably 1:10～1:0.01, more preferably 1:7～1:0.05, more preferably 1:5～1:0.1.
The viewpoint improving from the yield of the 5 hydroxymethyl furfural composition manufactured by molasses is considered, the concentration with respect to solvent as the molasses that use in manufacture method of the present invention, be preferably 0.01～70 % by weight, 0.1～65 % by weight more preferably, 1～60 % by weight more preferably, further be preferably 3～40 % by weight, be further preferably 5～20 % by weight.
(in and operation)
As required, after operation I finishes or after aftermentioned operation II finishes, acid catalyst can be neutralized.From the viewpoint of the stability forming of the 5 hydroxymethyl furfural composition manufactured by molasses, consider, preferably neutralize.As the nertralizer using in neutralization, such as enumerating 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, consider, 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 that they are as in the molecule of the molasses of initiation material and the anhydrousugar or sugared condensation body, 5 hydroxymethyl furfural polycondensation forms each other 5 hydroxymethyl furfural polymer, 5 hydroxymethyl furfural and initiation material and the reaction intermediate that form of intermolecular dehydration, the humus that is formed solid-state castoff by the mistake product of 5 hydroxymethyl furfural.As required, can remove by filter this solid content, also can not filter and wait until the ensuing manufacturing processes such as extraction process and complete.
[operation II]
Manufacture method of the present invention has the operation (following, to be sometimes only called " operation II ") of the 5 hydroxymethyl furfural that obtains being manufactured by molasses with organic solvent extraction reactant mixture after the dehydration of operation I.
(organic solvent)
The 5 hydroxymethyl furfural in the reactant mixture being obtained by operation I is reclaimed in an organic solvent extraction.
Organic solvent as using, can be used for example unsaturated and representative examples of saturated aliphatic ketone (as aliphatic ketone, can enumerate non-annularity aliphatic ketone, annular aliphatic ketone.), unsaturated and representative examples of saturated aliphatic ethers (as aliphatic ethers, can enumerate non-annularity 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, from polarity, deliquescent viewpoint, consider, can use two kinds of mixtures that combine arbitrarily among them.Particularly, can enumerate 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 combination arbitrarily.Wherein, the viewpoint improving from the extraction efficiency of the 5 hydroxymethyl furfural composition manufactured by molasses is considered, be preferably methyl iso-butyl ketone (MIBK), cyclohexanone, butanols, oxolane, amylalcohol, carrene, chloroform, ethyl acetate, propyl acetate, butyl acetate, toluene, 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, the viewpoint improving from the extraction efficiency of the 5 hydroxymethyl furfural composition manufactured by molasses is considered, in weight rate, water is made as at 1 o'clock, the organic solvent amount of using in extraction is preferably 0.1～50, 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 (for example 3 times) is used.
The operation that reclaims 5 hydroxymethyl furfural from reactant mixture extraction can be the dehydration of operation I, also can be in the dehydration of operation I, and can also be above-mentioned in both.From the viewpoint that the productivity ratio of 5 hydroxymethyl furfural composition improves and accessory substance suppresses, consider, the operation reclaiming from reactant mixture extraction is preferably dehydration and after dehydration the two.
(enrichment process)
After manufacture method of the present invention can be included in operation II and finishes, further organic solvent is removed in distillation, by the concentrated operation of 5 hydroxymethyl furfural composition of being manufactured by molasses.Concentrated condition is not particularly limited, but considers from the viewpoint of the heat endurance of the inhibition of side reaction, the 5 hydroxymethyl furfural composition manufactured by molasses, such as enumerating reduced pressure concentration, the method for using permeable membrane, transpiration (evapotranspiring), freeze drying etc.While carrying out reduced pressure concentration, on the basis that can distill except the sufficient reduced pressure of desolventizing, preferably at 150 ℃, carry out below, more preferably below 120 ℃, further preferably below 100 ℃, further preferably below 80 ℃, further preferably below 60 ℃.Now, can only distill and remove with reducing pressure, can limit be removed by the distillation of the gas toppings such as nitrogen (ト ッ ピ Application グ) limit in addition.
The viewpoint improving from mould strength is considered, more than 5 hydroxymethyl furfural content in the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention is preferably 60 % by weight, 70 % by weight more preferably, more preferably more than 72 % by weight, more than being further preferably 80 % by weight, in addition, be preferably below 95 % by weight, more preferably below 90 % by weight.
In addition, the viewpoint improving from mould strength is considered, 5 hydroxymethyl furfural content in the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention is preferably 60～95 % by weight, 70～90 % by weight more preferably, more preferably 72～90 % by weight, are further preferably 80～90 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, more than the content of the levulic acid in the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention is preferably 0.1 % by weight, in addition, be preferably below 5.0 % by weight, more preferably below 3.0 % by weight, more preferably below 1.5 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, in the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention, weight average molecular weight is more than the content of more than 1000 high-molecular weight compounds is preferably 0.1 % by weight, more preferably more than 0.5 % by weight, more preferably more than 1.2 % by weight, in addition, be preferably below 5.0 % by weight, more preferably below 3.0 % by weight, more preferably below 2.0 % by weight.
The viewpoint improving from the intensity of casting mold is considered, more than the content of the 5 hydroxymethyl furfural composition of being manufactured by molasses of the present invention in adhesive composition is preferably 1 % by weight, more preferably more than 4 % by weight, more preferably more than 5 % by weight, more than being further preferably 6 % by weight, more than being further preferably 10 % by weight, in addition, be preferably below 50 % by weight, more preferably below 40 % by weight, more preferably, below 30 % by weight, be further preferably below 20 % by weight, be further preferably 12 % by weight.In addition, from the same viewpoint, be preferably 1～50 % by weight, 4～40 % by weight more preferably, more preferably 5～30 % by weight, are further preferably 6～20 % by weight, are further preferably 10～12 % by weight.In addition, the viewpoint improving from the intensity of casting mold is considered, more than the content of the 5 hydroxymethyl furfural of being manufactured by molasses of the present invention in adhesive composition is preferably 1 % by weight, more preferably more than 3 % by weight, more preferably more than 4 % by weight, more than being further preferably 5 % by weight, in addition, be preferably below 45 % by weight, more preferably below 35 % by weight, more preferably, below 25 % by weight, be further preferably below 15 % by weight.In addition, from the same viewpoint, be preferably 1～45 % by weight, 3～35 % by weight more preferably, more preferably 4～25 % by weight, are further preferably 5～15 % by weight.
From the viewpoint that the final strength of casting mold is improved, consider, more than the content of the levulic acid in adhesive composition of the present invention is preferably 0.001 % by weight, 0.01 % by weight more preferably, in addition, be preferably below 2.5 % by weight, more preferably below 1.5 % by weight, more preferably below 0.5 % by weight.
In addition, from the viewpoint that the final strength of casting mold is improved, consider, weight average molecular weight in adhesive composition of the present invention is more than the content of more than 1000 high-molecular weight compounds is preferably 0.001 % by weight, more preferably more than 0.01 % by weight, more preferably more than 0.08 % by weight, in addition, be preferably below 2.5 % by weight, more preferably below 1.0 % by weight, more preferably below 0.60 % by weight.
< acid setting resin >
As acid setting resin, known resin in the past can be used, for example, the self-hardening resins such as furane resins, phenolic resins can be used, but from the viewpoint of the casting mold productivity ratio of the performance based on mould strength and the environment side of the raw material based on plant origin, consider, preferably furane resins.As furane resins, can use in the condensation product of condensation product, furfuryl alcohol and the phenols of condensation product, furfuryl alcohol and urea of the condensation product, furfuryl alcohol and the aldehydes that are selected from furfuryl alcohol, furfuryl alcohol and the condensation product of condensation product, furfuryl alcohol and the melamine of aldehydes and aldehydes and furfuryl alcohol and urea and aldehydes a kind above or comprise the two or more cocondensation compound being selected from described group.Wherein, from making successfully to carry out, make the viewpoint of deep curability and final strength raising to consider with the curing reaction of foundry goods sand (cast thing sand), preferably use be selected from the condensation product of condensation product, furfuryl alcohol and urea of furfuryl alcohol, furfuryl alcohol and aldehydes and the condensation product of furfuryl alcohol and urea and aldehydes a kind above and their cocondensation compound, more preferably use the condensation product of furfuryl alcohol and/or furfuryl alcohol and urea and aldehydes.Preferably in furfuryl alcohol, under the existence of urea and formaldehyde, synthesize the condensation product of furfuryl alcohol and urea and aldehydes.
As described aldehydes, can enumerate formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde etc., among them, can suitably use more than a kind.From the viewpoint that the final strength of casting mold is improved, consider, preferably use formaldehyde, the viewpoint that the formaldehyde generation during from moulding reduces is considered, is preferably used furfural, terephthalaldehyde.
When manufacturing the condensation product of furfuryl alcohol and urea and aldehydes, with respect to 1 mole of furfuryl alcohol, preferably use 0.05～0.5 mole of urea and 0.1～1.5 mole of aldehydes.
In addition, during by the synthetic acid setting resin of the raw material that comprises urea and formaldehyde, the viewpoint of the generation of the formaldehyde when can make the viewpoint that the deep curability of casting mold and final strength improve and can reduce moulding is considered, formaldehyde during synthetic acid setting resin and the proportioning of urea are preferably formaldehyde/urea=1.5～4.0 with molar ratio computing, and more preferably 3.0～4.0.
From fully showing the viewpoint of final strength, consider, the content of the acid setting resin in adhesive composition is preferably 55～99 % by weight, more preferably 60～95 % by weight, more preferably 80～90 % by weight.
From the viewpoint that viewpoint that the deep curability of casting mold and final strength improve and storage-stable are improved, consider, the pH of acid setting resin is preferably 2.0～8.5, and more preferably 3.0～6.0, more preferably 3.5～5.0.For the pH of acid setting resin is controlled in above-mentioned scope, can regulate by add the acidic aqueous solutions such as the alkaline aqueous solutions such as sodium hydrate aqueous solution or oxalic acid 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 the pliability of the casting mold obtaining is brought to preferred impact.Amino content can be estimated with nitrogen content (% by weight).It should be noted that, when model is extracted casting mold, needing the pliability of casting mold.Particularly when the casting mold of the shape of moulding complexity, if the pliability of casting mold is high, in the time of can preventing from pulling out type, stress concentrates on the part of wall thickness of casting mold and the veining that causes.With regard to adhesive composition of the present invention, from making the viewpoint of breaking of the final strength viewpoint improving and the casting mold that prevents from obtaining, consider, nitrogen content in adhesive composition is preferably 0.8～6.0 % by weight, 1.8～6.0 % by weight more preferably, 2.2～5.0 % by weight more preferably, further be preferably 2.3～4.5 % by weight, be further preferably 2.5～4.0 % by weight.For the nitrogen content in adhesive composition is adjusted in above-mentioned scope, can regulate the content of the nitrogen-containing compound in adhesive composition.As nitrogen-containing compound, be preferably condensation product, urea resin and the urea-modified resin etc. of condensation product, melamine and the aldehydes of urea, melamine, urea and aldehydes.Can come the nitrogen content in adhesive composition quantitative by Kjeldahl's method.Further, also can be by quantitatively obtaining to being derived from the carbonyl (C=O yl) of urea the nitrogen content that is derived from urea, urea resin, furfuryl alcohol-urea resin (urea-modified resin) and furfuryl alcohol-urea-formaldehyde resin with 13C-NMR.
Other additives of < >
In addition, can in adhesive composition, further contain the additives such as silane coupler.If for example contain silane coupler, can make final strength improve, therefore preferably.As silane coupler, can use N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, 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-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, the epoxy silanes such as 3-glycidoxy propyl-triethoxysilicane, ureido silane, hydrosulphonyl silane, sulfide silane, methacryloxypropyl silane, acryloyl-oxy base silane etc.Be preferably amino silane, epoxy silane, ureido silane, more preferably amino silane, more preferably N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane.The viewpoint consideration improving from final strength, the content of silane coupler in adhesive composition is preferably 0.01～0.5 % by weight, more preferably 0.05～0.3 % by weight.It should be noted that, can be used as a composition of acid setting resin and contain silane coupler.
Casting mold of the present invention contains fire resistance particle, curing agent and making molds adhesive composition of the present invention with composition.
As fire resistance particle, can use the known particle in the past such as silica sand, chromite sand, zircon sand, olivine sand, aluminum oxide sand, mullite sand, mullite synthesizing sand, in addition, also can use the particle that the fire resistance particle after using is reclaimed and obtain, the particle after regeneration processing etc.
As curing agent, the acidic aqueous solution etc. that can use sulfonic acid based compound, phosphoric acid based compound, sulfuric acid etc. such as containing xylene monosulfonic acid (particularly meta-xylene sulfonic acid) or toluenesulfonic acid (particularly p-methyl benzenesulfonic acid) is the more than a kind of known curing agent in the past.Further, can in curing agent, contain more than a kind solvent or the carboxylic acids being selected from alcohols, ether alcohol class and ester class.Among them, from realizing the raising of deep curability of casting mold, the viewpoint of the raising of final strength consider, be preferably alcohols, ether alcohol class, more preferably ether alcohol class.In addition, if contain above-mentioned solvent, carboxylic acids, can reduce the amount of moisture in curing agent, so the further change of the deep curability of casting mold is good, final strength further improves simultaneously.The viewpoint consideration improving from final strength, described solvent, the content of described carboxylic acids in curing agent are preferably 5～50 % by weight, more preferably 10～40 % by weight.In addition, from the viewpoint that the viscosity of curing agent is reduced, consider, preferably contain methyl alcohol, ethanol.
Can suitably set fire resistance particle in mixing sand and the ratio of adhesive composition and curing agent, but with respect to fire resistance particle 100 weight portions, scope, the curing agent that adhesive composition is preferably 0.5～1.5 weight portion is preferably the scope of 0.07～1 weight portion.If such ratio, easily obtains the sufficient casting mold of final strength.Further, from reduce amount of moisture contained casting mold, the viewpoint of deep curability raising of casting mold and the viewpoint of the mixing efficiency of use blender considered as far as possible, with respect to acid setting resin 100 weight portions in adhesive composition, the content of curing agent is preferably 10～70 weight portions, more preferably 15～60 weight portions, more preferably 20～55 weight portions.
Adhesive composition of the present invention is applicable to have and makes to contain the manufacture method of the casting mold of the operation of the mixture solidified of adhesive composition and curing agent for fire resistance particle, making molds.That is, the manufacture method of casting mold of the present invention is to use the adhesive composition of the invention described above as making molds, to use the manufacture method of the casting mold of adhesive composition.
In the manufacture method of casting mold of the present invention, can directly utilize the processing of the manufacture method of casting mold in the past to manufacture casting mold.For example, by the adhesive composition of the invention described above and the curing curing agent of this adhesive composition is added in fire resistance particle, with batch mixer, continuous mixing device etc., they are mixing, can obtain thus said mixture (mixing sand).In the manufacture method of casting mold of the present invention, the viewpoint improving from final strength is considered, preferably in fire resistance particle, adds after described curing agent, adds adhesive composition of the present invention.
With regard to composition of the present invention,
<1> contains the 5 hydroxymethyl furfural composition manufactured by molasses and the making molds adhesive composition of acid setting resin.
The present invention is preferred following composition or manufacture method or purposes further.
<2> is according to the making molds adhesive composition of described <1>, wherein, described 5 hydroxymethyl furfural composition forms through following operation manufacture: under the existence of acid catalyst, in solvent, molasses are carried out to dehydration and obtain the operation of reactant mixture and the operation that obtains 5 hydroxymethyl furfural composition with organic solvent extraction reactant mixture.
<3> is according to the making molds adhesive composition of described <2>, wherein, in described solvent, molasses are carried out 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 be selected from 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 more than a kind.
<5> is according to the making molds adhesive composition of described <2>～<4>, wherein, described acid catalyst be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid more than a kind.
<6> is according to the making molds adhesive composition of described <1>～<5>, wherein, more than the content of described 5 hydroxymethyl furfural composition in adhesive composition is preferably 1 % by weight, more preferably more than 4 % by weight, more preferably more than 5 % by weight, more than being further preferably 6 % by weight, more than being further preferably 10 % by weight, in addition, be preferably below 50 % by weight, more preferably below 40 % by weight, more preferably below 30 % by weight, further be preferably below 20 % by weight, further be preferably below 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 more than being preferably 1 % by weight, more preferably more than 3 % by weight, more preferably more than 4 % by weight, more than being further preferably 5 % by weight, in addition, be preferably below 45 % by weight, more preferably below 35 % by weight, more preferably below 25 % by weight, further be preferably below 15 % by weight.
<8> is according to the making molds adhesive composition of described <1>～<7>, wherein, more than the content of the 5 hydroxymethyl furfural in described 5 hydroxymethyl furfural composition is preferably 60 % by weight, more preferably more than 70 % by weight, more preferably more than 72 % by weight, more than being further preferably 80 % by weight, in addition, be preferably below 95 % by weight, more preferably below 90 % by weight.
<9> is according to the making molds adhesive composition of described <1>～<8>, wherein, more than the content of levulic acid in adhesive composition is preferably 0.001 % by weight, more preferably more than 0.01 % by weight, in addition, be preferably below 2.5 % by weight, more preferably below 1.5 % by weight, more preferably below 0.5 % by weight.
<10> is according to the making molds adhesive composition of described <1>～<9>, wherein, more than the content of the levulic acid in described 5 hydroxymethyl furfural composition is preferably 0.1 % by weight, in addition, be preferably below 5.0 % by weight, more preferably below 3.0 % by weight, more preferably below 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 more than 1000 high-molecular weight compounds content in adhesive composition is for more than being preferably 0.001 % by weight, more preferably more than 0.01 % by weight, more preferably more than 0.08 % by weight, in addition, be preferably below 2.5 % by weight, more preferably below 1.0 % by weight, more preferably below 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 more than the content of more than 1000 high-molecular weight compounds is preferably 0.1 % by weight, more preferably more than 0.5 % by weight, more preferably more than 1.2 % by weight, in addition, be preferably below 5.0 % by weight, more preferably below 3.0 % by weight, 2.0 % by weight more preferably.
<13> is according to the making molds adhesive composition of described <1>～<12>, wherein, molasses are the liquid that glues shape and pitchy that is producing while refining granulated sugar by the liquid glucose from sugarcane, beet, also comprise sugar composition in addition.
<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, the making molds adhesive composition that it contains fire resistance particle, curing agent and described <1>～<15>.
Mono-kind of <17> by the making molds described in described <1>～<15> with adhesive composition the purposes for Casting mold manufacturing.
The manufacture method of a <18> casting mold, it has following operation: the mixture solidified by the making molds that contains fire resistance particle, curing agent and described <1>～<15> with adhesive composition.
Embodiment
Below, with embodiment specifically illustrating etc., the present invention will be described.It should be noted that, as follows the assessment item in embodiment etc. is measured.
In <5-hydroxymethylfurfural composition and the content > of the levulic acid in adhesive composition
By the chromatography of ions, by following method, calculate content.
Device: DX-320 (Japanese Dionex company system)
Post: Ion Pac AS11HC
Eluent: 10mM KOH (0min) → 40mM KOH (25min)
Flow: 1.5mL/min
Automatically TVS (Autosuppressor): ASRS-300 (Japanese Dionex company system)
Detect: electrical conductivity
MS device: LCMS-2010EV (Shimadzu Seisakusho Ltd.'s system)
Flow: 1mL/min
In <5-hydroxymethylfurfural composition and the content > of the high-molecular weight compounds in adhesive composition
With gel permeation chromatography, by following method, calculate content.
Detector: RI
Post: TSKgel α-M * 2 (Dong Cao company system)
Temperature: 40 ℃
Eluent: DMF
Flow: 1.0mL/min
Conversion standard: polystyrene
Furfuryl alcohol content > in < adhesive composition
By gas chromatography, measure.(with furfuryl alcohol production standard curve)
Condition determination:
Inner mark solution: 1,6-hexylene glycol
Post: PEG-20M Chromosorb WAW DMCS 60/80mesh (GL Sciences company system)
Column temperature: 80～200 ℃ (8 ℃/min)
Sample introduction temperature: 210 ℃
Detector temperature: 250 ℃
Carrier gas: 50mL/min (He)
Moisture > in < adhesive composition
Moisture test method by the chemicals shown in JIS K 0068 is measured.
Nitrogen content > in < adhesive composition
By the Kjeldahl's method shown in JIS M 8813, measure.
Weight nitroxide % in adhesive composition is 3.00 % by weight in embodiment 1～5 and comparative example 1.
Sugared conversion ratio and hexose content > during <HMF manufactures
By high performance liquid chromatography, measure.
Detector: colona CAD
Post: Asahipak NH2P-50
Temperature: 25 ℃
Eluent: the water that a) acetonitrile b) contains 30% methyl alcohol
Flow: 1.0mL/min
HMF content > during <HMF manufactures
By high performance liquid chromatography, measure.
Detector: RI
Post: CARBO Sep COREGEL-87H
Temperature: 80 ℃
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, by following method, calculated content.
Detector: RI
Post: TSKgel α-M * 2 (Dong Cao company system)
Temperature: 40 ℃
Eluent: containing the water of 30% methyl alcohol
Flow: 0.6mL/min
Conversion standard: polystyrene
Organic acid content > in < molasses
By the chromatography of ions, by following method, calculated content.
Device: DX-320 (Japanese Dionex company system)
Post: Ion Pac AS11HC
Eluent: 10mM KOH (0min) → 40mM KOH (25min)
Flow: 1.5mL/min
Automatically TVS: ASRS-300 (Japanese Dionex company system)
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, by following method, calculated content.
Device: DX-320 (Japanese Dionex company system)
Post: Carbo Pac PA1 (4.0mm * 250mm)
Sample concentration: 100ppm
Eluent: A 100mM NaOH B 100mM NaOH/CH3COONa C ultra-pure water
Flow: 1.0mL/min
Detect: electrochemical detector
Protein content > in < molasses
As analytical equipment, use fully automatic high-speed amino acid analysis machine (model JLC-500/V, company of NEC system) to measure.
Ash content > in < molasses
Decrement and residue (residual minute) test method(s) by the chemicals shown in JIS K 0067 are measured.
Moisture > in < molasses
According to the moisture test method of the chemicals shown in JIS K 0068, measure.
Composition > in < molasses
The molasses that use in the present invention for 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 be more than 3500 high-molecular weight compounds 6.5 % by weight.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, used the blackstrap of Kaset Thai Sugar company system as molasses.This blackstrap is the liquid that glues shape and pitchy that is producing while refining granulated sugar by the liquid glucose from sugarcane, beet, also contain sugar composition in addition.
Production Example 1 (HMF1) > of <5-hydroxymethylfurfural composition
In 500mL titanium electromagnetic type autoclave processed (Dong high pressure company system), add the blackstrap (Kaset Thai Sugar company system), the ion exchange water of 40.0g of 20.0g, the phosphoric acid of the methyl iso-butyl ketone (MIBK) of 160g (Wako Pure Chemical Industries, Ltd.'s system) and 2.0g (purity 85%, Aldrich system).After container is airtight, with nitrogen, inner space is fully replaced.Limit is fully stirred content limit and is warming up to 140 ℃ afterwards, arrives 140 ℃ of back continuation insulations, 3 hours limits of stirring and reacts.It should be noted that, gauge pressure during reaction is 0.4MPa.After reaction finishes, limit maintains stirring limit the temperature of content is cooled to below 30 ℃.After cooling, content filtered and carry out, after the removing of solid state component, from water-soluble liquid phase and methyl isobutyl ketone solution, gathering respectively mutually sample, with pure water dilution, with liquid chromatography for measuring the concentration of 5 hydroxymethyl furfural of each phase.With regard to HMF1, by RI detection method, measure the peak area of the 5 hydroxymethyl furfural in the chromatogram obtain, by the relational expression of the concentration-area of ready-made 5 hydroxymethyl furfural, calculate the concentration in sample.Consequently, the blackstrap amount adding of take is benchmark, has confirmed the generation of the 5 hydroxymethyl furfural of 16.0 % by weight (3.20g).In 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 being 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 extracting operation 3 times, methyl isobutyl ketone solution after the methyl isobutyl ketone solution that extracting operation by water-soluble liquid phase is obtained and the reaction by above-mentioned separated and collected finish is mixed, by revolving steaming instrument, methyl iso-butyl ketone (MIBK) distillation is removed, 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, and weight average molecular weight is that more than 1000 high-molecular weight compounds is 1.5 % by weight.
Production Example 2 (HMF2) > of <5-hydroxymethylfurfural composition
In 500mL titanium electromagnetic type autoclave processed (Dong high pressure company system), add the blackstrap (Kaset Thai Sugar company system), the ion exchange water of 40.0g of 20.0g, the phosphoric acid of the methyl iso-butyl ketone (MIBK) of 160g (Wako Pure Chemical Industries, Ltd.'s system) and 2.0g (purity 85%, Aldrich system).After container is airtight, with nitrogen, inner space is fully replaced.Limit is fully stirred content limit and is warming up to 140 ℃ afterwards, arrives 140 ℃ of back continuation insulations, 3 hours limits of stirring and reacts.It should be noted that, gauge pressure during reaction is 0.4MPa.After reaction finishes, limit maintains stirring limit the temperature of content is cooled to below 30 ℃.After cooling, content is filtered and carry out after the removing of solid state component, limit is stirred filtrate limit and is splashed into 50 % by weight sodium hydrate aqueous solutions and neutralize, and the pH of filtrate is adjusted to 7.After neutralization, content is filtered and carry out, after the removing of solid state component, with the same method of the manufacture with HMF1, having measured the concentration of the 5 hydroxymethyl furfural of each phase.Consequently, take the blackstrap amount that adds has confirmed the generation of the 5 hydroxymethyl furfural of 11.6 % by weight (4.65g) as benchmark.In 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, obtained the concentrate of HMF2.The weight of concentrate is 4.293g, wherein the weight of 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, and weight average molecular weight is that more than 1000 high-molecular weight compounds is 1.7 % by weight.
Production Example 3 (HMF3) > of <5-hydroxymethylfurfural composition
Except being set to D-Fructose, use raw material reacts similarly to Example 1.Consequently, in the molar basis of fructose, confirmed to be equivalent to the generation of 72% HMF.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, and weight average molecular weight is that more than 1000 high-molecular weight compounds is 1.1 % by weight.
Production Example 4 (HMF4) > of <5-hydroxymethylfurfural composition
Except being set to D-Fructose, use raw material reacts similarly to Example 2.Consequently, confirmed to be equivalent to the generation of 66% HMF in 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, and weight average molecular weight is that more than 1000 high-molecular weight compounds is 1.0 % by weight.
The manufacture > of < condensation product 1
In three-neck flask, by furfuryl alcohol 100 weight portions and paraformaldehyde 35 weight portions and urea 13 weight portions mixing, with 25% sodium hydrate aqueous solution, be adjusted to pH9.Be warming up to after 100 ℃, with uniform temp, make its reaction after 1 hour, with 37% hydrochloric acid, be adjusted to pH4.5, further at 100 ℃, make its reaction 1 hour.Afterwards, with 25% sodium hydrate aqueous solution, be adjusted to pH7, add urea 5 weight portions, at 100 ℃, make its reaction 30 minutes, obtained reactant 1.By above-mentioned analytical method, obtain unreacted furfuryl alcohol, using the part of having removed unpolymerized furfuryl alcohol 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 of composition that becomes 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) >
Under 25 ℃, the condition of 55%RH, with respect to silica sand (Fremantle) 100 weight portions, add curing agent (kaoquaker company カ オ processed 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 portions shown in table 1, they are obtained by mixing to mixing sand.Afterwards, the columniform test piece frame that just mixing mixing sand is filled to diameter 50mm, high 50mm pulled out type after 3 hours, from filling 24 hours, be used in the method for recording in JIS Z 2604-1976 and measure compressive strength (MPa), as " compressive strengths after 24 hours ".The higher expression mould strength of numerical value is higher.Show the result in table 1.
As from table 1 clear and definite, it is more excellent that the adhesive composition of embodiment 1～5 and the adhesive composition of comparative example 1～3 are compared compressive strength.
Claims (18)
1. a making molds adhesive composition, it contains 5 hydroxymethyl furfural composition and the acid setting resin of being manufactured by molasses.
2. making molds adhesive composition according to claim 1, wherein,
Described 5 hydroxymethyl furfural composition forms through following operation manufacture:
Under the existence of acid catalyst, in solvent, molasses are carried out to dehydration and obtain reactant mixture operation and
With organic solvent extraction reactant mixture, obtain the operation of 5 hydroxymethyl furfural composition.
3. making molds adhesive composition according to claim 2, wherein,
In described solvent, molasses are carried out in the operation of dehydration, described solvent is two coating systems of water and organic solvent.
4. according to the making molds adhesive composition described in claim 2 or 3, wherein,
Described organic solvent be selected from 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 more than a kind.
5. according to the making molds adhesive composition described in claim 2～4 wantonly 1, wherein,
Described acid catalyst be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and boric acid more than a kind.
6. according to the making molds adhesive composition described in claim 1～5 wantonly 1, wherein,
The content of described 5 hydroxymethyl furfural composition in adhesive composition is more than 1 % by weight and below 50 % by weight.
7. according to the making molds adhesive composition described in claim 1～6 wantonly 1, wherein,
The content of described 5 hydroxymethyl furfural in adhesive composition is more than 1 % by weight and below 45 % by weight.
8. according to the making molds adhesive composition described in claim 1～7 wantonly 1, wherein,
The content of the 5 hydroxymethyl furfural in described 5 hydroxymethyl furfural composition is more than 60 % by weight and below 95 % by weight.
9. according to the making molds adhesive composition described in claim 1～8 wantonly 1, wherein,
The content of levulic acid in adhesive composition is more than 0.001 % by weight and below 2.5 % by weight.
10. according to the making molds adhesive composition described in claim 1～9 wantonly 1, wherein,
The content of the levulic acid in described 5 hydroxymethyl furfural composition is more than 0.1 % by weight and below 5.0 % by weight.
11. according to the making molds adhesive composition described in claim 1～10 wantonly 1, wherein,
Weight average molecular weight is that the more than 1000 high-molecular weight compounds content in adhesive composition is more than 0.001 % by weight and below 2.5 % by weight.
12. according to the making molds adhesive composition described in claim 1～11 wantonly 1, wherein,
Weight average molecular weight in described 5 hydroxymethyl furfural composition is that the content of more than 1000 high-molecular weight compounds is more than 0.1 % by weight and below 5.0 % by weight.
13. according to the making molds adhesive composition described in claim 1～12 wantonly 1, wherein,
Molasses are the liquid that glues shape and pitchy that is producing while refining granulated sugar by the liquid glucose from sugarcane, beet, also comprise sugar composition in addition.
14. according to the making molds adhesive composition described in claim 1～13 wantonly 1, wherein,
Molasses are blackstrap.
15. according to the making molds adhesive composition described in claim 1～14 wantonly 1, 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 described in wantonly 1 in fire resistance particle, curing agent and described claim 1～15.
17. 1 kinds are used for the making molds described in described claim 1～15 wantonly 1 purposes of Casting mold manufacturing with adhesive composition.
The manufacture method of 18. 1 kinds of casting molds, it has following operation:
The mixture solidified of the use of the making molds described in wantonly 1 adhesive composition in fire resistance particle, curing agent and described claim 1～15 will be contained.
Applications Claiming Priority (5)
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| JP2012053718 | 2012-03-09 | ||
| JP2012-053718 | 2012-03-09 | ||
| JP2013-000592 | 2013-01-07 | ||
| JP2013000592A JP6026891B2 (en) | 2012-03-09 | 2013-01-07 | Binder composition for mold making |
| PCT/JP2013/055505 WO2013133131A1 (en) | 2012-03-09 | 2013-02-28 | Binder composition for producing template, and method for producing template |
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| CN104105558A true CN104105558A (en) | 2014-10-15 |
| CN104105558B CN104105558B (en) | 2016-04-06 |
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| JP (1) | JP6026891B2 (en) |
| CN (1) | CN104105558B (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108717093A (en) * | 2018-04-26 | 2018-10-30 | 胡贝贞 | The ion chromatography of sucrose-tandem mass spectrum is combined detection method in tealeaves |
| CN109577009A (en) * | 2019-01-30 | 2019-04-05 | 山东科技大学 | One kind is for casting filter screen biomass organic material-inorganic sol composite coating, preparation method and application |
| CN111203271A (en) * | 2020-02-26 | 2020-05-29 | 南京林业大学 | Preparation method and application of cellulose supported catalyst |
| CN112512722A (en) * | 2018-08-24 | 2021-03-16 | 花王株式会社 | Binder composition for mold making |
| CN113573825A (en) * | 2019-03-08 | 2021-10-29 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Formaldehyde scavenger for binder systems |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6062715B2 (en) * | 2012-10-31 | 2017-01-18 | 花王株式会社 | Binder composition for mold making |
| JP6474322B2 (en) * | 2014-06-17 | 2019-02-27 | 花王株式会社 | Binder composition for mold making |
| CN106311960A (en) * | 2015-06-23 | 2017-01-11 | 姚伟 | Bonding agent and preparing method thereof |
| JP6971412B2 (en) * | 2018-10-03 | 2021-11-24 | 花王株式会社 | Blotting agent composition for molding |
| WO2021100838A1 (en) * | 2019-11-22 | 2021-05-27 | キンセイマテック株式会社 | Casting sand and kit for sand mold |
| WO2024117039A1 (en) * | 2022-11-29 | 2024-06-06 | 花王株式会社 | Binder composition for casting mold |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5691960A (en) * | 1979-12-25 | 1981-07-25 | Kinsei Kogyo Kk | Production of mold |
| US4439568A (en) * | 1981-11-06 | 1984-03-27 | The Quaker Oats Company | Fabrication of composite articles |
| US20080207796A1 (en) * | 2006-09-29 | 2008-08-28 | Clingerman Michael C | Furanic resin aggregate binders and method |
| CN102367242A (en) * | 2011-11-08 | 2012-03-07 | 河北师范大学 | Method for preparing 5-hydroxymethylfurfural from carbohydrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235034A (en) * | 1985-04-10 | 1986-10-20 | Kao Corp | Binder composition for casting mold |
| JPH04327336A (en) * | 1991-04-25 | 1992-11-16 | Kao Corp | Composition for manufacturing mold and refractory aggregate |
-
2013
- 2013-01-07 JP JP2013000592A patent/JP6026891B2/en active Active
- 2013-02-28 CN CN201380008936.2A patent/CN104105558B/en not_active Expired - Fee Related
- 2013-02-28 IN IN7035DEN2014 patent/IN2014DN07035A/en unknown
- 2013-02-28 WO PCT/JP2013/055505 patent/WO2013133131A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5691960A (en) * | 1979-12-25 | 1981-07-25 | Kinsei Kogyo Kk | Production of mold |
| US4439568A (en) * | 1981-11-06 | 1984-03-27 | The Quaker Oats Company | Fabrication of composite articles |
| US20080207796A1 (en) * | 2006-09-29 | 2008-08-28 | Clingerman Michael C | Furanic resin aggregate binders and method |
| CN102367242A (en) * | 2011-11-08 | 2012-03-07 | 河北师范大学 | Method for preparing 5-hydroxymethylfurfural from carbohydrate |
Non-Patent Citations (2)
| Title |
|---|
| 侯平然 等: "转化糖浆中5-羟甲基糠醛的形成", 《冷饮与速冻食品工业》 * |
| 冯红伟，扶雄: "紫外分光光度法测定糖蜜中5-羟甲基糠醛含量", 《食品工业科技》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108717093A (en) * | 2018-04-26 | 2018-10-30 | 胡贝贞 | The ion chromatography of sucrose-tandem mass spectrum is combined detection method in tealeaves |
| CN112512722A (en) * | 2018-08-24 | 2021-03-16 | 花王株式会社 | Binder composition for mold making |
| CN112512722B (en) * | 2018-08-24 | 2023-02-28 | 花王株式会社 | Binder composition for mold making |
| CN109577009A (en) * | 2019-01-30 | 2019-04-05 | 山东科技大学 | One kind is for casting filter screen biomass organic material-inorganic sol composite coating, preparation method and application |
| CN109577009B (en) * | 2019-01-30 | 2021-01-26 | 山东科技大学 | Biomass organic material-inorganic sol composite coating for casting filter screen, preparation method and application |
| CN113573825A (en) * | 2019-03-08 | 2021-10-29 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Formaldehyde scavenger for binder systems |
| CN111203271A (en) * | 2020-02-26 | 2020-05-29 | 南京林业大学 | Preparation method and application of cellulose supported catalyst |
| CN111203271B (en) * | 2020-02-26 | 2022-10-04 | 南京林业大学 | Preparation method and application of cellulose supported catalyst |
Also Published As
| Publication number | Publication date |
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| JP6026891B2 (en) | 2016-11-16 |
| IN2014DN07035A (en) | 2015-04-10 |
| WO2013133131A1 (en) | 2013-09-12 |
| JP2013212536A (en) | 2013-10-17 |
| CN104105558B (en) | 2016-04-06 |
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