CN1171991A - Binder composition for hardening carbon dioxide gas - Google Patents
Binder composition for hardening carbon dioxide gas Download PDFInfo
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- CN1171991A CN1171991A CN 97110004 CN97110004A CN1171991A CN 1171991 A CN1171991 A CN 1171991A CN 97110004 CN97110004 CN 97110004 CN 97110004 A CN97110004 A CN 97110004A CN 1171991 A CN1171991 A CN 1171991A
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Abstract
To provide a binder composition for gaseous carbon dioxide hardening obtaining the high mold strength and the stability of mold surface by constituting the composition. The composition of resin kit for the gaseous carbon dioxide hardening mold contains (a) 0.1-60wt.% parts of the epoxy compound, (b) 15-99.7wt. parts of alkali water soluble phenol resin water solution, (c) 0.1-20wt. parts of the hardening promoter and (d) 0.1-10wt.
Description
The invention relates to the binder composition for hardening carbon dioxide gas and the carbon dioxide hardening casting mold resin combination that use when making casting mold as curing agent with carbon dioxide.In addition, the invention relates to the mould composition that uses this adhesive composition or this resin combination to make, and the process for making molds that uses this adhesive composition or this casting mold to constitute with resin combination.Can make intensity and the high casting mold of mo(U)ld face stability according to the present invention.
So far, the binding agent as using when making casting mold uses various organic binder bonds.In recent years, the energy-conservation and viewpoint of making the protection of environment and earth environment when making from reaching casting mold is used the organic system binding agent that leans on low gas shape of toxicity or aerosol shape material to harden.Even in such a organic binder bond, the organic binder bond that also special focal attention can harden with security good carbon dioxide gas.
As an example that comprises with the composition of the organic binder bond of carbon dioxide gas physical efficiency sclerosis, open the composition that has disclosed the alkaline aqueous solution that comprises resol resin type phenolic resins and curing agent borate etc. in the flat 4-76947 communique the spy.
Carbon dioxide one works in such a composition, just hardens, and its reason is as follows.That is, the water in carbon dioxide and the said composition reacts, and generates carbonic acid.Because the pH of the effect said composition (being aqueous solution) of carbonic acid reduces.Its result, hardening accelerator and resol resin reactions such as borate make this resin crosslinks.But with the actual casting mold that manufactures of such composition, not talkative have enough intensity and a surface-stable degree, and such casting mold also can not meet the demands far away.
In addition, to improve mould strength is purpose, open to have disclosed in the flat 4-147743 communique the spy and use the casting mold that the alkalescent phenol resin aqueous solution constitutes or the manufacture method of core, open the composition that has disclosed the alkaline aqueous solution that comprises fusible type bis-phenol urea formaldehyde in the flat 5-320477 communique the spy.According to the invention that is disclosed in these communiques, see the effect that mould strength improves, but far can not reach the level that meets the demands.
On the other hand, open the spy that to have disclosed the water-soluble phenolic that makes alkalescence in advance in the flat 4-298591 communique be resole resin mixes formation room temperature vulcanizing type with the hydrophily epoxy resin oligomer adhesive composition.But if use this adhesive composition moulding, setting rate is minimum.Open to have disclosed in the flat 7-9073 communique the spy and be purpose, carry out the invention that result of study produces with the shortcoming of improving said composition.That is, the composition that use the binding agent contain fusible type water soluble phenol resin, contains the curing agent of compound with epoxy radicals and organic ester is made casting mold, opens existing description the among the flat 7-9073 the spy.According to this method,, can't meet the demands though improved the setting rate of casting mold.
The inventor furthers investigate in view of the variety of problems in the above-mentioned prior art.It found that, make casting mold by using the carbon dioxide hardening of forming by water soluble phenol resin, hardening accelerator, silane coupling agent and epoxide with adhesive composition, reach the casting mold setting rate of anti-practicality, and can make mould strength and the remarkable good casting mold of mo(U)ld face stability, and and then contain at least a compound of selecting in the group that the metallic element that is subordinated to periodic table 1B-8 family forms if use, then in the making molds that uses reclaimed sand, improve mould strength.The present invention finishes with regard to being based on above-mentioned cognition.
Promptly, first kind of form of the present invention is about binder composition for hardening carbon dioxide gas, it contains alkaline aqueous solution, (c) hardening accelerator of (a) epoxide, (h) water soluble phenol resin and (d) silane coupling agent, (a) and (b), (c) become subtotaling with (d) be 100 parts by weight, (a) composition is the 0.1-60 parts by weight, (b) composition is the 15-99.7 parts by weight, and (c) composition is the 0.1-20 parts by weight, and (d) composition is the 0.1-10 parts by weight.
Second kind of form of the present invention is about hardening carbon dioxide gas casting mold resin combination, it is by (I) composition that contains (a) epoxide and the alkaline aqueous solution that contains (b) water soluble phenol resin, (c) hardening accelerator and (d) (II) of silane coupling agent become to be grouped into, (I) composition and (II) composition be in mutually not contact condition, (a), (b), (c) and (d) total of composition is 100 parts by weight, (a) composition is the 0.1-60 parts by weight, and (b) composition is the 15-99.7 parts by weight, (c) composition is the 0.1-20 parts by weight, and (d) composition is the 0.1-10 parts by weight.
The third form of the present invention is the mould composition about the above-mentioned carbon dioxide hardening that contains 100 parts by weight fire resistance bulk materials and 0.1-10 parts by weight is made with the composition sclerosis of adhesive composition.
The 4th kind of form of the present invention is about mould composition, this mould composition is to use 100 parts by weight fire resistance bulk materials and above-mentioned binder composition for hardening carbon dioxide gas or hardening carbon dioxide gas casting mold resin combination, its (a) and (b), (c) and (d) total of composition be that the amount of 0.1-10 parts by weight is modulated into composition, with carbon dioxide the said composition sclerosis is manufactured.
The 5th kind of form of the present invention is about the making molds method, it is to add the above-mentioned binder composition for hardening carbon dioxide gas of 0.1-10 parts by weight and form composition in 100 parts by weight fire resistance bulk materials, mixing resultant composition, fill it in the casting mold model, in model, make above-mentioned composition sclerosis and constitute with 0.1-30 parts by weight carbon dioxide.
The 6th kind of form of the present invention is about the making molds method, it adds above-mentioned binder composition for hardening carbon dioxide gas or hardening carbon dioxide gas casting mold with resin combination (I) composition and (II) composition in 100 parts by weight fire resistance bulk materials, its (a) and (b), (c) and (d) total of composition be the amount of 0.1-10 parts by weight and form composition, mixing resultant composition, said composition is filled in the pouring mold type, in model, makes said composition sclerosis and constitute with 0.1-30 parts by weight carbon dioxide.
In the present invention, (a) alkaline aqueous solution of epoxide, (b) water soluble phenol resin, (c) hardening accelerator and (d) silane coupling agent can be in turn or be simultaneously mixing with casting mold sand, perhaps also can be modulated into the mixture of forming by at least two kinds in these in advance, mixing with casting mold sand again.But it is good using the carbon dioxide hardening casting mold resin combination of the present invention of two-liquid type.Promptly, in the alkaline aqueous solution of water soluble phenol resin, dissolve quantitative hardening accelerator and silane coupling agent respectively, be adjusted to (II) composition of said composition, (II) composition is added in the casting mold sand to good separately or with the form of mixtures that (I) and (II) become to be grouped into epoxide ((I) composition of said composition).This is because if add epoxide in advance in the alkaline aqueous solution of water soluble phenol resin, then phenolic resins and epoxide finish reaction.On the other hand, why adding hardening accelerator in advance for good in the alkaline aqueous solution of water soluble phenol resin, is because if there is hardening accelerator, then when carbon dioxide is absorbed by the aqueous solution of phenolic resins, because of the effect of hardening accelerator, instantaneously can form ionic resin.As hardening accelerator, exemplify the words of using borax to be illustrated, deduction is, when above-mentioned phenolic resins and borax contact with carbon dioxide in strong basicity, forms the macroion type resin from oxygen atom ions binding shape on the boron atom of the phenolic hydroxyl group of phenolic aldehyde village fat.
When the moulding of casting mold, use fire resistance bulk materials such as sand.The fire resistance bulk material is the greensand mold reclaimed sand of the bentonite that for example contains waterglass reclaimed sand, use as binding agent etc., and with under the situation from the reclaimed sand (comprising the occasion of organic ester hardening and the occasion of carbon dioxide hardening) of the composition lining sand of the water soluble phenol resin that uses as binding agent, in order to improve mould strength, it is good re-using (e) contain at least a element of selecting from the group that the 1B-8 family metallic element of periodic table is formed compound.It is desirable containing such a compound in adhesive composition of the present invention.In addition, casting mold of the present invention with resin combination in (e) composition both can be contained in (I) composition, can be contained in again in (II) composition, also can be contained among both, but preferably be contained in (II) composition.In the case, (II) composition for example forms the form of dispersion liquid or solution.
The invention relates to by the carbon dioxide hardening formed with the organic system water soluble phenol resin of carbon dioxide hardening with adhesive composition, carbon dioxide hardening casting mold with resin combination, with the mould composition and the process for making molds of carbon dioxide hardening.Use epoxide simultaneously with water soluble phenol resin in the present invention, and then as required, use contains at least a compound of selecting in the 1B-8 family metallic element that is subordinated to periodic table, thereby significantly improves setting rate, intensity and the surface-stable degree of casting mold.In the present invention,, improve the crosslink density of resin, solved above-mentioned problem with this by the interaction between water soluble phenol resin, epoxide and the hardening accelerator.Have again in the present invention, when use contains at least a compound of selecting from the 1B-8 family metallic element of periodic table, greensand mold reclaimed sand and waterglass reclaimed sand, perhaps on reclaimed sand surface, be attached with the alkali composition in the remnant, utilize the compound that contains such metallic element to carry out modification from the casting mold that uses water soluble phenol resin to manufacture.Therefore reach the intensity of casting mold and the raising of surface-stable degree.In addition, in the present invention, as curing agent carbon dioxide safe to use, so can improve operating environment.
Explain the present invention below.
(a) explanation of epoxide
As the typical example of the epoxide (compound) that uses in the present invention, can enumerate the D-sorbite polyglycidyl ether with epoxy radicals, the sorbitan polyglycidyl ether, the polyglycereol polyglycidyl ether, triglycidyl group trihydrocyanic acid ester, the trimethylolpropane polyglycidyl ether, the glycerine polyglycidyl ether, the diglycerol polyglycidyl ether, the pentaerythrite polyglycidyl ether, the dihydroxy methylpropane polyglycidyl ether, the neopentyl diglycidyl ether, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, the polypropylene glycol glycidol ether, phenol ring oxidative ethane episome glycidol ether, lauryl alcohol oxirane episome glycidol ether, C
1-C
18Alcohol glycidol ether, adipic acid diglycidyl ether, phthalic acid diglycidyl ether.
In the present invention, contain the hardening accelerators such as borax of specified rate, use the carbon dioxide hardening of forming by the alkaline aqueous solution and the epoxide of water soluble phenol resin to carry out making molds with adhesive composition.By the existence of this three (hardening accelerator, phenolic resins and epoxy resin), the intensity and the surface-stable degree of the setting rate when improving the casting mold manufacturing, the casting mold that is shaped to.Its reason is as follows.Promptly, because epoxide is water miscible, in the alkaline aqueous solution of water soluble phenol resin, dissolve with molecular level, and in the presence of hardening accelerators such as borax, then by the contacting of carbon dioxide and adhesive composition, glycidyl ether, phenolic aldehyde hydroxyl and boron atom should mutually combine.Therefore, epoxide can be that a glycidyl ether is only arranged, but has more than two better.This be because, glycidyl ether is many more, the crosslink density of resin increases more, forms the better polymer architecture of rigidity.
In epoxide,, can enumerate phenol ring oxidative ethane episome glycidol ether, lauryl alcohol oxirane episome glycidol ether, C as example with a glycidyl ether
1-C1
8Alcohol glycidol ether, allyl glycidyl ether, 2-ethylhexyl glycidol ether, phenyl glycidyl ether, glycerine glycidol ether and propylene glycidol ether.
In epoxide, as example, can enumerate the D-sorbite diglycidyl ether with two glycidyl ethers, the sorbitan diglycidyl ether, the polyglycereol diglycidyl ether, the trimethylolpropane diglycidyl ether, glycerin diglycidyl ether, two glycerin diglycidyl ethers, the pentaerythrite diglycidyl ether, the trimethylolpropane diglycidyl ether, the neopentyl diglycidyl ether, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol-S diglycidyl ether, the terephthalic acid (TPA) diglycidyl ether, the quinhydrones diglycidyl ether, 2-glycidyl phthalic acid acid amides, dibromobenzene diglycidyl ether and dibromoneopentyl glycol diglycidyl ether.
In epoxide, as example, can enumerate D-sorbite polyglycidyl ether, sorbitan polyglycidyl ether, polyglycereol polyglycidyl ether, trimethylolpropane polyglycidyl ether, glycerine polyglycidyl ether, T 55, two glycerine polyglycidyl ethers, pentaerythrite polyglycidyl ether, three-glycidyl three (2-ethoxy) isocyanates, novolaks phenol polyglycidyl ether and metacresol phenol novolaks polyglycidyl ether with three above glycidyl ethers.
From setting rate, mould strength after 24 hours and the viewpoint of mo(U)ld face stability, in these epoxides, preferably show the water-soluble rate more than 20%.
Water-soluble rate (% represents with volume) at this said epoxide defines as described below.That is, at 25 ℃, in 90 volume parts water, add 10 volume parts epoxides, the mixture of vibration gained.Then, leave standstill this mixture, measure the volume of the epoxide that is not dissolved in water.Calculate the volume that is dissolved in the epoxide the water from its value, calculate the ratio (percentage) of the volume that is dissolved in the epoxide in the water and the volume of originally epoxide subsequently.
(a) use amount of epoxide as 100 parts by weight, is in the scope of 0.1-60 parts by weight, preferably in the scope of 1-30 parts by weight with the total of (a)-(d) composition.
In addition, when using the high epoxide of viscosity, can dilute, perhaps also can use and the epoxide more than two kinds that its viscosity is irrelevant with the low epoxide of other viscosity.
Other for example also can be with gylcol ether and epoxide and usefulness such as carbitol, diethylene glycol-butyl ether, polyethylene glycol, polyethylene glycol-alkyl ethers.
The epoxide of Shi Yonging also can be rough (thick) epoxide that contains halogens such as chlorine element in the present invention.In general epoxide synthetic, in the presence of lewis acid catalyst, adduction chloropropylene oxide in polyalcohols such as glycerine etc. is followed, and makes in the compound of gained and the equimolar alkaline reaction of chloropropylene oxide.At this moment, secondary salt and the water of generating.These accessory substances also can be mixed in the epoxide of key reaction product, and would be better about the chlorine element is mixed in the epoxide to good.Allow the existence of chlorine element, self-evident is useful economically, but in the present invention, moreover, and owing to there is the chlorine element in adhesive composition, also is of value to the raising mould strength.The amount of chlorine element as benchmark, better is 0.01-30% (weight) with the amount of the epoxide that comprises impurity such as chlorine element, preferably 0.1-20% (weight).But,, be not particularly limited about the secondary living salt that in the epoxide that is reaction product, is mixed in and the amount of secondary unboiled water.
(b) explanation of the alkaline aqueous solution of water soluble phenol resin
The alkaline aqueous solution of the so-called water soluble phenol resin that uses in the present invention, be instigate from phenol and bisphenols, select at least a and from aldehydes, select at least a, in water, in the presence of a large amount of alkaline matters, react and obtain the alkaline aqueous solution of resol resin.
As example, can enumerate phenol, cresols, resorcinol etc., and, can enumerate bisphenol-A, Bisphenol F, bisphenol S, bisphenol Z etc. as the example of bisphenols in this said phenol.In addition, as the example of aldehydes, can enumerate twain-aldehyde compounds such as formaldehyde, acetaldehyde, furfural, glyoxal, glutaraldehyde, terephthalic acid (TPA) dialdehyde.When the phenolic resins among synthetic the present invention, as raw material phenol, can use a kind of phenol or bis-phenol, perhaps also can use at least two kinds that from the group of phenol and bisphenols composition, select.Under given condition, phenols and aldehydes are reacted, just obtain the alkaline aqueous solution of given water soluble phenol resin.
As the water soluble phenol resin that uses in adhesive composition and carbon dioxide hardening casting mold at carbon dioxide hardening of the present invention, use bisphenols for well as its raw material with resin combination.That is, the bisphenols formaldehyde resin, and the cocondensation resin of being made up of phenol bisphenols and aldehydes is good.Its reason is that the phenol raw material uses the bisphenols formaldehyde resin to reach the cocondensation resin of being made up of phenol bisphenols and aldehydes, and is higher than the mould strength of the phenolic resins that only uses phenols.When synthetic such a cocondensation resin, with respect to phenol, better be to use the bisphenols of 0.05-99.5 times of molar range, preferably use the bisphenols of 0.1-0.9 times of molar range.In addition, as the water soluble phenol resin that uses in resin combination with adhesive composition and carbon dioxide hardening casting mold at carbon dioxide hardening of the present invention, its raw material preferably uses the phenols more than two kinds.
Water soluble phenol resin among the present invention, also can use phenols (comprising bisphenols) and aldehydes and add urea, melamine, cyclohexanone etc. can with the compound (monomer) of aldehydes reaction as raw material, make them carry out the cocondensation polymerization and form.Perhaps also can in (b) of the present invention composition, contain urea, melamine, cyclohexanone etc.Equally,, when relevant water soluble phenol resin of the present invention is synthetic, also can carry out cocondensation, perhaps be contained in (b) composition as monohydric alcohol compounds such as the methyl alcohol of aliphatic alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, butanols.And then the polyacrylate of water soluble polymer, cellulose derivative, polyvinyl alcohol, lignin derivative etc. also can react when above-mentioned phenolic resins synthetic, perhaps add in (b) composition.Among them, the cocondensation resin of phenol bisphenol-A cresols isopropyl alcohol formaldehyde is desirable especially.
The alkaline aqueous solution of water soluble phenol resin, can utilize conventional method, make from the group that phenol and bisphenols are formed, select at least a (below be called phenol system compound) with from aldehydes, select at least a, in the presence of alkali metal hydroxide, in water system, react and obtain.At this moment, the use amount of alkali metal hydroxide with respect to phenol system compound, is doubly mole of 0.7-5.0, preferably 1.0-4.0 times of mole.When the amount of alkali metal hydroxide was very few, gained phenolic resins setting rate was little, and did not show sufficient mould strength after the sclerosis.On the other hand, when the amount of alkali metal hydroxide was too much, the alkalescence of gained phenolic resin aqueous solution was strong excessively, was undesirable in safety work.As the example of the suitable alkaline matter that uses when the manufacturing of the alkaline aqueous solution of water soluble phenol resin, can enumerate NaOH, potassium hydroxide, lithium hydroxide and the mixture more than two kinds in them, wherein, potassium hydroxide preferably.
When water soluble phenol resin synthetic, the consumption of aldehydes is doubly mole, preferably 1.1-5.5 times of molar range of 1.0-6.0 with respect to phenol system compound.If aldehydes is few, with the compatibility variation of the hardening accelerator [(C) composition] of (b) composition of gained, on the other hand, if too much, (b) to contain quantitative change many for the unreacted aldehyde of composition.
Under the situation of using the monohydric alcohol compound, with respect to phenol system compound, with 0.0001-0.5 times of mole, better with the use of the amount in 0.01-0.2 times of molar range monohydric alcohol compound.Its consumption by adding the effect that the monohydric alcohol compound produces, on the contrary, if surpass 0.5 times of mole, does not have the tendency that can not fully improve mould strength during less than 0.0001 times of mole.
As (b) composition that uses among the present invention, it better is 20-80% (weight) that its solid formation divides, and it is 40-70% (weight) that preferably solid formation divides.If the solid formation branch of use, then produces the tendency that the intensity of gained casting mold reduces less than (b) composition of 20% (weight).On the contrary, divide (b) composition that surpasses 80% (weight) Gu form, the viscosity height, therefore the viscosity of adhesive composition of the present invention also uprises.The sand composition of forming with such adhesive composition with by casting mold sand is mixing, and it is difficult reaching homogeneous, easily produces mixing irregular.Producing under the mixing irregular situation, the gained mould strength is not enough.
(b) the solid formation of composition divides one of assay method for example to descend.At first, on shell, gather the about 2g of (b) composition, measure its weight exactly with Libra.Then, be with dry 3 hours of (b) composition in 105 ℃ the drying machine at baking temperature.Mensuration remains in the weight that the solid formation on the shell divides.Calculate the percentage of the preceding weight of dried weight relatively dry, divide (weight %) as solid formation with this.
Carbon dioxide hardening in total 100 parts by weight of (a)-(d) composition, better is the 15-99.7 parts by weight with (b) components in proportions in the adhesive composition, preferably the 30-80 parts by weight.When (b) components in proportions was less than 15 parts by weight or above 99.7 parts by weight, with the casting mold that such adhesive composition is shaped to, intensity significantly reduced.
(c) explanation of hardening accelerator
In the present invention, it is good using boron compound as hardening accelerator.In addition, boron compound also can also be used with hardening accelerator in addition.
As the example of boron compound, can enumerate boric acid (in the alkaline aqueous solution of water soluble phenol resin, forming borate), reach borate families such as sodium tetraborate (borax), potassium borate+hydrate, kodalk, potassium pentaborate, sodium pentaborate.
The use amount of such hardening accelerator in total 100 parts by weight of (a)-(d) composition, is the scope of 0.1-20 parts by weight, preferably the scope of 3-10 parts by weight.The use amount of hardening accelerator is during less than 0.1 parts by weight, the setting rate and the intensity of casting mold are insufficient, on the other hand, if surpass 20 parts by weight, then influence the proterties of the alkaline aqueous solution of water soluble phenol resin, usually, the mixture viscosity of the water soluble phenol resin aqueous solution and hardening accelerator uprises, or hardening accelerator is observed and is produced sedimentary tendency the dissolubility deterioration of the water soluble phenol resin aqueous solution.
Except that boron compound, can enumerate aluminate, stannate and titanate as the example of hardening accelerator use.So-called aluminate is the salt that is generated by aluminium oxide and metal hydroxides, as its object lesson, can enumerate sodium aluminate, potassium aluminate and lithium aluminate.In addition, so-called stannate is the salt that is generated by tin oxide and metal hydroxides, as its object lesson, can enumerate sodium stannate and potassium stannate.In addition, so-called titanate is the salt that is generated by titanium oxide and metal hydroxides, as its object lesson, can enumerate sodium titanate and potassium titanate.
As hardening accelerator, can only use a kind of in the above-claimed cpd, also can use the mixture more than two kinds in them.But, preferably only use boron compound, perhaps boron compound uses with the hardening accelerator beyond the boron compound that exemplifies above.In addition, hardening accelerator beyond the hardening accelerator that exemplifies above and the hardening accelerator that exemplifies above also can use together.
(d) explanation of silane coupling agent
Carbon dioxide hardening of the present invention contains silane coupling agent with adhesive composition.As its desirable concrete example, can enumerate gamma-aminopropyl-triethoxy-silane, γ-(2-aminoethyl) aminopropyl trimethoxysilane and γ-glycidoxypropyl trimethoxy silane.The consumption of silane coupling agent is the 0.1-10 parts by weight in total 100 parts by weight of (a)-(d) composition, preferably in the scope of 0.1-3 parts by weight.The amount of silane coupling agent is during less than 0.1 parts by weight, and mould strength is low, and when surpassing 10 parts by weight, the tendency that has setting rate to reduce.
(e) contain the explanation of the compound of periodic table 1B-8 family metallic element
As the metallic element example that comprises in the compound that contains periodic table 1B-8 family metallic element that uses in the present invention, can enumerate Cu, Ag in the 1B family, Mg in 2 families, Ca, Sr, Ba, Zn, Cd, Sc in 3 families, Y, Al, Ga, In, Tl, Ti in 4 families, Zr, Hf, Sn, Pb, the V in 5 families, Nb, Ta, Bi, the Cr in 6 families, Mo, W, Po, Mn in 7 families, Tc, Re, the Fe in 8 families, Co, Ni.Among these, the metallic element that belongs to family of 2 families-4 and 8 families is for well.
In for the compound that contains such metallic element of the present invention, the various forms such as oxide, hydroxide, inorganic acid salt, acylate and complex that metal powder and metal are arranged, in the present invention, no matter such a compound is which kind of form can be used.Such metallic element so long as finally be included in the mould composition gets final product, and is not contained any restriction of the compound form of metallic element.Enumerate the object lesson of the compound that contains such metallic element below, but (e) of the present invention composition is not limited to these concrete examples.
When (e) form of composition is metal powder, example as the metallic element that belongs to periodic table 1B-8 family that constitutes metal powder, can enumerate Cu, Ag, Mg, Ca in 2 families, Sr, Ba, Zn, Cd etc. in the 1B family, Al in 3 families, Sc, Ga etc., Ti in 4 families, Zr, Sn etc., the Sb in 5 families, Bi etc., the Cr in 6 families, Mo etc., Mn in 7 families, Tc etc., the Fe in 8 families, Co, Ni etc.The B of so-called metalloid, Si, As, Te etc. are unfavorable.In addition, when (e) form of composition is alloyed powder,, can enumerate duralumin, magnalium, ferromanganese etc. as the alloy example of alloyed powder.Have again, in the compound that contains the metallic element that belongs to periodic table 1B-8 family, except that metal powder and alloyed powder,, can enumerate salt, double salt, hydroxide, the oxide of metal as the typical example of compound; Alkyl such as alkyl, aryl is combined in the organo-metallic compound that metallic atom constitutes above; The nitride of metal, alkoxide, hydride, carbide, peroxide, sulfide, phosphide, nitration thing, anilid, phenates, six amides; The metal acid imide; Ferrocene and similar compound thereof; Dibenzene-chromium and similar compound thereof; Inorganic heteropolymer; Metal carbonyl; Metalloenzyme; Inclusion compound; The metal-complexing thing; Chelate; And coordination high polymer.
In the compound that contains the metallic element that belongs to periodic table 1B-8 family, if use the compound of representing with following formula (1), just can seek service life, i.e. the raising of the prolongation of the possible time of making molds and mould strength is gratifying.
In MaXb (1) formula, each integer more than 1 naturally of a and b, M is the metallic element that belongs to periodic table 1B-8 family, and X represents anion atoms group, the organic acid anion atoms group of hydrogen atom, carbon atom, alkyl, sulphur atom, nitrogen-atoms, phosphorus atoms, oxygen atom, halogen atom, hydroxyl, alkoxyl, amino, imino group, nitro, inorganic acid or shows the atomic group of metal ion blockade property.But it is a kind of that M and X are not limited to separately.
Example as M, same as described above, can enumerate Cu, Ag in the 1B family, Mg in 2 families, Ca, Sr, Ba, Zn, Cd etc., the Al in 3 families, Sc, Ga etc., the Ti in 4 families, Zr, Sn etc., Sb in 5 families, Bi etc., Cr in 6 families, Mo etc., the Mn in 7 families, Tc etc., the Fe in 8 families, Co, Ni etc.The B of so-called metalloid, Si, As, Te etc. are unfavorable.
As X is the concrete example of the compound of hydrogen atom, can enumerate AlH
3, CaH
2And BaH
2
As X is the concrete example of the compound of carbon atom, can enumerate Al
4C
3And CaC
2
As X is the compound example of alkyl such as alkyl, aryl, can enumerate the organo-metallic compound that alkyl is combined on the metallic atom and constitute, and can enumerate Al (CH more specifically
3)
3, Al (C
2H
5)
3, Al (C
6H
5)
3, (C
2H
5)
2AlI, (C
2H
5)
2AlH, (C
2H
5)
2AlCN, Al (i-C
4H
9)
3, (CH
2=CH)
3Al, Zn (C
6H
5)
2, (CH
2=CH)
2, Zn and Ca (C
2H
5)
2R-Mg-X Grignard reagents such as (in the formula, R represent alkyl or aryl, and X represents halogen atom); Ferrocene (Fe (C
5H
5)
2), Zn (C
5H
5)
2, Ni (C
5H
5)
2, Mn (C
5H
5)
2And V (C
5H
5)
2Deng ferrocene and similar compound thereof; Cr (C
6H
6)
2, Mo (C
6H
6)
2And V (C
6H
6)
2Deng dibenzene-chromium and similar compound thereof; And phenates classes such as Al-phenates, Zn-phenates and Ca-phenates.
As X is the concrete example of the compound of sulphur atom, can enumerate ZnS, Cu
2S and CuS.
As X is the concrete example of the compound of nitrogen-atoms.Can enumerate the aluminium nitride that contains the Al-N key.
As X is the concrete example of the compound of phosphorus atoms, can enumerate AlP.
As X is the concrete example of the compound of oxygen atom, can enumerate oxides such as magnesia, calcium oxide, barium monoxide, zinc oxide, aluminium oxide.
And then, the complex chemical compound that constitutes by the combination more than two kinds in these oxides, the complex chemical compound that is made of the oxide of above-mentioned oxide and other elements or salt combination also is fit to use in the present invention.
The typical example that is such complex chemical compound, uses in the present invention is as follows.
At first be the cement class, can enumerate hydraulic lime, Roman cement, Parker's cement, Portland cement, alumine cement, blast-furnace cement, silica cement, pulverized fuel ash cement, masonry cement, dilatancy cement and special cement as its example; The blast furnace slag class can be enumerated blast furnace slag, magnesium refining slag, ferrochrome slag as its example; Bentonite and mullite synthesizing etc.Chemical constitution as the representative of main complex chemical compound among these is mCaOnSiO
2, mCaOnAl
2O
3, mBaOnAl
2O
3, CaOmAl
2O
3NSiO
2, CaOmMgOnSiO
2, mCaCO
3NMgCO
3, mCaOnFeO
31CaOmAl
2O
3NFe
2O
3And mAl
2O
3NSiO
2(in these chemical constitutions, l, m, n are respectively the integers more than 0 or 1.)。
Example as other complex chemical compounds has zeolite, square fluorite, the such aluminosilicate of long fluorite, and phyllosilicate such as mica.
X is in the compound of oxygen atom, can enumerate CaO as the example of peroxide
2, BaO
2And BaO
4
As X is the concrete example of the compound of halogen atom, can enumerate calcium chloride, magnesium chloride, barium chloride, copper chloride, zinc chloride, calcium bromide, aluminum fluoride, palladium bichloride, molybdenum chloride, manganese chloride, iron chloride and nickel chloride.
As X is the concrete example of the compound of hydroxy, can enumerate aluminium hydroxide, calcium hydroxide, magnesium hydroxide and zinc hydroxide.
As X is the concrete example of the compound of alkoxyl, can enumerate Al[OCH (CH
3)
2]
3And Zn (OCH
3)
2
As X is the concrete example of the compound of amino, can enumerate Ca (NH
2)
2And Al (NHPh)
3
As X is the concrete example of the compound of nitro, can enumerate CuNO
2
Be the concrete example of compound of the anion atoms group of inorganic acid as X, can enumerate SO
4, SO
3, S
2O
3, S
2O
6, SiF
6, MoO
4, MnO
4, NO
3, NO
2, ClO
3, ClO, CO
3, HCO
3, CrO
4, IO
3, PO
3, PO
4, HPO
3, HPO
4, H
2PO
4, P
2O
7, H
2PO
2, SiO
3, BO
2, BO
3, B
4O
7And Fe (CN)
6
As X is the concrete example of the compound of organic acid anion atoms group, can enumerate anion of carboxylic acid atomic groups such as formic acid, acetate, oxalic acid, tartaric acid, benzoic acid, the anion atoms group of organic sulfonic acids such as sulfamic acid, xylene monosulfonic acid, toluenesulfonic acid, phenolsulfonic acid, benzene sulfonic acid, alkyl benzene sulphonate, and the anion atoms group of organic phosphoric acid such as methyl acid phosphate, ethyl phosphonic acid.
As X is to show that metal ion blocks the object lesson of compound of the atomic group of property, can enumerate following compound.
At acetate is among the representative of aminocarboxylic acid type, comprise that X in the formula (1) is respectively ethylenediamine tetra-acetic acid (EDTA) or its salt, NTA (NTA) or its salt, anti-form-1, the compound of 2-1,2-diaminocyclohexane tetraacetic acid (CyDTA) or its salt, diethylenetriamine pentaacetic acid (DTPA) or its salt, teiethylene tetramine-hexacetic acid (TTHA) or its salt, glycoletherdiaminotetraacetic acid (GEDTA) or its salt, iminodiacetic acid (IDA) or its salt, polyalkylene ethylenediamine tetraacetic acid (EDTA) or its salt or N-hydroxyl alkylideneimino oxalic acid or its salt; At phenyl is among the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively 2-hydroxyphenyl iminodiacetic acid or its salt, phenylimino oxalic acid or its salt, 2-acrinyl iminodiacetic acid or its salt, benzyl iminodiacetic acid or its salt or N, the compound of N '-ethylenebis [2-salicyl)] amion acetic acid or salt; In the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively the compound of β-mercapto ethyl iminodiacetic acid or its salt with sulfydryl; In the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively the compound of ether diamine tetrem phenol or its salt with ehter bond; In the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively the compound of ethyl thioether ethylenediamine tetraacetic acid (EDTA) or its salt with thioether bond; In representative, comprise that the X in the formula (1) is respectively β-aminoethane sulfonic acid-N, the compound of N-oxalic acid or its salt with sulfonic aminocarboxylic acid type; In the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively the compound of nitrilo-oxalic acid-methylene phosphonic acid or its salt with phosphonate group; In the representative of aminocarboxylic acid type, comprise that the X in the formula (1) is respectively N, N '-two glycyl ethylene diamine-N ', N with peptide bond ", N , the compound of N " "-tetraacethyl or its salt; In the representative of hydroxycarboxylic acid type, comprise that the X in the formula (1) is respectively the compound of gluconic acid or its salt, citric acid or its salt or tartaric acid or its salt, also have, in the representative of phosphatic type, comprise that the X in the formula (1) is respectively the compound of tripolyphosphate or its salt, hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) or its salt or nitrilo-triphenylethylene phosphonic acids (NTP) or its salt; As other example, the X that can enumerate in the formula (1) is the compound of acetylacetone,2,4-pentanedione.
In addition, compound with formula (1) expression, go up at metallic element (M) under the situation of coordination high polymer (X), example as the coordination high polymer that on X, has suitable metal ion blockade energy, can enumerate in its molecule, have at least a macromolecule of from the group that amino, as to contain nitrogen-atoms heterocyclic moiety, schiff bases base section, alcohol moiety, carboxylic moiety, ketone part, ester moiety, amido link, amino carboxylic acid part, phosphonic acids part, phosphine part and sulfydryl are formed, selecting.
When the X in the formula (1) is inclusion compound, example as such inclusion compound, can enumerate cyclic polyether (crown ether), cyclic polyamines (azepine crown compound), the poly-thiophene ether (thiophene crown compound) of ring-type, compound donor crown compound, hetero ring type crown compound (cryptand), macromolecule crown compound, ring-type phenol (カ Network ス ア レ-Application) and cyclodextrine derivatives, as the concrete example of the compound of representing with (1), can enumerate dibenzo-18-crown-6 (DB18C6) and Ca
2+The coordination thing, and cryptate [222] and Ca
2+The coordination thing.
Other, Ni (CO)
4, Mn
2(CO)
10Deng metalloenzyme such as metal carbonyl, carboxypeptidase A, thermolysin and zirconium aluminium based compound also is (e) of the present invention composition.
As other examples that contain the compound that belongs to periodic table 1B-8 family metallic element, can enumerate aluminic acid compound, aluminic acid compound, titanic acid compound and zirconic acid compound.As the concrete example of aluminic acid compound, can enumerate magnesium aluminate, sodium aluminate, potassium aluminate and lithium aluminate; As the concrete example of stannic acid compound, can enumerate sodium stannate, potassium stannate and lithium stannate; As the concrete example of titanic acid compound, can enumerate lithium titanate, sodium titanate, potassium titanate and barium titanate; As the concrete example of zirconic acid compound, can enumerate lithium zirconate, sodium zirconate and potassium zirconium.
In above-mentioned (e) composition, AlCl
3, Al
2O
3Powder, aluctyl, Al (O-iPr)
3, the compound that contains aluminium such as aluminium acetate, alumine cement, aluminum phosphate, aluminum phenoxide is desirable, the acylate of aluminium is desirable especially.
By the boride one in (e) composition and above-mentioned (c) hardening accelerator is worked, can improve service life, i.e. the pot life of making molds.
In the present invention, (e) use amount of composition is not particularly limited, but per 100 parts by weight of total of above-mentioned (a)-(d) composition, is converted into the amount of metallic element, better is the 0.0005-5 parts by weight, preferably the 0.001-3 parts by weight.When (e) use amount of composition is very few, increase the service life, promptly the effect of the pot life of making molds is little.On the other hand, even use (e) composition that surpasses 5 parts by weight, its effect reaches capacity, can not desired effects improve, and be uneconomic.
Moreover (e) composition can be added in the casting model powder in advance, perhaps also might as well be dissolved in (b) composition.
When (e) composition used with the form of metal dust, particularly when this metal dust directly added in the casting model powder, the size of metal dust was to the big influence of its reactive generation.That is, the reactivity of metal dust becomes function with the particles of powder size.Therefore, it is good using thin as far as possible powder, usually, uses the following powder of its average grain diameter 10000 μ m, preferably uses the following powder of 2000 μ m.
The carbon dioxide hardening explanation of adhesive composition
Carbon dioxide hardening adhesive composition of the present invention is the adhesive composition that contains above-mentioned (a)-(d) composition with above-mentioned ratio.This adhesive composition can also contain above-mentioned (e) composition.In addition, only otherwise influence effect of the present invention, this adhesive composition can also contain other compositions.As the example of other such compositions, can enumerate gylcol ethers such as glycol-ether, carbitol, triethylene glycol ethers.
The explanation of resin combination of carbon dioxide hardening casting mold.
Carbon dioxide hardening casting mold resin combination of the present invention.By (I) composition that contains (a) epoxide and the alkaline aqueous solution that contains (b) water soluble phenol resin, (c) hardening accelerator and (d) (II) of silane coupling agent become to be grouped into, (I) composition is in mutual non-contact state mutually with (II) composition, (a) and (b), (c) and (d) total of composition be 100 parts by weight, (a) composition is the 0.1-60 parts by weight, (b) composition is the 15-99.7 parts by weight, (c) composition is the 0.1-20 parts by weight, and (d) composition is the 0.1-10 parts by weight.(I) composition and/or (II) composition also can contain above-mentioned (e) composition.In addition, only otherwise influence effect of the present invention, (I) composition and/or (II) composition also can contain other compositions.
As an example of the concrete form of resin combination of the present invention, can enumerate (I) composition and (II) composition packing respectively separately, in its container (for example case) of packing into.In the case, (I) subpackage of composition and (II) subpackage of composition can respectively pack into one, also can respectively pack into two the bag more than.When the latter, (I) each of the subpackage of composition (perhaps (II) composition) can form independently (for example, forming each one bag), also can link together, but can be the form of cutting off (for example, contain the wire eyelet, or form) in use as the spiral cut-out.
The explanation of mould composition
A kind of form of mould composition of the present invention is to make with carbon dioxide to contain 100 parts by weight fire resistance bulk materials and 0.1-10 parts by weight, the composition sclerosis of the binder composition for hardening carbon dioxide gas of the present invention that best 1-5 parts by weight are above-mentioned.In addition, other forms of mould composition of the present invention are with 100 parts by weight fire resistance bulk materials, above-mentioned binder composition for hardening carbon dioxide gas of the present invention or hardening carbon dioxide gas casting mold resin combination, the amount that adds up to the 0.1-10 parts by weight, is preferably the 1-5 parts by weight with (a)-(d) composition is used, the modulation group compound makes the said composition sclerosis with carbon dioxide.
The kind of the fire resistance bulk material that in making molds, uses, import silica sand, homemade silica sand, aluminum oxide sand, zircon sand, chromite sand, mullite synthesizing sand (ceramic hollow bead), olivine ore in sand form, metal dust, metal oxide powder arranged, contain bentonitic greensand mold reclaimed sand, contain the waterglass reclaimed sand of sodium metasilicate, from alkalescent phenol resin lining, i.e. the reclaimed sand of the casting mold made from alkalescent phenol resin etc.In the present invention, these can both use as the fire resistance bulk material.In addition, in the present invention, their granularity and size distribution etc. are not particularly limited.
When modulation mould composition of the present invention, usually in the fire resistance bulk material, add carbon dioxide hardening of the present invention with adhesive composition or carbon dioxide hardening casting mold with (I) composition of resin combination and (II) composition, form composition, said composition is mixing, then make composition (for example mixing sand) sclerosis after mixing.Carbon dioxide hardening is with (I) composition and (II) interpolation of composition with resin combination of adhesive composition or carbon dioxide hardening casting mold, and the mixing of the composition that becomes to be grouped into of fire resistance bulk material and interpolation like this often carried out simultaneously.In the present invention, in the fire resistance bulk material, add the composition that comprises above-mentioned (a)-(d) composition, perhaps add (I) composition that comprises (a) composition and (II) composition that comprises (b)-(d) composition respectively.Moreover, though efficient is weaker, also can when the mixing sand of modulation, (a)-(d) composition be added in the fire resistance bulk material respectively individually.
In addition, when the mixing sand of modulation, as being the purpose additive, even use gylcol ethers such as glycol-ether, carbitol, triethylene glycol ethers also harmless to improve mould strength.
The explanation of making molds method
A kind of mode of making molds method of the present invention is, in 100 parts by weight fire resistance bulk materials, add the carbon dioxide hardening adhesive composition of the invention described above of 0.1-10 parts by weight, best 1-5 parts by weight, form composition, the composition of gained is mixing, composition is filled in the pouring mold type, in model, use the curing agent carbon dioxide of 0.1-30 parts by weight, best 0.2-12 parts by weight, make the composition sclerosis.In addition, the another way of making molds method of the present invention is, in 100 parts by weight fire resistance bulk materials, add above-mentioned carbon dioxide hardening of the present invention with adhesive composition or carbon dioxide hardening casting mold with (I) composition of resin combination and (II) composition, add up to the 0.1-10 parts by weight with its (a)-(d) composition, preferably the amount of 1-5 parts by weight is added, form composition, the composition of gained is mixing, be filled into then in the pouring mold type, in model with the 0.1-30 parts by weight, preferably curing agent-the carbon dioxide of 0.2-12 parts by weight makes the composition sclerosis.Make carbon dioxide by being in the casting mold composition in the model, thereby make sclerosis such as phenolic resins.
When implementing making molds method of the present invention, usually, in the fire resistance bulk material, add carbon dioxide hardening of the present invention with adhesive composition or carbon dioxide hardening casting mold with (I) composition of resin combination and (II) composition, form composition, said composition is mixing.Carbon dioxide hardening often carries out with the mixing of the composition that becomes to be grouped into of adding like this with (I) composition of resin combination and the interpolation and the fire resistance bulk material of (II) composition simultaneously with adhesive composition or carbon dioxide hardening casting mold.In the present invention, in the fire resistance bulk material, add the composition that contains (a)-(d) composition, perhaps add (I) composition that contains (a) composition respectively, contain (II) composition of (b)-(d) composition.Moreover, though less efficient also can be distinguished in the fire resistance bulk material and add (a)-(d) composition separately.
Making molds method of the present invention is for example pressed decompression moldings such as molding applicable to VRH molding (VacuumReplace Hardening Process), suction, and its applicable object does not limit especially.In molding of the present invention, be supply method and the also especially qualifications such as flow, its ventilation temperature of sclerosis with atmospheric carbon dioxide.In addition, use gas as sclerosis, can use the gas that forms with air and nitrogen dilution carbon dioxide, at this moment, the dilution rate of carbon dioxide etc. is not done special restriction.The dilution that uses such carbon dioxide can efficient well also be ventilated as sclerosis gas.
Followingly illustrate in greater detail the present invention with reference to embodiment and comparative example.But the present invention is not limited in these embodiment.
The determination method of compression strength
The compression strength of the diameter 50mm of moulding, high 50mm sample (casting mold) in following embodiment and comparative example, " test method of casting model powder (the JIS Z-2601-1993) " that define according to Japanese Standards Association (JIS) measures.Measurement result is with W/A (kgf/cm
2) expression.(unit: kgf), A represents the sectional area (unit: cm of sample in loading when W represents sample destruction
2).
The determination method of mo(U)ld face stability
The surface-stable degree of the diameter 50mm of moulding, high 50mm sample (casting mold) in following examples and comparative example is measured according to " the surface-stable degree test method(s) that machine casting mold is arranged " put down in writing in the test method that machine casting mold is arranged in the contact meeting report book (1) of many kinds produced in small quantities type high efficiency foundry engieering contact meeting evaluation assessment working group (working group).Specifically, by the following stated mensuration: measuring the weight of said sample, then, is to vibrate 2 minutes on the 10 purpose sieves it at width of mesh, then, measures the sample weight after vibrating.Calculate the ratio (weight percent) of the sample weight before sample weight and the vibration after the vibration.Its value is high more, means that the surface-stable degree is high more.3% difference of mo(U)ld face stability, being illustrated in has tangible difference on the performance, i.e. and expression has marked difference.
The determination method of the water-soluble rate of epoxide
In the glass tube that has scale (diameter 25mm, high 250mm) of capacity 100CC, under room temperature (25 ℃), put into 90CC ion exchange water and 10CC epoxide respectively exactly.This glass tube is adjusted in 25 ℃ the water-bath in water temperature placed 1 hour.After this, this glass tube is carried out 1 minute high vibration, turn back in the water-bath again.After leaving standstill in 10 minutes, from water-soluble, take out this glass tube, obtain the volume of aqueous layer (part or all of epoxide is dissolved in the layer that forms in the ion exchange water) and epoxide layer according to the scale of glass tube respectively.
If epoxide is insoluble to water, be 10CC equally when then the volume of epoxide layer is with the experiment beginning.The water-soluble rate of this moment is 0%.To water under the consoluet situation (situation of no epoxide layer), water-soluble rate is 100% at epoxide.The part of epoxide is dissolved in water, when the volume of remaining epoxide layer was 1CC, 2CC, 3CC, 4CC, 5CC, 6CC, 7CC, 8CC and 9CC respectively, then water-soluble rate was respectively 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% and 10%.
Synthesizing of phenolic resins
Synthesis example 1
In 1 liter flask, put into 94g phenol and 101g 50% potassium hydroxide aqueous solution, make the interior temperature of reaction system reach 70 ± 3 ℃ then and like that slowly add 65.2g paraformaldehyde (purity 92%).After paraformaldehyde add to finish, the solution of gained was kept 3 hours at 90 ℃, react.Reaction makes reactant mixture be cooled to 35 ℃ after finishing.The polyethylene glycol (below be called PEG600), the 1.9g gamma-aminopropyl-triethoxy-silane that in reactant mixture, add 123.4g 50% potassium hydroxide aqueous solution, 30g borax, 33g mean molecule quantity 600.So just obtain containing the hardening carbon dioxide gas casting mold aqueous solution of water soluble phenol resin (Gu form branch: 65%).
Synthesis example 2
In 1 liter flask, put into 84.6g phenol, 22.0g nonyl phenol and 101g 50% potassium hydroxide aqueous solution, make the interior temperature of reaction system become 70 ± 3 ℃ then and like that slowly add 65.2g paraformaldehyde (purity 92%).After paraformaldehyde add to finish, the solution of gained was kept 3 hours at 90 ° of C, react.Reaction is cooled to 35 ℃ with reactant mixture after finishing.In reactant mixture, add 123.4g 50% potassium hydroxide aqueous solution, 30g borax, 33gPEG600,1.9g gamma-aminopropyl-triethoxy-silane.So just obtain containing the hardening carbon dioxide gas casting mold aqueous solution of water soluble phenol resin (Gu form branch: 67%).
Synthesis example 3
In 1 liter flask, put into 114g bisphenol-A and 101g 50% potassium hydroxide aqueous solution, make the interior temperature of reaction system become 70 ± 3 ℃ then and like that slowly add 65.2 g paraformaldehyde (purity 92%).After paraformaldehyde add to finish, the solution of gained was kept 3 hours at 90 ℃, react.Reaction is cooled to 35 ℃ with reactant mixture after finishing.In reactant mixture, add 123.4g 50% potassium hydroxide aqueous solution, 30g borax, 33g PEG600,1.9g gamma-aminopropyl-triethoxy-silane.So just obtain containing the hardening carbon dioxide gas casting mold aqueous solution of water soluble phenol resin (Gu form branch: 68%).
Synthesis example 4
In 1 liter flask, put into 75.2g phenol, 22.8 g bisphenol-As and 101g 50% potassium hydroxide aqueous solution, make the interior temperature of reaction system become 70 ± 3 ℃ then and like that slowly add 65.2g paraformaldehyde (purity 92%).After the interpolation of paraformaldehyde finishes, the solution of gained was kept 3 hours at 90 ℃, react.Reaction is cooled to 35 ℃ with reactant mixture after finishing.In reactant mixture, add 123.4g 50% potassium hydroxide aqueous solution, 30g borax, 33g PEG600,1.9g gamma-aminopropyl-triethoxy-silane.So just obtain containing the carbon dioxide hardening casting mold aqueous solution of water soluble phenol resin (Gu form branch: 67%).
Synthesis example 5
Embodiment 1 according to the fair 4-76947 of spy carries out synthetic test.That is, use 50% potassium hydroxide aqueous solution as catalyst, making formaldehyde/phenol (mol ratio) is that 1.3,50% potassium hydroxide aqueous solution (hydroxyl ion)/phenol (mol ratio) is 0.06, and the temperature of reaction system is controlled at 65 ℃, carries out reaction in 1 hour.Then, will react the temperature that is with 1 minute 1 ℃ speed and be heated to 75 ℃.After this, reaction being tied up to 75 ℃ kept 30 minutes.And then be heated to 85 ℃ with the temperature that 1 minute speed of 1 ℃ will be reacted system.After this, add 15g 50% potassium hydroxide aqueous solution in the sample (reactant mixture) of 25g, the viscosity (at 25 ℃) that continues to react to the gained dilution is 5000cps.Gather the matrix material resin that 25g generates in this reaction,, make it dissolving to wherein adding 35g 50% potassium hydroxide aqueous solution, 5g borax, 0.39g silane coupling agent (A1102, Japanese ュ ニ カ-(strain) system, gamma-aminopropyl-triethoxy-silane).So just obtain containing the carbon dioxide hardening casting mold aqueous solution of water soluble phenol resin (Gu form branch: 68%).
Synthesis example 6
The embodiment 1 that opens flat 4-147743 according to the spy carries out compound experiment.That is, the 94g phenol of packing in 1 liter four-hole boiling flask is while stirring to wherein slowly adding 101g 50% potassium hydroxide aqueous solution and 65.2g 92% paraformaldehyde.Then, the solution of gained is warming up to 90 ℃, carries out reaction in 3 hours at 90 ℃.Then, make reactant mixture be cooled to 40 ℃.In this reactant mixture, add 123.4g 50% potassium hydroxide aqueous solution, 30g borax and 1.9g gamma-aminopropyl-triethoxy-silane.Become 15% (weight) again and add diethylene glycol-butyl ether like that, and dissolve.So just obtain containing the hardening carbon dioxide gas casting mold aqueous solution of water soluble phenol resin (Gu form branch: 65%).
Synthesis example 7
The embodiment 1 that opens flat 5-320477 according to the spy carries out compound experiment.That is, pack in 1 liter four-hole boiling flask 228g bisphenol-A and 170g water are while stirring to wherein slowly adding 152g 48% potassium hydroxide aqueous solution and 114.1g 92% paraformaldehyde.Then, the solution of gained is warming up to 90 ℃, carries out reaction in 70 minutes at 90 ℃.So just obtain bakelite type bis-phenol urea formaldehyde.This resin is cooled to 40 ℃, then,, adds borax, the gained mixture is mixed with the amount of 8% (weight) with respect to the amount of gained bakelite type bis-phenol urea formaldehyde.Then,, become 15% (weight) and add diethylene glycol-butyl ether like that, become 0.5% (weight) and add gamma-aminopropyl-triethoxy-silane like that, and dissolve with respect to the amount of gained bakelite type bis-phenol urea formaldehyde.So just obtain containing the hardening carbon dioxide gas casting mold aqueous solution of water soluble phenol resin (Gu form branch: 65%).
Synthesis example 8
The embodiment 1 that opens flat 4-298591 according to the spy carries out compound experiment.That is, in 1 liter of four-hole boiling flask, pack into 94g phenol, 203g 37% formalin (being that the formaldehyde containing ratio is 37%), 90g distilled water and 24g 93% sodium hydrate aqueous solution.With the mixture of 300 rev/mins of limits stirring gained, the limit is 50 ℃ of reactions 1 hour, 80 ℃ of reactions 7 hours.With the reactant mixture cool to room temperature of gained, then add T 55 with the amount that becomes 20% (weight).So just obtain containing the casting mold aqueous solution of water soluble phenol resin.
Synthesis example 9
The embodiment 1 that opens flat 7-9073 according to the spy carries out compound experiment.That is, in 50% potassium hydroxide aqueous solution, add and the equimolar phenol of potassium hydroxide, stir resulting mixture, make the phenol dissolving.The limit remains on 80 ℃ with the temperature of obtained aqueous solution, and 50% formalin (being formaldehyde containing ratio 50%) is slowly added on the limit in obtained aqueous solution, and relative 1 moles of phenol makes formaldehyde become 2 moles, makes phenol and formaldehyde carry out condensation reaction.Make reaction solution remain on 80 ℃ and proceed reaction, reach 120CPC (at 25 ℃) until the viscosity of reaction solution.When reaching this viscosity, cooled reaction solution is to room temperature.Subsequently, in reaction solution, reach 0.70 such amount and add 50% potassium hydroxide with molal quantity with respect to the potassium hydroxide of 1 moles of phenol hydroxyl.So just obtain resin aqueous solution.Add 0.5 parts by weight gamma-aminopropyl-triethoxy-silane with respect to this resin aqueous solution of 100 parts by weight, obtain viscosity 70CPS, contain the casting mold aqueous solution of water-soluble phenolic resins.
Embodiment 1-21
(comprise chlorine element etc., be 12g based on the amount of the mixture of epoxide to the carbon dioxide hardening casting mold that will contain the water soluble phenol resin that synthesis example 1 obtains with the 12g epoxide shown in aqueous solution 48g and the table 1.Below identical.The amount of the chlorine element in this mixture in the table 1 record) mix, be modulated into the carbon dioxide hardening adhesive composition.With respect to homemade No. 6 silica sands of 2kg, add 60g carbon dioxide hardening adhesive composition, the mixture with mixing blender mixing gained obtains sand mixture.This sand mixture is filled in the hardening carbon dioxide gas pouring mold type of 8 cylinder type samples that are selected from diameter 50mm, high 50mm.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in Table 1.
Table 1
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Embodiment 1 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ??9.0 | ????24.9 | ????62.3 | ????99.8 |
| Embodiment 2 | Synthesis example 1 | ????48 | T 55 | ????87 | ????12 | ??15.3 | ????23.3 | ????58.3 | ????99.7 |
| Embodiment 3 | Synthesis example 1 | ????48 | T 55 | ????80 | ????12 | ??22.7 | ????22.2 | ????55.5 | ????99.5 |
| Embodiment 4 | Synthesis example 1 | ????48 | The trimethylolpropane diglycidyl ether | ????23 | ????12 | ??8.0 | ????18.0 | ????45.0 | ????98.5 |
| Embodiment 5 | Synthesis example 1 | ????48 | Two T 55s | ????75 | ????12 | ??15.0 | ????22.0 | ????55.0 | ????99.5 |
| Embodiment 6 | Synthesis example 1 | ????48 | The polyglycereol polyglycidyl ether | ????100 | ????12 | ??13.6 | ????24.1 | ????60.3 | ????99.8 |
| Embodiment 7 | Synthesis example 1 | ????48 | Ethylene glycol diglycidylether | ????100 | ????12 | ??5.3 | ????21.2 | ????53.0 | ????99.0 |
| Embodiment 8 | Synthesis example 1 | ????48 | The diethylene glycol diglycidyl ether | ????95 | ????12 | ??10.2 | ????22.3 | ????55.8 | ????99.2 |
| Embodiment 9 | Synthesis example 1 | ????48 | Polyethyleneglycol diglycidylether | ????91 | ????12 | ??22.0 | ????22.7 | ????56.8 | ????99.5 |
| Embodiment 10 | Synthesis example 1 | ????48 | Propylene glycol diglycidylether | ????94 | ????12 | ??12.5 | ????23.4 | ????58.5 | ????99.5 |
Table 1 is continuous
Comparative example 1
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [S] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Embodiment 11 | Synthesis example 1 | ????48 | The DPG diglycidyl ether | ????88 | ????12 | ????5.6 | ????22.4 | ????56.0 | ????99.4 |
| Embodiment 12 | Synthesis example 1 | ????48 | Polypropylene glycol diglycidyl ether | ????31 | ????12 | ????3.0 | ????17.0 | ????47.0 | ????98.0 |
| Embodiment 13 | Synthesis example 1 | ????48 | Resorcinolformaldehyde resin | ????0 | ????12 | ????0.1 | ????17.2 | ????45.0 | ????98.3 |
| Embodiment 14 | Synthesis example 1 | ????48 | Pentaerythrite four glycidol ethers | ????27 | ????12 | ????17.0 | ????18.0 | ????45.0 | ????98.0 |
| Embodiment 15 | Synthesis example 1 | ????48 | The polytetramethylene diglycidyl ether | ????0 | ????12 | ????2.0 | ????18.5 | ????46.2 | ????98.1 |
| Embodiment 16 | Synthesis example 1 | ????48 | 2-ethylhexyl-glycidol ether | ????0 | ????12 | ????3.2 | ????17.4 | ????43.5 | ????98.0 |
| Embodiment 17 | Synthesis example 1 | ????48 | Phenol ethylene oxide adduct-glycidol ether | ????50 | ????12 | ????5.0 | ????18.1 | ????45.3 | ????98.3 |
| Embodiment 18 | Synthesis example 1 | ????48 | The adipic acid diglycidyl ether | ????26 | ????12 | ????2.2 | ????17.5?? | ????44.0 | ????98.0 |
| Embodiment 19 | Synthesis example 1 | ????48 | Bisphenol A diglycidyl ether | ????0 | ????12 | ????0.8 | ????16.8 | ????42.0 | ????97.5 |
| Embodiment 20 | Synthesis example 1 | ????48 | The phenolic resins polyglycidyl ether | ????0 | ????12 | ????2.5 | ????17.3 | ????43.3 | ????97.5 |
| Embodiment 21 | Synthesis example 1 | ????48 | Dibromo phenyl-glycidol ether | ????0 | ????12 | ????3.5 | ????16.4 | ????41.0 | ????97.1 |
With respect to homemade No. 6 silica sands of 2kg, add hardening carbon dioxide gas casting mold that 48g contains the water soluble phenol resin that synthesis example 1 obtains respectively with the aqueous solution and 12g BC.Mixture with the mixing gained of mixing blender obtains sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃, relative humidity 60%.
The results are shown in the table 2.
Comparative example 2-4
With respect to homemade No. 6 silica sands of 2kg, add the hardening carbon dioxide gas casting mold aqueous solution that 60g contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 5-7.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 2.
Comparative example 5
With respect to homemade No. 6 silica sands of 2kg, add the casting mold aqueous solution that 60g contains the water soluble phenol resin that synthesis example 8 obtains.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 2.
Comparative example 6
With respect to homemade No. 6 silica sands of 2kg, interpolation has the compound (デ Na コ-Le EX-512) of epoxy radicals and these compositions (6g) of the hardener composition that 5.4g acetate glycol ester is formed, mixing resulting mixture by 0.6g.Then,, obtain sand mixture with the mixing mixture that obtains of mixing blender to wherein adding the casting mold aqueous solution that 30g contains the water soluble phenol resin that synthesis example 9 obtains.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 2.
Table 2
Annotate)
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Comparative example 1 | Synthesis example 1 | ?48 | ?- | - | ?- | ????- | ????12.0 | ????33.5 | ????93.0 |
| Comparative example 2 | Synthesis example 5 | ?60 | ?- | - | ?- | ????- | ????9.5 | ????18.5 | ????85.0 |
| Comparative example 3 | Synthesis example 6 | ?60 | ?- | - | ?- | ????- | ????10.2 | ????34.5 | ????93.5 |
| Comparative example 4 | Synthesis example 7 | ?60 | ?- | - | ?- | ????- | ????12.5 | ????35.5 | ????94.0 |
| Comparative example 5 | Synthesis example 8 | ?60 | T 55 * | 99 | (12)** | ????9.0 | ????0.0 | ????38.2 | ????95.2 |
| Comparative example 6 | Synthesis example 9 | ?30 | テナコ- ルEX-512 | 100 | 0.6 | ????- | ????4.0 | ????39.9 | ????96.2 |
*: this epoxide is contained in the binding agent.
*: be the 12g among the addition 60g of binding agent.
Embodiment 22-42
With the ratio shown in the table 3 mix contain the water soluble phenol resin that synthesis example 2 obtains the hardening carbon dioxide gas casting mold with the epoxide shown in the aqueous solution and the table 3, be modulated into the carbon dioxide hardening adhesive composition.Reclaimed sand (the calcination loss amount: 0.7%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, add the 60g binder composition for hardening carbon dioxide gas, with the mixing mixture that obtains of mud refining blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the casting intensity (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI type %).The environmental condition of this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 3.
Table 3
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Embodiment 22 | Synthesis example 2 | ????24 | T 55 | ????99 | ????36 | ????9.0 | ????28.0 | ????70.0 | ????99.9 |
| Embodiment 23 | Synthesis example 2 | ????30 | T 55 | ????99 | ????30 | ????9.0 | ????26.0 | ????65.0 | ????99.8 |
| Embodiment 24 | Synthesis example 2 | ????48 | T 55 | ????99 | ????12 | ????9.0 | ????22.0 | ????55.0 | ????99.5 |
| Embodiment 25 | Synthesis example 2 | ????30 | Two T 55s | ????75 | ????30 | ????11.0 | ????21.4 | ????53.6 | ????99.3 |
| Embodiment 26 | Synthesis example 2 | ????30 | Ethylene glycol diglycidylether | ????100 | ????30 | ????5.3 | ????21.4 | ????53.5 | ????99.5 |
| Embodiment 27 | Synthesis example 2 | ????36 | The polyglycereol polyglycidyl ether | ????100 | ????24 | ????20.0 | ????22.7 | ????56.8 | ????99.8 |
| Embodiment 28 | Synthesis example 2 | ????36 | The polyglycereol polyglycidyl ether | ????100 | ????24 | ????25.0 | ????22.8 | ????57.0 | ????99.0 |
| Embodiment 29 | Synthesis example 2 | ????30 | The diethylene glycol diglycidyl ether | ????100 | ????30 | ????15.0 | ????25.6 | ????64.0 | ????99.8 |
| Embodiment 30 | Synthesis example 2 | ????48 | The diethylene glycol diglycidyl ether | ????100 | ????12 | ????15.0 | ????22.4 | ????56.0 | ????99.0 |
| Embodiment 31 | Synthesis example 2 | ????24 | Polyethyleneglycol diglycidylether | ????100 | ????36 | ????20.5 | ????28.8 | ????72.0 | ????99.9 |
Table 3 is continuous
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Embodiment 32 | Synthesis example 2 | ????48 | Polyethyleneglycol diglycidylether | ????100 | ????12 | ????20.5 | ????23.2 | ????58.0 | ????99.7 |
| Embodiment 33 | Synthesis example 2 | ????24 | Propylene glycol diglycidylether | ????99 | ????36 | ????3.3 | ????27.2 | ????68.0 | ????99.7 |
| Embodiment 34 | Synthesis example 2 | ????48 | Propylene glycol diglycidylether | ????99 | ????12 | ????3.3 | ????20.8 | ????52.0 | ????98.3 |
| Embodiment 35 | Synthesis example 2 | ????30 | The DPG diglycidyl ether | ????85 | ????30 | ????5.6 | ????21.5 | ????53.8 | ????99.0 |
| Embodiment 36 | Synthesis example 2 | ????54 | The DPG diglycidyl ether | ????85 | ????6 | ????5.6 | ????23.2 | ????57.9 | ????98.1 |
| Embodiment 37 | Synthesis example 2 | ????36 | Polypropylene glycol diglycidyl ether | ????90 | ????24 | ????10.0 | ????21.8 | ????54.5 | ????98.0 |
| Embodiment 38 | Synthesis example 2 | ????54 | Polypropylene glycol diglycidyl ether | ????91 | ????6 | ????10.0 | ????20.8 | ????52.0 | ????98.3 |
| Embodiment 39 | Synthesis example 2 | ????30 | Bisphenol A diglycidyl ether | ????0 | ????30 | ????0.5 | ????17.2 | ????43.0 | ????97.2 |
| Embodiment 40 | Synthesis example 2 | ????48 | Bisphenol A diglycidyl ether | ????0 | ????12 | ????0.8 | ????17.2 | ????43.1 | ????97.0 |
| Embodiment 41 | Synthesis example 2 | ????36 | The phenolic resins polyglycidyl ether | ????0 | ????24 | ????1.3 | ????17.3 | ????43.3 | ????97.5 |
| Embodiment 42 | Synthesis example 2 | ????42 | Dibromo phenyl-glycidol ether | ????0 | ????18 | ????2.3 | ????16.5 | ????41.2 | ????97.5 |
Comparative example 7
Reclaimed sand (the calcination loss amount: 0.7%), add hardening carbon dioxide gas casting mold that 30g contains the water soluble phenol resin that synthesis example 2 obtains respectively with the aqueous solution and 30g ethyl carbitol of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 4.
Comparative example 8-10
Reclaimed sand (the calcination loss amount: 0.7%), add the hardening carbon dioxide gas casting mold aqueous solution that 60g contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 5-7 of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 4.
Comparative example 11
Reclaimed sand (the calcination loss amount: 0.7%), add the casting mold aqueous solution that 60g contains the water soluble phenol resin that synthesis example 8 obtains of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 4.
Comparative example 12
Reclaimed sand (the calcination loss amount: 0.7%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, interpolation has the compound (デ Na コ-Le EX-512) of epoxy radicals and these compositions (6g) of the curing agent group thing that the 5.4g ethylene monoacetate is formed, mixing resulting mixture by 0.6g.Then, to wherein adding the casting mold aqueous solution that 30g contains the water soluble phenol resin that synthesis example 9 obtains,, obtain sand mixture with the mixing mixture that obtains of mixing blender.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 4.
Table 4
Annotate)
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose in the epoxide [weight %] | ||||
| Comparative example 7 | Synthesis example 2 | ?30 | - | - | - | ????- | ????9.8 | ????25.3 | ????85.3 |
| Comparative example 8 | Synthesis example 5 | ?60 | - | - | - | ????- | ????8.5 | ????16.2 | ????85.0 |
| Comparative example 9 | Synthesis example 6 | ?60 | - | - | - | ????- | ????8.3 | ????28.3 | ????90.3 |
| Comparative example 10 | Synthesis example 7 | ?60 | - | - | - | ????- | ????10.3 | ????31.3 | ????92.0 |
| Comparative example 11 | Synthesis example 8 | ?60 | T 55 * | 99 | (12)** | ????9.0 | ????0.0 | ????35.7 | ????93.2 |
| Comparative example 12 | Synthesis example 9 | ?30 | デナコ- ルEX-512 | 100 | 0.6 | ????- | ????5.0 | ????39.0 | ????94.5 |
*: this epoxide is included in the binding agent.
*: be the 12g among the content of binder 60g.
Implement 43-67
Reclaimed sand (the calcination loss amount:0.5%) of adhering to domestic No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg; Add respectively hardening carbon dioxide gas foundry goods of the present invention with (II) composition of resin combination and the epoxide shown in the table 5 (hardening carbon dioxide gas casting mold of the present invention with (I) composition of resin combination) with the amount shown in the table 5, above-mentioned (II) composition be the water soluble phenol resin that obtains to the arbitrary example that contains among the synthesis example 1-4 hardening carbon dioxide gas with casting mold with belong to shown in dissolving or the scatter table 5 in the aqueous solution in the periodic table 1B-8 family metallic element any metal dust or the compound that contains such a metallic element (in table 5, put down in writing the amount that is converted into this metallic element. Below identical)) and form.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%), the environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 5.
Table 5
| The casting mold resin combination | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2]???? | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose [weight %] | The containing metal element compound | Addition [g] | ||||
| Embodiment 43 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Acetate Cu | ??2500 | ????24.4 | ????61.0 | ????99.9 |
| Embodiment 44 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Hydroxide Ca | ??2500 | ????30.1 | ????75.3 | ????99.8 |
| Embodiment 45 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Chlorination Zn | ??2500 | ????30.5 | ????76.3 | ????99.5 |
| Embodiment 46 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Lactic acid Al | ??2500 | ????31.2 | ????78.0 | ????99.3 |
| Embodiment 47 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Metatitanic acid K | ??2500 | ????28.8 | ????72.0 | ????99.5 |
| Embodiment 48 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Acetate V | ??2500 | ????24.8 | ????62.0 | ????99.8 |
| Embodiment 49 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Chromic acid K | ??2500 | ????22.8 | ????57.0 | ????99.0 |
| Embodiment 50 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Ferromanganese powder | ??2500 | ????23.2 | ????58.0 | ????99.8 |
| Embodiment 51 | Synthesis example 1 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Acetate Ni | ??2500 | ????24.1 | ????60.3 | ????99.0 |
| Embodiment 52 | Synthesis example 2 | ????24 | Polyethyleneglycol diglycidylether | ????91 | ????36 | ????15.8 | Portland cement | ??45000 | ????28.8 | ????72.0 | ????99.9 |
| Embodiment 53 | Synthesis example 2 | ????48 | Polyethyleneglycol diglycidylether | ????91 | ????12 | ????15.8 | Aluminum oleate | ??3000 | ????28.8 | ????72.0 | ????99.7 |
| Embodiment 54 | Synthesis example 2 | ????24 | Glycerine four glycidol ethers | ????100 | ????36 | ????8.0 | Alumina powder | ??45000 | ????27.2 | ????68.0 | ????99.7 |
| Embodiment 55 | Synthesis example 3 | ????24 | Propylene glycol diglycidylether | ????95 | ????36 | ????5.7 | Hydroxide Mg | ??30 | ????27.6 | ????69.0 | ????99.3 |
| Embodiment 56 | Synthesis example 3 | ????25 | The DPG diglycidyl ether | ????86 | ????35 | ????5.6 | Hydroxide Al | ??150 | ????28.1 | ????70.3 | ????99.6 |
| Embodiment 57 | Synthesis example 3 | ????30 | The DPG diglycidyl ether | ????86 | ????30 | ????5.6 | Acetate Al | ??500 | ????28.8 | ????72.0 | ????99.2 |
Table 5 is continuous
| The casting mold resin combination | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose [weight %] | The containing metal element compound | Addition [g] | ||||
| Embodiment 58 | Synthesis example 3 | ????48 | Polypropylene glycol diglycidyl ether | ????31 | ????12 | ????15.8 | Sodium aluminate | 35000 | ????230 | ????65.0 | ????99.0 |
| Embodiment 59 | Synthesis example 4 | ????48 | Propylene glycol diglycidylether | ????95 | ????12 | ????6.0 | Sodium aluminate | 2000 | ????30.2 | ????75.5 | ????98.3 |
| Embodiment 60 | Synthesis example 4 | ????25 | The DPG diglycidyl ether | ????86 | ????35 | ????5.6 | Lactic acid Al | 50 | ????31.1 | ????77.7 | ????99.0 |
| Embodiment 61 | Synthesis example 4 | ????54 | The DPG diglycidyl ether | ????86 | ????6 | ????5.6 | EDTA Na 2Zn | 4500 | ????30.0 | ????75.0 | ????98.1 |
| Embodiment 62 | Synthesis example 4 | ????36 | Polypropylene glycol diglycidyl ether | ????86 | ????24 | ????15.8 | Al(O- iPr) 3 | 300 | ????28.9 | ????72.3 | ????98.0 |
| Embodiment 63 | Synthesis example 4 | ????48 | T 55 | ????99 | ????12 | ????8.0 | Lactic acid Al/ sodium aluminate | 2500 | ????27.5 | ????68.7 | ????98.3 |
| Embodiment 64 | Synthesis example 4 | ????30 | Bisphenol A diglycidyl ether | ????0 | ????30 | ????5.0 | The Al phenates | 20 | ????21.0 | ????62.0 | ????95.2 |
| Embodiment 65 | Synthesis example 4 | ????48 | Bisphenol A diglycidyl ether | ????0 | ????12 | ????5.0 | Aluminium powder | 4200 | ????22.5 | ????63.5 | ????95.5 |
| Embodiment 66 | Synthesis example 4 | ????36 | The phenolic resins polyglycidyl ether | ????0 | ????24 | ????5.5 | Hydroxide Al | 230 | ????21.5 | ????64.0 | ????95.7 |
| Embodiment 67 | Synthesis example 4 | ????42 | Dibromo phenyl-glycidol ether | ????0 | ????18 | ????4.9 | Sodium zirconate | 200 | ????20.0 | ????61.7 | ????95.0 |
Comparative example 13-16
Reclaimed sand (the calcination loss amount: 0.5%), add hardening carbon dioxide gas casting mold that 60g contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 1-4 respectively with the aqueous solution and 30g Macrogol 600 of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 6.
Comparative example 17-19
Reclaimed sand (the calcination loss amount: 0.5%), add the hardening carbon dioxide gas casting mold aqueous solution that 60g contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 5-7 of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After ventilating 30 fens, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 6.
Comparative example 20
Reclaimed sand (the calcination loss amount: 0.5%), add the casting mold aqueous solution that 60g contains the water soluble phenol resin that synthesis example 8 obtains of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 6.
Comparative example 21
Reclaimed sand (the calcination loss amount: 0.5%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, interpolation has the compound (デ Na コ-Le EX-512) of epoxy radicals and these compositions (6g) of the hardener composition that the 5.4g ethylene monoacetate is formed, the mixing mixture that obtains by 0.6g.Then, to wherein adding the casting mold aqueous solution that 30g contains the water soluble phenol resin that synthesis example 9 obtains,, obtain sand mixture with the mixing mixture that obtains of mixing blender.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 6.
Table 6
Annotate)
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose [weight %] | The containing metal element compound | Addition [ppm] | ||||
| Comparative example 13 | Synthesis example 1 | ?60 | - | - | ?- | ????- | ????- | ???- | ????8.0 | ????25.3 | ????85.3 |
| Comparative example 14 | Synthesis example 2 | ?60 | - | - | ?- | ????- | ????- | ???- | ????9.2 | ????27.3 | ????87.3 |
| Comparative example 15 | Synthesis example 3 | ?60 | - | - | ?- | ????- | ????- | ???- | ????9.9 | ????29.5 | ????87.5 |
| Comparative example 16 | Synthesis example 4 | ?60 | - | - | ?- | ????- | ????- | ???- | ????9.8 | ????30.3 | ????88.3 |
| Comparative example 17 | Synthesis example 5 | ?60 | - | - | ?- | ????- | ????- | ???- | ????6.2 | ????12.5 | ????83.2 |
| Comparative example 18 | Synthesis example 6 | ?60 | - | - | ?- | ????- | ????- | ???- | ????8.3 | ????22.3 | ????84.3 |
| Comparative example 19 | Synthesis example 7 | ?60 | - | - | ?- | ????- | ????- | ???- | ????10.3 | ????28.0 | ????86.5 |
| Comparative example 20 | Synthesis example 8 | ?60 | T 55 * | 99 | (12)** | ????9.0 | ????- | ???- | ????0.1 | ????32.7 | ????90.2 |
| Comparative example 21 | Synthesis example 9 | ?30 | テナコ- ルEX-512 | 100 | 0.6 | ????- | ????- | ???- | ????5.5 | ????35.0 | ????91.2 |
*: this epoxide is included in the binding agent.
*: be the 12g among the content of binder 60g.
Embodiment 68-92
Reclaimed sand (the calcination loss amount: 0.5%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, add the hardening carbon dioxide gas casting mold aqueous solution that contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 1-4 respectively with the amount shown in the table 7, and use the carbon dioxide hardening casting mold resin combination of forming by epoxides, add its constituent.And then, in above-mentioned reclaimed sand, add the compound that contains any metal dust in the periodic table 1B-8 family metallic element shown in the table 7 or contain these metallic elements in addition.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 7.
Table 7
| The casting mold resin combination | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2 | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Addition [g] | Water-soluble rate [%] | Chlorine dose [amount amount %] | The compound of containing metal element | Addition [g] | ||||
| Embodiment 68 | Synthesis example 1 | ????48 | T 55 | ????12 | ????99 | ??9.0 | Acetate Cu | ??500 | ????24.4 | ??61.0 | ????98.6 |
| Embodiment 69 | Synthesis example 1 | ????48 | T 55 | ????12 | ????99 | ??15.3 | Oxychloride Ca | ??500 | ????30.0 | ??75.0 | ????99.0 |
| Embodiment 70 | Synthesis example 1 | ????48 | T 55 | ????12 | ????75 | ??18.0 | Chlorination Zn | ??500 | ????30.1 | ??75.3 | ????99.5 |
| Embodiment 71 | Synthesis example 1 | ????48 | The polyglycereol polyglycidyl ether | ????12 | ????70 | ??13.6 | Lactic acid Al | ??500 | ????23.0 | ??71.0 | ????98.2 |
| Embodiment 72 | Synthesis example 1 | ????48 | The ethylene glycol bisthioglycolate ethylene oxidic ester | ????12 | ????100 | ??5.3 | Metatitanic acid K | ??500 | ????28.8 | ??72.0 | ????99.5 |
| Embodiment 73 | Synthesis example 1 | ????48 | The diethylene glycol diglycidyl ether | ????12 | ????95 | ??15.3 | Acetate V | ??500 | ????24.8 | ??62.0 | ????99.0 |
| Embodiment 74 | Synthesis example 1 | ????48 | Polyethyleneglycol diglycidylether | ????12 | ????100 | ??18.0 | Complex acid K | ??500 | ????22.8 | ??57.0 | ????99.0 |
| Embodiment 75 | Synthesis example l | ????48 | T 55 | ????12 | ????99 | ??22.0 | Ferromanganese powder | ??500 | ????23.2 | ??58.0 | ????99.1 |
| Embodiment 76 | Synthesis example 1 | ????48 | T 55 | ????12 | ????99 | ??25.0 | Acetate Ni | ??500 | ????24.1 | ??60.3 | ????99.0 |
| Embodiment 77 | Synthesis example 2 | ????24 | Polyethyleneglycol diglycidylether | ????36 | ????100 | ??20.3 | Portland cement | ??3000 | ????28.8 | ??72.0 | ????99.9 |
| Embodiment 78 | Synthesis example 2 | ????48 | Polyethyleneglycol diglycidylether | ????12 | ????100 | ??18.0 | Lactic acid Al | ??3000 | ????28.8 | ??72.0 | ????99.7 |
| Embodiment 79 | Synthesis example 2 | ????24 | T 55 | ????36 | ????100 | ??22.0 | Alumina powder | ??45000 | ????27.2 | ??68.0 | ????99.7 |
| Embodiment 80 | Synthesis example 3 | ????30 | Propylene glycol diglycidylether | ????30 | ????99 | ??15.3 | Hydroxide Mg | ??50000 | ????27.6 | ??69.0 | ????99.3 |
| Embodiment 81 | Synthesis example 3 | ????30 | The DPG diglycidyl ether | ????30 | ????95 | ??18.5 | Hydroxide Al | ??150 | ????28.1 | ??70.3 | ????99.6 |
| Embodiment 82 | Synthesis example 3 | ????30 | The DPG diglycidyl ether | ????30 | ????85 | ??22.3 | Acetate Al | ??500 | ????28.8 | ??72.0 | ????99.2 |
Table 7 is continuous
Comparative example 22-25
| The casting mold resin combination | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2 | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Addition [g] | Water-soluble rate [%] | Chlorine dose [weight %] | The compound of containing metal element | Addition [g] | ||||
| Embodiment 83 | Synthesis example 3 | ????48 | Polypropylene glycol diglycidyl ether | ????12 | ????85 | ????15.3 | Sodium aluminate | ??35000 | ????27.8 | ????69.5 | ????99.3 |
| Embodiment 84 | Synthesis example 4 | ????48 | Propylene glycol diglycidylether | ????12 | ????85 | ????2.3 | Sodium aluminate | ??2000 | ????31.2 | ????78.0 | ????99.8 |
| Embodiment 85 | Synthesis example 4 | ????30 | The DPG diglycidyl ether | ????30 | ????95 | ????5.7 | Lactic acid Al | ??50 | ????32.1 | ????80.3 | ????99.7 |
| Embodiment 86 | Synthesis example 4 | ????54 | The DPG diglycidyl ether | ????6 | ????85 | ????10.3 | EDTA Na 2Zn | ??4500 | ????32.2 | ????80.4 | ????99.7 |
| Embodiment 87 | Synthesis example 4 | ????36 | Polypropylene glycol diglycidyl ether | ????24 | ????83 | ????15.3 | Al(O- iPr)3 | ??300 | ????31.7 | ????79.3 | ????99.5 |
| Embodiment 88 | Synthesis example 4 | ????48 | T 55 | ????12 | ????98 | ????25.0 | Lactic acid Al/ sodium aluminate | ??2500 | ????31.4 | ????76.5 | ????99.7 |
| Embodiment 89 | Synthesis example 4 | ????30 | Bisphenol A diglycidyl ether | ????30 | ????0 | ????0.5 | The Al phenates | ??20 | ????15.2 | ????65.0 | ????98.1 |
| Embodiment 90 | Synthesis example 4 | ????48 | Bisphenol A diglycidyl ether | ????12 | ????0 | ????0.8 | Aluminium powder | ??4200 | ????18.2 | ????63.2 | ????97.8 |
| Embodiment 91 | Synthesis example 4 | ????36 | The phenolic resins polyglycidyl ether | ????24 | ????0 | ????0.9 | Hydroxide Al | ??230?? | ????19.0 | ????66.5 | ????98.8 |
| Embodiment 92 | Synthesis example 4 | ????42 | Dibromo phenyl one glycidol ether | ????18 | ????0 | ????0.2 | Sodium zirconate | ??5200 | ????20.0 | ????68.0 | ????98.9 |
Reclaimed sand (the calcination loss amount: 0.5%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, add hardening carbon dioxide gas the casting mold aqueous solution and 10g BC that 60g contains the water soluble phenol resin that arbitrary example obtains among the synthesis example 1-4 respectively, carry out mixingly, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature.Relative humidity 60%.
The results are shown in the table 8.
Comparative example 26-28
Reclaimed sand (the calcination loss amount: 0.5%), add the hardening carbon dioxide gas casting mold aqueous solution that 60g contains the water soluble phenol resin that the arbitrary example among the synthesis example 5-7 obtains of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 hardening carbon dioxide gas pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.With carbon dioxide air pressure 2kgf/cm
2, carbon dioxide throughput 20L/min condition, ventilation 60g carbon dioxide.After 30 minutes, measure the mould strength (being setting rate) of sample from the ventilation beginning, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 8.
Comparative example 29
Reclaimed sand (the calcination loss amount: 0.5%), add 60g and contain the casting mold aqueous solution that water soluble phenolic resin that synthesis example 8 obtains refers to of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg.With the mixing mixture that obtains of mixing blender, obtain sand mixture.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature.Relative humidity 60%.
The results are shown in the table 8.
Comparative example 30
Reclaimed sand (the calcination loss amount: 0.5%) of adhering to homemade No. 6 silica sands of the remaining water soluble phenol resin hardening thing that hardening carbon dioxide gas arranged with respect to 2kg, interpolation has the compound (テ Na コ-Le EX-512) of epoxy radicals and these compositions (6g) of the hardener composition that the 5.4g ethylene glycol-acetate is formed, the mixture of mixing gained by 0.6g.Then, to wherein adding the casting mold aqueous solution that 30g contains the water soluble phenol resin that synthesis example 9 obtains,, obtain sand mixture with the mixing mixture that obtains of mixing blender.This sand mixture is filled in 8 pouring mold types that are selected from diameter 50mm, high 50mm cylinder type sample.After 30 minutes, measure the mould strength (being setting rate) of sample, after 24 hours, measure mould strength and mo(U)ld face stability (SSI%).Environmental condition during this test is 25 ℃ of temperature, relative humidity 60%.
The results are shown in the table 8.
Table 8
Annotate)
| Adhesive composition | Mould strength [kgf/cm after 30 minutes 2] | Mould strength [kgf/cm after 24 hours 2] | Mo(U)ld face stability [SSI%] | ||||||||
| The kind of binding agent | Addition [g] | The kind of epoxide | Water-soluble rate [%] | Addition [g] | Chlorine dose [weight %] | The containing metal element compound | Addition [ppm] | ||||
| Comparative example 22 | Synthesis example 1 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????8.0 | ????26.0 | ????85.3 |
| Comparative example 23 | Synthesis example 2 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????8.3 | ????28.0 | ????87.3 |
| Comparative example 24 | Synthesis example 3 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????9.2 | ????29.5 | ????87.5 |
| Comparative example 25 | Synthesis example 4 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????9.5 | ????31.0 | ????88.3 |
| Comparative example 26 | Synthesis example 5 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????7.0 | ????13.0 | ????81.5 |
| Comparative example 27 | Synthesis example 6 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????8.5 | ????23.5 | ????85.4 |
| Comparative example 28 | Synthesis example 7 | ?60 | - | ??- | ??- | ????- | ????- | ????- | ????11.0 | ????29.0 | ????87.0 |
| Comparative example 29 | Synthesis example 8 | ?60 | T 55 * | ??99 | ??(12)** | ????9.0 | ????- | ????- | ????0.0 | ????33.0 | ????91.0 |
| Comparative example 30 | Synthesis example 9 | ?30 | テナコ- ルEX-512 | ??100 | ??0.6 | ????- | ????- | ????- | ????6.3 | ????36.0 | ????92.5 |
*: this epoxide is included in the binding agent.
*: be the 12g among the content of binder 60g.
Claims (12)
1 binder composition for hardening carbon dioxide gas, it is characterized in that, contain: (a) alkaline aqueous solution of epoxide, (b) water soluble phenol resin, (c) hardening accelerator and (d) silane coupling agent, (a) and (b), (c) and (d) total of composition be 100 parts by weight, (a) composition is the 0.1-60 parts by weight, (b) composition is the 15-99.7 parts by weight, and (c) composition is the 0.1-20 parts by weight, and (d) composition is the 0.1-10 parts by weight.
The described binder composition for hardening carbon dioxide gas of 2 claims 1, it is characterized in that, also contain (e) composition, should (e) composition be to contain at least a compound of from the group that the metallic element of periodic table 1B-8 family is formed, selecting, (a) and (b), (c) and (d) per 100 parts by weight of total of composition, (e) to be converted into the metallic element amount be the 0.0005-5 parts by weight to the content of composition.
The described binder composition for hardening carbon dioxide gas of 3 claims 2, wherein, (e) composition is the compound by following formula (1) expression:
In MaXb (1) formula, a and b are respectively the integers more than 1, M is the metallic element of periodic table 1B-8 family, X represents anion atoms group, the organic acid anion atoms group of hydrogen atom, carbon atom, alkyl, sulphur atom, nitrogen-atoms, phosphorus atoms, oxygen atom, halogen atom, hydroxyl, alkoxyl, amino, imino group, nitro, inorganic acid or shows that metal ion blocks the atomic group of property, but that M and X are not limited to respectively is a kind of.
The described binder composition for hardening carbon dioxide gas of 4 claims 1, wherein, (C) composition contains the boron compound as essential composition.
The described binder composition for hardening carbon dioxide gas of 5 claims 1, wherein, (a) composition has the water-soluble rate more than 20%.
The described binder composition for hardening carbon dioxide gas of 6 claims 1, wherein, (a) composition has at least two glycidyl ethers in a molecule.
7 hardening carbon dioxide gas casting mold resin combinations, it is characterized in that, it is by the alkaline aqueous solution that contains (a) epoxide (I) composition and contain (b) water soluble phenol resin, (c) hardening accelerator becomes to be grouped into (II) of (d) silane coupling agent, (I) composition is in mutual non-contact state mutually with (II) composition, (a), (b), (c) and (d) total of composition is 100 parts by weight, (a) composition is the 0.1-60 parts by weight, (b) composition is the 15-99.7 parts by weight, (c) composition is the 0.1-20 parts by weight, and (d) composition is the 0.1-10 parts by weight.
The described carbon dioxide hardening casting mold of 8 claims 7 resin combination, it is characterized in that, (II) composition also contains (e), should (e) contain at least a compound of from the group that the metallic element of periodic table 1B-8 family is formed, selecting, (a) and (b), (c) and (d) per 100 parts by weight of total of composition, it is the 0.0005-5 parts by weight that content (e) is converted into metallic element.
9 mould compositions, it makes the composition sclerosis of the binder composition for hardening carbon dioxide gas that contains 100 parts by weight fire resistance bulk materials, the record of 0.1-10 parts by weight claim 1 with carbon dioxide.
10 mould compositions, it is with the binder composition for hardening carbon dioxide gas of 100 parts by weight fire resistance bulk materials and claim 1 record or the hardening carbon dioxide gas casting mold resin combination of claim 7 record, with its (a) and (b), (c) and (d) total of composition be that the amount of 0.1-10 parts by weight is modulated into composition, use carbon dioxide that the said composition sclerosis is made to form.
11 process for making molds, comprise: the binder composition for hardening carbon dioxide gas that in 100 parts by weight fire resistance bulk materials, adds claim 1 record of 0.1-10 parts by weight, form composition, the composition of gained is mixing, composition is filled in the pouring mold type, composition is hardened in model with 0.1-30 parts by weight carbon dioxide.
12 process for making molds, comprise: the hardening carbon dioxide gas casting mold that adds the binder composition for hardening carbon dioxide gas of claim 1 record or claim 7 record in 100 parts by weight fire resistance bulk materials is with (I) composition of resin combination and (II) composition, with its (a) and (b), (c) and (d) total of composition be that the amount of 0.1-10 parts by weight is added, form composition, the composition of mixing gained, composition is filled in the pouring mold type, uses 0.1-30 parts by weight carbon dioxide in model, to make the composition sclerosis.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15237/1996 | 1996-01-31 | ||
| JP01523796A JP3453469B2 (en) | 1996-01-31 | 1996-01-31 | Binder composition for curing carbon dioxide |
| JP15237/96 | 1996-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1171991A true CN1171991A (en) | 1998-02-04 |
| CN1108207C CN1108207C (en) | 2003-05-14 |
Family
ID=11883270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97110004A Expired - Lifetime CN1108207C (en) | 1996-01-31 | 1997-01-31 | Binder composition for hardening carbon dioxide gas |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3453469B2 (en) |
| CN (1) | CN1108207C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100460487C (en) * | 2001-02-01 | 2009-02-11 | 呼世滨 | Fuel additive and fuel products containing it |
| WO2011097818A1 (en) * | 2010-02-11 | 2011-08-18 | 济南圣泉集团股份有限公司 | Phenolic resin binder composition |
| CN104220188A (en) * | 2012-03-23 | 2014-12-17 | 旭有机材工业株式会社 | Urethane-type curable organic binder for mold, and molding sand composition and mold obtained using same |
| CN109093059A (en) * | 2018-07-17 | 2018-12-28 | 安徽江淮车轮有限公司 | A kind of preparation method of the not viscous silica sand of Automobile steel ring casting |
| CN109465391A (en) * | 2018-12-20 | 2019-03-15 | 青岛连山铸造有限公司 | A kind of preparation method casting 350km axle box molding sand |
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| AU4026401A (en) * | 2000-02-07 | 2001-08-20 | Nagoya Oilchemical | Resin composition, molding material, and molded object |
| AU2004242413B2 (en) * | 2000-02-07 | 2006-04-27 | Nagoya Oilchemical Co., Ltd. | A molding material, and a molded article |
| CN107457349A (en) * | 2017-09-27 | 2017-12-12 | 马鞍山松鹤信息科技有限公司 | A kind of environmental-protecting type casting material binding agent and its preparation technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162393A (en) * | 1991-04-25 | 1992-11-10 | Foseco International Limited | Production of foundry sand moulds and cores |
| CN1024399C (en) * | 1992-01-10 | 1994-05-04 | 常州市压缩机配件厂 | Casting technique with stacked cold and hard sand mould |
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1996
- 1996-01-31 JP JP01523796A patent/JP3453469B2/en not_active Expired - Lifetime
-
1997
- 1997-01-31 CN CN97110004A patent/CN1108207C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100460487C (en) * | 2001-02-01 | 2009-02-11 | 呼世滨 | Fuel additive and fuel products containing it |
| WO2011097818A1 (en) * | 2010-02-11 | 2011-08-18 | 济南圣泉集团股份有限公司 | Phenolic resin binder composition |
| CN102753619A (en) * | 2010-02-11 | 2012-10-24 | 济南圣泉集团股份有限公司 | Phenolic resin binder composition |
| AU2010345651B2 (en) * | 2010-02-11 | 2013-11-28 | Jinan Shengquan Group Share-Holding Co., Ltd. | Phenolic Resin Adhesive Composition |
| CN102753619B (en) * | 2010-02-11 | 2014-10-01 | 济南圣泉集团股份有限公司 | Phenolic resin binder composition |
| CN104220188A (en) * | 2012-03-23 | 2014-12-17 | 旭有机材工业株式会社 | Urethane-type curable organic binder for mold, and molding sand composition and mold obtained using same |
| CN104220188B (en) * | 2012-03-23 | 2015-11-25 | 旭有机材工业株式会社 | Mold urethane cures type organic binder bond and the molding sand composition using it to obtain and mold |
| US9359466B2 (en) | 2012-03-23 | 2016-06-07 | Asahi Yukizai Corporation | Urethane-type curable organic binder for mold, and molding sand composition and mold obtained using the same |
| CN109093059A (en) * | 2018-07-17 | 2018-12-28 | 安徽江淮车轮有限公司 | A kind of preparation method of the not viscous silica sand of Automobile steel ring casting |
| CN109465391A (en) * | 2018-12-20 | 2019-03-15 | 青岛连山铸造有限公司 | A kind of preparation method casting 350km axle box molding sand |
| CN109465391B (en) * | 2018-12-20 | 2020-10-27 | 青岛连山铸造有限公司 | Preparation method of molding sand for casting 350km axle box |
| CN116492843A (en) * | 2023-05-25 | 2023-07-28 | 北京市中环博业环境工程技术有限公司 | Denitration method |
| CN116492843B (en) * | 2023-05-25 | 2024-03-12 | 北京市中环博业环境工程技术有限公司 | Denitration method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09206885A (en) | 1997-08-12 |
| JP3453469B2 (en) | 2003-10-06 |
| CN1108207C (en) | 2003-05-14 |
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