CN1046871C - Binder composition for mold and method for producing mold - Google Patents

Binder composition for mold and method for producing mold Download PDF

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CN1046871C
CN1046871C CN94103921A CN94103921A CN1046871C CN 1046871 C CN1046871 C CN 1046871C CN 94103921 A CN94103921 A CN 94103921A CN 94103921 A CN94103921 A CN 94103921A CN 1046871 C CN1046871 C CN 1046871C
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phenol
mold
aqueous solution
binder composition
phenolic compounds
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CN1110199A (en
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船田等
吉田昭
水野涉
京近直喜
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Kao Corp
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Kao Corp
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Abstract

The present invention relates to an adhesive compound for a casting mould, which comprises specific alkalescence phenolic resin. The present invention provides a method for producing casting moulds by the adhesive compound.

Description

Binder composition for mold
The present invention relates to be used for the adhesive composition that mold is produced, its purpose is to improve the flowability and the fillibility of being mixed the mixed sand that forms by the refractory particle material with this adhesive composition.The invention still further relates to the method for producing mold with this adhesive composition.
The invention still further relates to and be used for the adhesive composition that mold is produced, more particularly, relate to and can prevent the mold that the obtains adhesive composition that intensity descends when the sand temperature is low, even and this adhesive composition when mold uses more a spot of curing agent, also can improve its intensity.The invention still further relates to the method for producing mold with this adhesive composition in addition.
The invention still further relates to the adhesive composition that is used for mold production, more particularly, relate to the adhesive composition that can improve resulting mold strength.In addition, the invention still further relates to the method for producing mold with this adhesive composition.
The conventional method of producing mold is that the refractory particle material is mixed the formation mixed sand with adhesive composition, with this mixed sand model (pattern) of packing into, solidifies the adhesive in this adhesive composition then.As adhesive, various curable resins can use, as furane resins, water miscible phenolic resins, polyurethane resin etc.Wherein water miscible phenolic resins solidifies with organic ester and carbon dioxide, therefore, they are considered to be in to produce in the gentle curing mold of the self-curing process and can prevent the adhesive (JP-A-50-130627 that working environment worsens, JP-B-61-43132, and JP-B-61-37022) (representing the unexamined patent application of Japanese unexamined patent and Japan respectively) at this used JP-A and JP-B.Wherein water soluble phenol resin is meant the phenol formaldehyde resin of alkalescence, is to form or obtain by adding alkali behind phenol and the formaldehyde condensation polymer again by phenol and formaldehyde condensation polymer in the presence of alkali.
Yet, certain shortcoming is arranged when mixing the mixed sand production mold that forms with the adhesive composition that contains above-mentioned alkaline phenol formaldehyde resin by the refractory particle material, this is because compare with the adhesive that use contains furane resins, the flowability of this mixed sand is on duty mutually, to such an extent as to the model (pattern) of can not closely packing into.The mixed sand of mobile difference also has a shortcoming, is exactly that wherein refractory particle material and adhesive are difficult to mix.In addition, the use a model mixed sand of filling capacity (pattern-filling property) difference usually can cause the mould surface that obtains coarse or surface strength is low.Therefore, when being used to produce mold with the mixed sand that obtains as adhesive of phenol formaldehyde resin of alkalescence, resulting foundry goods has some defectives, as carries sand, burning secretly, penetrates and serious mouse tail etc., thereby causes casting quality to descend.
Therefore, proposed a kind of fluorine compounds surfactant (JP-A-2-299741) or fatty alcohol (JP-A-3-134067) are added in the adhesive composition that contains the alkaline phenol formaldehyde resin as flow improver additive.Yet the compatibility of fluorine compounds surfactant and fatty alcohol and alkaline phenol formaldehyde resin is poor, and can not substantially improve the flowability of mixed sand.In addition, fluorine compounds surfactant and fatty alcohol also have another shortcoming, are exactly their price comparison height, thereby have improved the cost of the foundry goods that obtains.
On the other hand, proposed to replace phenolic resins that phenol and formaldehyde condensation polymer obtain as adhesive (JP-A-62-40948 and JP-A-63-40636) with bis-phenol.In this technology, bis-phenol adopts bisphenol-A, Bisphenol F, bisphenol-c etc. separately, and therefore the phenolic resins that obtains is the binary polymer that is formed by bis-phenol and formaldehyde condensation polymer.
Its intensity of mold that obtains with this bis-phenol formaldehyde binary condensation resin obtains improvement to a certain degree, but can not be satisfied fully.Although promptly also having a shortcoming is exactly when having obtained satisfied fully mold strength when higher with the refractory particle material temperature (sand temperature) of mixed with resin, can cause mold strength significantly to descend when hanging down in sand temperature.This adhesive resin also has another shortcoming to cause that also mold strength significantly descends when the consumption of curing agent reduces.
The phenolic resins that has also proposed to obtain with polyhydroxy phenol replacement phenol and formaldehyde condensation polymer is as adhesive (JP-A-1-166853).Yet, promptly use this technology that mold strength is improved fully.
In these cases, the above-mentioned shortcoming when mixing with the refractory particle material in order to overcome the alkaline phenol formaldehyde resin, the present inventor has carried out extensive studies.The result, the present inventor finds and can improve flowability and the model filling capacity that is mixed the mixed sand that obtains by the alkaline phenol formaldehyde resin with the refractory particle material by the structure of improving alkaline phenol formaldehyde resin itself, promptly not only to use phenol and formaldehyde condensation polymer, but produce adhesive resin with the copolycondensation of these compounds and a kind of specific phenol.The present invention finishes on the basis of this discovery.
The object of the present invention is to provide binder composition for mold.
Therefore, a kind of embodiment of the present invention (after this being called first embodiment) relates to a kind of binder composition for mold, and it comprises phenolic compounds and/or the polyhydroxy phenol of following formula (2) expression, the alkyl phenol of following formula (3) expression and the alkalescent phenol resin that the aldehyde compound copolycondensation obtains of following formula (1) expression as main component.
Figure C9410392100061
In formula (1), R 1And R 2Represent hydrogen atom respectively or contain the alkyl of 2 or 2 following carbon atoms.
Figure C9410392100062
In formula (2), R 3Expression hydrogen atom, hydroxyl or contain the alkyl of 2 or 2 following carbon atoms.
Figure C9410392100071
In formula (3), R 4Expression contains the aliphatic group or the aryl radical of 3 or 3 above carbon atoms.
First embodiment of the present invention also relates to the method for producing mold, comprises the refractory particle material mixed with this adhesive composition obtaining mixed sand, with this mixed sand model of packing into, and solidifies this mixed sand.
Reduce to minimum adhesive composition even under the situation about reducing for the consumption that obtains a kind of or curing agent lower in the sand temperature mold strength is descended, the present inventor has further carried out extensive studies.Found that when the binary polymer adhesive that replaces obtaining as adhesive with a kind of ter-polymers phenolic resins that obtains by specific phenolic compounds, a kind of specific bis-phenol and a kind of aldehyde compound copolycondensation by a kind of bis-phenol and formaldehyde condensation polymer, though in the sand temperature under the lower or curing agent consumption situation seldom also can so that to the intensity of mold descend and reduce to minimum.The present invention finishes on the basis of this discovery.
Therefore, another embodiment of the present invention (after this being called second embodiment) relates to a kind of binder composition for mold, and it comprises the phenolic compounds by following formula (1), (2) or (3) expression as main component, the bis-phenol of following formula (4) expression and the alkalescent phenol resin that the aldehyde compound copolycondensation obtains. In formula (1), R 1And R 2Represent hydrogen atom respectively or contain the alkyl of 2 or 2 following carbon atoms.
Figure C9410392100081
In formula (2), R 3Expression hydrogen atom, hydroxyl or contain the alkyl of 2 or 2 following carbon atoms.
Figure C9410392100082
In formula (3), R 4Expression contains the aliphatic group or the aryl radical of 3 or 3 above carbon atoms, preferably contains the aliphatic group or the aryl radical of 3-9 carbon atom, more preferably contains the aliphatic group of 3-9 carbon atom.
Figure C9410392100083
In formula (4), X represents R 5-C-R 6, S, O or O=S=O, at this R 5And R 6Represent hydrogen atom, trifluoromethyl respectively, contain saturated or unsaturated alkyl or their derivative or the phenyl or derivatives thereof of 1-6 carbon atom; R 7And R aRepresent hydrogen atom respectively, contain saturated or unsaturated alkyl or their derivative or the phenyl or derivatives thereof of 1-6 carbon atom.
In addition, second embodiment of the present invention also relates to the method for producing mold, comprises the refractory particle material mixed with this adhesive composition obtaining mixed sand, with this mixed sand model of packing into, and solidifies this mixed sand.
In order to obtain a kind of adhesive composition that can substantially improve the intensity of the mold that obtains, the present inventor has further carried out extensive studies.Found that the intensity of resulting mold can be improved fully when the binary polymer adhesive that replaces being obtained by a kind of phenol and formaldehyde condensation polymer as adhesive with a kind of ter-polymers phenolic resins that is obtained by specific phenolic compounds, a kind of specific polyhydroxy phenol and a kind of aldehyde compound copolycondensation.The present invention finishes on the basis of this discovery.
Therefore, another embodiment of the present invention (after this being called the 3rd embodiment) relates to a kind of binder composition for mold, comprises the phenolic compounds by following formula (1) expression as main component, the polyhydroxy phenol of following formula (2) expression and the alkalescent phenol resin that the aldehyde compound copolycondensation obtains.
Figure C9410392100091
In formula (1), R 1And R 2Represent hydrogen atom respectively or contain the alkyl of 2 or 2 following carbon atoms.
Figure C9410392100092
In formula (2), R 3Expression hydrogen atom, hydroxyl or contain the alkyl of 2 or 2 following carbon atoms.
In addition, the 3rd embodiment of the present invention also relates to the method for producing mold, comprises the refractory particle material mixed with this adhesive composition obtaining mixed sand, with this mixed sand model of packing into, and solidifies this mixed sand.
The binder composition for mold of first embodiment of the invention contains alkalescent phenol resin as main component.This alkalescent phenol resin is formed by phenolic compounds and/or polyhydroxy phenol, alkyl phenol and aldehyde compound copolycondensation.Phenol adopts a kind of in the polyhydroxy phenol of the phenolic compounds of above-mentioned formula (1) expression and above-mentioned formula (2) expression or their mixture.
The example of the phenolic compounds of formula (1) expression has phenol, cresols, 3,5-xylenol.
The example of the polyhydroxy phenol of formula (2) expression has with benzenediol and catechol.
The alkyl phenol of above-mentioned formula (3) expression mainly has a substituting group in contraposition, be the alkyl or phenyl that contains 3 or 3 above carbon atoms as substituting group.For example nonyl phenol, p-tert-butylphenol, isopropenyl phenol and phenyl phenol, they can use separately, also can be with the mixture of wherein two or more composition.The mixture that contains multiple phenolic compounds also can be used, as cashew nut shell liquid.
The example of aldehyde compound has formaldehyde, paraformaldehyde, furfural, glyoxal, and they can use separately, also can use the mixture of two or more composition wherein.
In the copolycondensation process of phenolic compounds and/or polyhydroxy phenol, alkyl phenol and aldehyde compound, the mol ratio of each compound is preferably as follows.That is the preferred 0.001-1000 of the ratio (mole of phenolic compounds and/or polyhydroxy phenol: the mole of alkyl phenol=1: (0.001-1000)) of the mole of alkyl phenol and the integral molar quantity of phenolic compounds and polyhydroxy phenol.The ratio of the mole of alkyl phenol and the integral molar quantity of phenolic compounds and polyhydroxy phenol is 0.01-90 more preferably.If in alkalescent phenol resin, the ratio of the mole of alkyl phenol and the integral molar quantity of phenolic compounds and polyhydroxy phenol is less than 0.001 or greater than 1000, even use such alkalescent phenol resin, the flowability of mixed sand and model filling capacity also aggravate.The integral molar quantity of phenolic compounds and polyhydroxy phenol wherein is meant the mole of phenolic compounds or polyhydroxy phenol when phenolic compounds and polyhydroxy phenol use separately, be meant the integral molar quantity of phenolic compounds and polyhydroxy phenol when phenolic compounds and polyhydroxy phenol use jointly.
In addition, the preferred 1.0-3.0 of ratio ((mole of the mole of the mole+polyhydroxy phenol of phenolic compounds+alkyl phenol): (mole of aldehyde compound)=1: (1.0-3.0)) of the mole of aldehyde compound and the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol.Specifically, more preferably 1.5-2.0 of the ratio of the mole of aldehyde compound and the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol.If the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol are less than 1.0 in alkalescent phenol resin, the intensity of the mold that then obtains will be tending towards descending.On the other hand, if the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol are greater than 3.0 in alkalescent phenol resin, then the alkalescent phenol resin of Chan Shenging will give out stronger aldehyde flavor, cause the worry that working environment is worsened.Mole at the phenolic compounds of this indication and polyhydroxy phenol is identical with above-mentioned definition.
The copolycondensation of phenolic compounds and/or polyhydroxy phenol, alkyl phenol and aldehyde compound is normally carried out in the aqueous solution, obtains the phenolic resins of alkalescence.Reaction is usually 50-100 ℃ of reaction 1-24 hour.In this reaction, aldehyde compound preferably drips gradually.The preferred potassium hydroxide of catalyst (KOH) that this reaction is used.Because alkalescent phenol resin of the present invention is mixed with alkaline aqueous solution, therefore the potassium hydroxide of aequum can add during copolycondensation, also can during copolycondensation, add the least possible potassium hydroxide earlier, after copolycondensation is finished, add the potassium hydroxide of aequum then again as catalysts.In addition, NaOH (NaOH) and lithium hydroxide (LiOH) also can add wherein to regulate pH to the basicity that requires with potassium hydroxide after copolycondensation is finished.In the alkaline aqueous solution of alkalescent phenol resin, the integral molar quantity of all alkali is preferably 0.2-1.2 with the ratio of the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol.Solids content in this alkaline aqueous solution, promptly the amount of anhydrous alkalescent phenol resin is preferably 30-75% (weight).
Solids content in this alkaline aqueous solution for example can be measured with the following method, gets this aqueous solution of 2.0g, and the usefulness hot air dryer descended dry 3 hours at 100 ℃, then the weight of weighing dry matter.
The molecular weight of the alkalescent phenol resin of first embodiment of the invention is preferably 500-8000.
The molecular weight of alkalescent phenol resin for example can be measured with the following method.At first in resin to be measured, add an amount of water and form mixture, and with sulfuric acid this mixture that neutralizes.After filtration the precipitate and separate that forms is come out then, and washing, drying.Dried matter is dissolved in the oxolane (THF), measures its molecular weight then.Measurement can be carried out with the GPC method, and makes standard with polystyrene.
The binder composition for mold of second embodiment of the invention contains alkalescent phenol resin as main component.This alkalescent phenol resin is formed by the bis-phenol and the aldehyde compound copolycondensation of phenolic compounds, formula (4) expression.The example of phenolic compounds has the phenolic compounds of following formula (1) expression, the polyhydroxy phenol of following formula (2) expression and the alkyl phenol of following formula (4) expression.These phenolic compounds can use the mixture that also can use two or more composition wherein separately.
Figure C9410392100121
(R in the formula, 1And R 2Represent hydrogen atom respectively or contain the alkyl of 2 or 2 following carbon atoms)
Figure C9410392100122
(R in the formula, 3Expression hydrogen atom, hydroxyl or contain the alkyl of 2 or 2 following carbon atoms.)
Figure C9410392100131
(R in the formula, 4Expression contains the aliphatic group or the aryl radical of 3 or 3 above carbon atoms, preferably contains the aliphatic group or the aryl radical of 3-9 carbon atom, more preferably contains the aliphatic group of 3-9 carbon atom.)
In these phenolic compounds, the example of the phenolic compounds of formula (1) expression has phenol, cresols, 3,5-xylenol.The example of the polyhydroxy phenol of formula (2) expression has resorcinol and catechol.The example of the alkyl phenol of formula (3) expression has nonyl phenol, p-tert-butylphenol, isopropenyl phenol and phenyl phenol.
The example of the bis-phenol of formula (4) expression has bisphenol-A, Bisphenol F, bisphenol-c, bis-phenol E, bisphenol Z, bisphenol S, bisphenol AF, bisphenol-ap, two sec-butyl bisphenol-As, diisopropyl bisphenol-A, 1,1-ethylidene bis-phenol series, Methylethyl methylene bis-phenol series, methyl-isobutyl methylene bis-phenol series, methyl hexyl methylene bis-phenol series, aminomethyl phenyl methylene bis-phenol series and 4,4 '-thiobisphenol.These compounds can use separately, also can use the mixture of two or more composition wherein.
The example of aldehyde compound has formaldehyde, paraformaldehyde, furfural and glyoxal, and they can use separately, also can use the mixture of two or more composition wherein.
In the copolycondensation process of phenolic compounds, bis-phenol and aldehyde compound, the mol ratio of each compound is preferably as follows.That is the preferred 1.0-5.0 of ratio ((mole of the mole+bis-phenol of phenolic compounds): (mole of aldehyde compound)=1: (1.0-5.0)) of the mole of aldehyde compound and the integral molar quantity of phenolic compounds and bis-phenol.More particularly, more preferably 1.5-3.0 of the ratio of the mole of aldehyde compound and the integral molar quantity of phenolic compounds and bis-phenol.If the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds and bis-phenol are less than 1.0 in alkalescent phenol resin, promptly use this alkalescent phenol resin, the intensity of the mold of production will be tending towards can not get sufficient improvement.And if in alkalescent phenol resin, the ratio of the mole of aldehyde compound and the integral molar quantity of phenolic compounds and bis-phenol is greater than 5.0, the alkalescent phenol resin of production will give out stronger aldehyde flavor, cause the worry that working environment is worsened.Bis-phenol and the preferred 0.001-1O00 of phenolic compounds mol ratio, more preferably 0.01-90.If the mol ratio of bis-phenol and phenolic compounds is less than 0.001 or greater than 1000, the intensity of the mold of production is tending towards can not get substantially improving.
The copolycondensation of phenolic compounds, bis-phenol and aldehyde compound is carried out in the aqueous solution usually, to prepare the phenolic resins of alkalescence.For example, the mode in the preferred aqueous solution that adopts phenolic compounds that aldehyde compound with scheduled volume joins scheduled volume gradually and bis-phenol is carried out copolycondensation.This reaction is usually 50-100 ℃ of reaction 1-24 hour.The preferred potassium hydroxide of catalyst (KOH) that this reaction is used.Because alkalescent phenol resin of the present invention is mixed with alkaline aqueous solution, therefore the potassium hydroxide of aequum can add during copolycondensation, also can during copolycondensation, add the least possible potassium hydroxide earlier, after copolycondensation is finished, add the potassium hydroxide of aequum then again as catalysts.In addition, NaOH (NaOH) and lithium hydroxide (LiOH) also can add wherein to regulate its pH to the basicity that requires with potassium hydroxide after copolycondensation is finished.Also can carry out copolycondensation with a kind of acid catalyst earlier, and then use base catalyst,, further carry out copolycondensation as potassium hydroxide.In the alkaline aqueous solution of this alkalescent phenol resin, the integral molar quantity of all alkali is preferably 0.2-1.2 with the ratio of the integral molar quantity of phenolic compounds hydroxyl and bisphenol hydroxy.In alkaline aqueous solution, the concentration of alkalescent phenol resin is preferably 30-7 5% (weight).
The molecular weight of the alkalescent phenol resin of second embodiment of the invention is preferably 500-8000.
The binder composition for mold of third embodiment of the invention contains a kind of alkalescent phenol resin as main component.This alkalescent phenol resin is obtained by phenolic compounds, polyhydroxy phenol and aldehyde compound copolycondensation.Phenolic compounds can adopt independent a kind of in the phenolic compounds of above-mentioned formula (1) expression or with the mixture of wherein two or more composition.The example of the phenolic compounds of formula (1) expression has phenol, cresols, 3,5-xylenol.Polyhydroxy phenol can adopt the compound of above-mentioned formula (2) expression separately, also can use the mixture of two or more composition wherein.The example of the polyhydroxy phenol of formula (2) expression has same benzenediol, catechol, hydroquinones and 1,3,5-trihydroxybenzene.The example of aldehyde compound has formaldehyde, paraformaldehyde, furfural, glyoxal, and they can use separately, also can use the mixture of two or more composition wherein.
In the copolycondensation process of phenolic compounds, polyhydroxy phenol and aldehyde compound, the mol ratio of each compound is preferably as follows.That is, polyhydroxy phenol and the preferred 0.001-1000 of phenolic compounds mol ratio, ((mole of phenol compound): (mole of polyhydroxy phenol)=1: (0.001-1000)).More particularly, more preferably 0.01-90 of polyhydroxy phenol and phenolic compounds mol ratio.If the mol ratio of polyhydroxy phenol and phenolic compounds is less than 0.001 or big son 1000, the intensity of the mold that obtains is tending towards can not get substantially improving.
In addition, the preferred 1.0-3.0 of ratio ((mole of the mole+polyhydroxy phenol of phenolic compounds): (mole of aldehyde compound)=1: (1.0-3.0)) of the mole of aldehyde compound and the integral molar quantity of phenolic compounds and polyhydroxy phenol.More particularly, more preferably 1.5-2.0 of the ratio of the mole of aldehyde compound and the integral molar quantity of phenolic compounds and polyhydroxy phenol.If in alkalescent phenol resin, the mol ratio of aldehyde compound is less than 1.0, and the intensity of the mold that obtains will be tending towards can not get sufficient improvement.And if the mol ratio of aldehyde compound is greater than 3.0, the alkalescent phenol resin that then obtains will give out stronger aldehyde flavor, cause the worry that working environment is worsened.
The copolycondensation of phenolic compounds, polyhydroxy phenol and aldehyde compound is carried out in the aqueous solution usually, to prepare the phenolic resins of alkalescence.Reaction is usually 50-100 ℃ of reaction 1-24 hour.In this reaction, preferred employing drips the mode of aldehyde compound gradually.The preferred potassium hydroxide of catalyst (KOH) that this reaction is used.Alkalescent phenol resin of the present invention is mixed with alkaline aqueous solution, therefore the potassium hydroxide of aequum can add during copolycondensation, also can during copolycondensation, add the least possible potassium hydroxide earlier, after copolycondensation is finished, add the potassium hydroxide of aequum then again as catalysts.In addition, NaOH (NaOH) and lithium hydroxide (LiOH) also can add wherein with potassium hydroxide after copolycondensation is finished, to regulate its pH to the basicity that requires.Also can carry out copolycondensation with a kind of acid catalyst earlier, and then use base catalyst,, further carry out copolycondensation as potassium hydroxide.In the alkaline aqueous solution of alkalescent phenol resin, the integral molar quantity of all alkali is preferably 0.2-1.2 with the ratio of the integral molar quantity of phenolic compounds and polyhydroxy phenol.In this alkaline aqueous solution, the concentration of alkalescent phenol resin is preferably 30-75% (weight).
The present invention's first, second, third embodiment is in the copolycondensation process of preparation alkalescent phenol resin, and alcohol also can be present in the reaction system.By add alcohol in preparation alkalescent phenol resin reaction system of the present invention, the flowability of resulting mixed sand and fillibility can be further improved.
The example of alcohol has the single hydroxyl alcohol that contains 2-10 carbon atom, as ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amylalcohol, isoamyl alcohol, hexanol, enanthol, octanol, nonyl alcohol and decyl alcohol.These alcohol can use separately, also can use the mixture of two or more composition wherein.
The mole of used alcohol is preferably 0.0001-0.5 with the ratio of the integral molar quantity of various phenolic compounds.Various phenolic compounds described here, at the first embodiment middle finger phenolic compounds of the present invention, polyhydroxy phenol and alkyl phenol, at various phenolic compounds of the second embodiment middle finger of the present invention and bis-phenol, at the 3rd embodiment middle finger phenolic compounds and polyhydroxy phenol of the present invention.
The binder composition for mold of first, second, third embodiment of the present invention contains alkalescent phenol resin as main component, also can further contain other following composition, for example preferably contains silane coupling agent, with the further mold that improves gained.Silane coupling agent can use common each kind, especially r-glycidoxypropyltrimewasxysilane, r-aminopropyltriethoxywerene werene, r-(2-amino-ethyl) TSL 8330, N-glycidyl-N, two [3-(trimethoxy silane base) propyl group] amine etc. of N-can use.
The flowability and the model filling capacity that are mixed the mixed sand that obtains by the refractory particle material with binder composition for mold of the present invention can also be further improved by various types of surfactants of adding or organonitrogen compound in this adhesive composition, these surfactants comprise non-ionic surface active agent, cationic surfactant, anion surfactant and amphoteric surfactant, and organonitrogen compound comprises urea, carbamide compound or amide compound.When using reclaimed sand as the refractory particle material, can improve the intensity of the mold that obtains by the salt that in binder composition for mold, adds various polyvalent metals, these polyvalent metal salts comprise calcium chloride and aluminium oxide etc.
When producing mold, generally can adopt the method that forms the self-curing mold or adopt the method that forms the gas-solid mold with adhesive composition of the present invention.In an example that forms the self-curing molding method, the organic ester of 0.1-5 part (weight) is added in 100 parts of (weight) refractory particle materials and with this mixture mixes.To the 0.4-15 part (weight) that wherein adds the alkaline aqueous solution form, the binder composition for mold of the present invention of preferred 0.6-5 part (weight) mixes this mixture again then.With the mixed sand that obtains the like this model of packing into, and leave standstill, this sand is solidified into the self-curing mold thus.In an example that forms the gas-solid molding method, with 0.4-15 part (weight), the binder composition for mold of the present invention of preferred 0.6-5 part (weight) is added in 100 parts of (weight) refractory particle materials, and mixes this mixture with the form of alkaline aqueous solution.With the mixed sand that the obtains model of packing into, carry out gas-solidization by means of being blown into compressed air.By the gas of 0.05-10 part (weight) or the organic ester of aerosol form are blown in this sand, make it obtain solidifying, thereby provide the mold of gas-solidization.Organic ester can use moieties to contain the alkyl methyl esters of 1-3 carbon atom, can preferably use methyl formate.When replacing the gas organic ester to solidify binder composition for mold with carbon dioxide, the an amount of compound that contains oxo-anions be can in this adhesive composition, add, the compound of oxo-anions and the acting in conjunction curing alkalescent phenol resin (JP-A-1-224263) of carbon dioxide contained by this.
The refractory particle material that the production mold is used can use each common kind.For example main quartz sand, chromite sand, zircon sand, olivine ore in sand form, aluminum oxide sand, mullite ore in sand form and the synthetic mullite ore in sand form of forming by quartz.Certainly, mainly by they regeneration or reclaim the sand that sand forms and also can be used as the use of refractory particle material.
The present invention will be described in more detail with reference to the following examples.But the present invention is not limited to this.
[preparation of binder composition for mold aqueous solution 1-1]
The amount of determining by the mol ratio of table shown in the 1-1 joins phenolic compounds and/or polyhydroxy phenol and alkyl phenol in 50% the potassium hydroxide aqueous solution.Stir the mixture to dissolve these compounds.Amount by the mol ratio shown in the table 1-1 is determined joins aldehyde compound in the above-mentioned solution that maintains 80 ℃ gradually.Be reflected at then and continue under 80 ℃ to carry out, reach 2500 up to weight average molecular weight at this reactant mixture neutral and alkali phenolic resins.Weight average molecular weight reaches time of 2500 and determines by the viscosity of detection reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide aqueous solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol.So just made the alkaline aqueous solution of alkalescent phenol resin.In per 100 parts of (heavy) these alkaline aqueous solutions, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare seven kinds of binder composition for mold aqueous solution in above-mentioned mode.The solid content of adhesive composition is 50% (weight) in each adhesive composition aqueous solution.
Table 1-1 embodiment phenolic compounds and hydrocarbyl phenol aldehyde compound mol ratio compactness
/ or the same 1.5 0.400 25.1 embodiment 53 of polyhydroxy phenol a b (mm) embodiment 1 phenol p-tert-butylphenol formaldehyde 1.0 0.001 26.3 embodiment, 2 the same the same 1.5 0.400 26.5 embodiment, 3 the same the same 3.0 990 26.9 embodiment, 4 metacresol nonyl phenols, 5-xylenol isopropyl-phenol formaldehyde/furfural=the same 2.0 50 26.1 Comparative Examples of 9/1 1.5 50 27.0 embodiment, 6 resorcinol nonyl phenol formaldehyde 2.0 0.400 25.3 embodiment, 7 the same phenyl phenols 1 phenol-the same 1.5-29.1
In table 1-1, a is meant the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds, polyhydroxy phenol and alkyl phenol (i.e. (mole of aldehyde compound)/(mole of the mole of the mole+polyhydroxy phenol of phenolic compounds+alkyl phenol)).B is meant the mole of alkyl phenol and the ratio of the integral molar quantity of phenolic compounds and polyhydroxy phenol (i.e. (mole of alkyl phenol)/(mole of the mole+polyhydroxy phenol of phenolic compounds)).A that the back will occur and b definition are the same.
[preparation of binder composition for mold aqueous solution 1-2]
Adopt method preparation seven kind binder composition for mold aqueous solution 1-2s identical with binder composition for mold aqueous solution 1-1, different is that the weight average molecular weight that reaction continues to carry out up at reactant mixture neutral and alkali phenolic resins reaches 1800.
[preparation of binder composition for mold aqueous solution 1-3]
In the preparation of binder composition for mold aqueous solution 1-2, the various alkalescent phenol resin aqueous solution that obtain after per 25 parts (weight) reaction is finished mix with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Can obtain seven kinds of binder composition for mold aqueous solution 1-3 like this.
[preparation of binder composition for mold aqueous solution 1-4]
Phenol joined in 50% the potassium hydroxide aqueous solution and stirring and dissolving.An amount of formaldehyde is joined in the above-mentioned solution that maintains 80 ℃ gradually, and the mol ratio that makes formaldehyde and phenol is 1.5.This is reflected at and continues under 80 ℃ to carry out then, reaches 2500 up to the weight average molecular weight of phenol formaldehyde resin in this reactant mixture.Weight average molecular weight reaches time of 2500 and determines by the viscosity of detection reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the mole of phenol.So just obtained the alkaline aqueous solution of phenol formaldehyde resin.In such aqueous solution of per 100 parts (weight), add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare a kind of binder composition for mold aqueous solution in this way.The solid content of adhesive composition (phenol formaldehyde resin and silane coupling agent) is 50% (weight) in this adhesive composition aqueous solution.
[preparation of binder composition for mold aqueous solution 1-5]
Adopt the method identical to prepare a kind of binder composition for mold aqueous solution 1-5 with binder composition for mold aqueous solution 1-4, different is in the preparation of 1-5, and the weight average molecular weight that reaction continues to carry out up to phenol formaldehyde resin in reactant mixture reaches 1800.
[preparation of binder composition for mold aqueous solution 1-6]
In the preparation of binder composition for mold aqueous solution 1-5, the various phenol formaldehyde resin aqueous solution that obtain after per 25 parts (weight) reaction is finished mix with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Can obtain a kind of binder composition for mold aqueous solution 1-6 like this.
Embodiment 1-7
In 100 parts of (weight) refractory particle material quartz sands, add 0.3 part of (weight) glycerol triacetate as curing agent.Mix this mixture.Add a kind of among seven kinds of 1.5 parts (weight) preceding binder composition for mold aqueous solution 1-1 that has made then, mix the gained mixture and can get seven kinds of mixed sand.Estimate the flowability and the fillibility of each mixed sand with following method.Promptly at a kind of internal diameter 50mm, inner effective length is that the test tube bottom of 100mm is loaded onto a gripper shoe, and each mixed sand is poured in this test tube by the sieve of a 3mm eyelet respectively.The excessive mixed sand that will exceed the edge is struck off, and this test tube that is loaded with material is handled with the leakage tester that GeorgeFischer Ltd. makes then, uses 10kg/cm 2Squeeze pressure compress this mixed sand.Measure the height drop-out value of this mixed sand.This highly falls, and Xmm (=C.B. (compactness)) is as the flowability of this mixed sand and the tolerance of fillibility.The results are shown in Table 1-1.The value of X is low more, represents that the flowability of this mixed sand and fillibility are good more.
Comparative Examples 1
Prepare a kind of mixed sand with the method identical with embodiment 1, different just replace binder composition for mold aqueous solution 1-1 with binder composition for mold aqueous solution 1-4.Estimate the C.B. of this mixed sand.The results are shown in Table 1-1.
Embodiment 8-14
In 100 parts of (weight) refractory particle material quartz sands, add a kind of among seven kinds of 2.0 parts of (weight) previously prepared binder composition for mold aqueous solution 1-2, mix obtaining seven kinds of mixed sand.Estimate the C.B. of each mixed sand with the method identical with embodiment 1.The results are shown in Table 1-2.In table 1-2, various phenolic compounds and/or polyhydroxy phenol and other content are all as showing the explanation of 1-1.
Comparative Examples 2
Prepare a kind of mixed sand with the method identical with embodiment 8, different just replace binder composition for mold aqueous solution 1-2 with binder composition for mold aqueous solution 1-5.Estimate the C.B. of this mixed sand.The results are shown in Table 1-2.
Table 1-2 embodiment phenolic compounds and hydrocarbyl phenol aldehyde compound mol ratio compactness
/ or the same 1.5 0.400 22.1 embodiment 12 3 of polyhydroxy phenol a b (mm) embodiment 8 phenol p-tert-butylphenol formaldehyde 1.0 0.001 23.1 embodiment, 9 the same the same 1.5 0.400 23.3 embodiment, 10 the same the same 3.0 990 23.2 embodiment, 11 metacresol nonyl phenols, 5-xylenol isopropyl-phenol formaldehyde/furfural=the same 2.0 50 24.0 Comparative Examples of 9/1 1.5 50 23.5 embodiment, 13 resorcinol nonyl phenol formaldehyde 2.0 0.400 23.6 embodiment, 14 the same phenyl phenols 2 phenol-the same 1.5-26.4
Embodiment 15-21
In 100 parts of (weight) refractory particle material quartz sands, add a kind of among seven kinds of 3.0 parts of (weight) previously prepared binder composition for mold aqueous solution 1-3, mix obtaining seven kinds of mixed sand.Estimate the C.B. of each mixed sand with the method identical with embodiment 1.The results are shown in Table 1-3.In table 1-3, various phenolic compounds and/or polyhydroxy phenol and other content are all as the explanation among the table 1-1.
Comparative Examples 3
Prepare a kind of mixed sand with the method identical with embodiment 15, different just replace binder composition for mold aqueous solution 1-3 with binder composition for mold aqueous solution 1-6.Estimate the C.B. of this mixed sand.The results are shown in Table 1-3.
Table 1-3 embodiment phenolic compounds and hydrocarbyl phenol aldehyde compound mol ratio compactness
/ or the same 1.5 0.400 22.2 embodiment 19 3 of polyhydroxy phenol a b (mm) embodiment 15 phenol p-tert-butylphenol formaldehyde 1.0 0.001 23.3 embodiment, 16 the same the same 1.0. 400 23.4 embodiment, 17 the same the same 3.0 990 23.4 embodiment, 18 metacresol nonyl phenols, 5-xylenol isopropyl-phenol formaldehyde/furfural=the same 2.0 50 24.2 Comparative Examples of 9/1 1.5 50 23.4 embodiment, 20 resorcinol nonyl phenol formaldehyde 2.0 0.400 23.8 embodiment, 21 the same phenyl phenols 3 phenol-the same 1.5-27.0
Table 1-1 clearly illustrates that to the result who shows 1-3, when with three kinds of compounds, when to be the alkalescent phenol resin that obtains of phenolic compounds and/or polyhydroxy phenol, alkyl phenol and aldehyde compound copolycondensation as the main component of adhesive composition prepared mixed sand, the mixed sand that makes had lower C.B. value than the phenol formaldehyde resin that obtains with phenol and formaldehyde condensation polymer as the mixed sand that the main component of adhesive composition prepares.Therefore, the mixed sand that obtains in the method that is better than aspect mobile and the fillibility by Comparative Examples 1-3 of the mixed sand that makes of the method by embodiment 1-21.
[preparation of binder composition for mold aqueous solution 2-1]
The amount of determining by the mol ratio of table shown in the 2-3 joins phenolic compounds and bis-phenol in 50% the potassium hydroxide aqueous solution.Stirring this mixture all dissolves up to wherein each compound.Amount by the mol ratio shown in the table 2-3 is determined joins aldehyde compound in the above-mentioned solution that maintains 80 ℃ gradually.This is reflected at and continues under 80 ℃ to carry out then, reaches 2500 up to the weight average molecular weight at this reactant mixture neutral and alkali phenolic resins.Weight average molecular weight reaches time of 2500 and determines by the viscosity of detection reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide aqueous solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the integral molar quantity of phenolic compounds and bis-phenol.So just obtained the alkaline aqueous solution of alkalescent phenol resin.In per 100 parts of (weight) these alkaline aqueous solutions, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare ten kinds of binder composition for mold aqueous solution in above-mentioned mode.The solid content of adhesive composition in each adhesive composition aqueous solution (alkalescent phenol resin and silane conjugates) is 50% (weight).
In table 2-3, c refers to the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds and bis-phenol, i.e. ((mole of aldehyde compound)/(mole of the mole+bis-phenol of phenolic compounds)).D refers to the mol ratio of bis-phenol and phenolic compounds, i.e. ((mole of the mole/phenolic compounds of bis-phenol)).Its definition of c that occurs later and d is the same.
[preparation of binder composition for mold aqueous solution 2-2]
Adopt method preparation four kind binder composition for mold aqueous solution 2-2s identical with binder composition for mold aqueous solution 2-1.Different just the mol ratio of phenolic compounds, bis-phenol and aldehyde compound is changed over shown in table 2-1, and the weight average molecular weight that reaction continues to carry out up at reactant mixture neutral and alkali phenolic resins reaches 1800.
[preparation of binder composition for mold aqueous solution 2-3]
In the preparation of binder composition for mold aqueous solution 2-2, the alkalescent phenol resin aqueous solution that obtains after per 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Can obtain four kinds of binder composition for mold aqueous solution 2-3 like this.
[preparation of binder composition for mold aqueous solution 2-4]
Phenol joined in 50% the potassium hydroxide aqueous solution and stirring and dissolving.An amount of formaldehyde is joined in the above-mentioned solution that maintains 80 ℃ gradually, and to make the mol ratio of formaldehyde and phenol be 1.5.This is reflected at and continues under 80 ℃ to carry out then, reaches 2500 up to the weight average molecular weight of phenol formaldehyde resin in this reactant mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the mole of phenol.So just obtained the alkaline aqueous solution of phenol formaldehyde resin.In per 100 parts of (weight) these aqueous solution, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare a kind of binder composition for mold aqueous solution in this mode.The solids content of adhesive composition (phenol formaldehyde resin and silane coupling agent) is 50% (weight) in this adhesive composition aqueous solution.
[preparation of binder composition for mold aqueous solution 2-5]
Bisphenol-A joined in 50% the potassium hydroxide aqueous solution and stirring and dissolving.An amount of formaldehyde is joined in the above-mentioned solution gradually, and the mol ratio that makes formaldehyde and bisphenol-A is 3.0.This is reflected at and continues under 80 ℃ to carry out then, reaches 2500 up to the weight average molecular weight of bisphenol-A formaldehyde resin in this reactant mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the mole of bisphenol-A.So just obtained the alkaline aqueous solution of bisphenol-A formaldehyde resin.In per 100 parts of (weight) these aqueous solution, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare a kind of binder composition for mold aqueous solution in this mode.In this adhesive composition aqueous solution, the solids content of adhesive composition (bisphenol-A formaldehyde resin and silane coupling agent) is 50% (weight).
[preparation of binder composition for mold aqueous solution 2-6]
Adopt the method identical to prepare a kind of binder composition for mold aqueous solution 2-6 with binder composition for mold aqueous solution 2-4, the different just reactions weight average molecular weight that continues to carry out up to phenol formaldehyde resin in reactant mixture reach 1800.
[preparation of binder composition for mold aqueous solution 2-7]
Adopt the method identical to prepare a kind of binder composition for mold aqueous solution 2-7 with binder composition for mold aqueous solution 2-5, the different just reactions weight average molecular weight that continues to carry out up to bisphenol-A formaldehyde resin in reactant mixture reach 1800.
[preparation of binder composition for mold aqueous solution 2-8]
In the preparation of binder composition for mold aqueous solution 2-6, the phenol formaldehyde resin aqueous solution that obtains after 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Obtain a kind of binder composition for mold aqueous solution 2-8 like this.
[preparation of binder composition for mold aqueous solution 2-9]
In the preparation of binder composition for mold aqueous solution 2-7, the bisphenol-A formaldehyde resin aqueous solution that obtains after 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Obtain a kind of binder composition for mold aqueous solution 2-9 like this.
Embodiment 22-25
In 100 parts of (weight) refractory particle material quartz sands (sand temperature: 10 ℃ or 35 ℃), add a kind of among four kinds of 2.0 parts of (weight) previously prepared binder composition for mold aqueous solution 2-2, mix obtaining four kinds of mixed sand.The gas that each mixed sand is put into the high 50mm of diameter 50mm respectively solidifies in the testing arrangement, injects 1.2 parts of (weight) methyl formates in per 100 parts of (weight) quartz sands, produces mold with this by the gas-solid method.Each mold is measured its compression strength (kg/cm after preparing 24 hours 2).The results are shown in Table 2-1.Compression strength decline degree calculates with following formula: ((sand temperature when the compression strength-sand temperature of mold is at 10 ℃ after 24 hours in the time of 35 ℃ after 24 hours the compression strength of mold)/(sand temperature during at 35 ℃ after 24 hours the compression strength of mold)) * 100.Compression strength decline degree in table 2-2 also is to use this formula to calculate.
Comparative Examples 4-7
Prepare various molds with the method identical with embodiment 22, different just replace binder composition for mold aqueous solution 2-2 with the mixture (Comparative Examples 6 and 7) of binder composition for mold aqueous solution 2-6 (Comparative Examples 4), binder composition for mold aqueous solution 2-7 (Comparative Examples 5) or binder composition for mold aqueous solution 2-6 and 2-7.Compression strength (the kg/cm of mold after 24 hours that obtains with the method evaluation identical with embodiment 22 2) and other character.The results are shown in Table 2-1.
Table 2-1 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio sand temperature compression strength compression strength
Resin 35/10 40.2/22.5 44.0 of the resin of 7 100 parts of (W) Comparative Examples 4 of resin 35/10 39.1/27.5,29.7 Comparative Examples of the resin of the same 2.0 100 35/10 41.2/33.3 of the same 2.0 50 35/10 38.7/31.7 of c d (C) decline degree (%) embodiment 22 phenol bisphenol-A formaldehyde 2.0 0.440 35/10 38.5/31.8 17.4 embodiment, 23 p-tert-butylphenols 18.1 embodiment, 24 metacresol Bisphenol F 19.2 embodiment 25 phenol bisphenol-A formaldehyde/furfurals=6 100 parts of (W) Comparative Examples 4 of 9/1 2.0 0.400 35/10 23.1/19.4,16.0 Comparative Examples the same 3.0-35/10 43.1/22.1 48.7 Comparative Examples of 4 P-F 1.5-35/10 35.5/28.6,19.4 Comparative Examples 5-bisphenol-As+25 parts of (W) Comparative Examples 5+400 parts of (W) Comparative Examples 5
Embodiment 26-29
In 100 parts of (weight) refractory particle material quartz sands (sand temperature: 10 ℃ or 35 ℃), add a kind of among four kinds of 3.0 parts of (weight) previously prepared binder composition for mold aqueous solution 2-3, mix obtaining four kinds of mixed sand.The gas that each mixed sand is put into the high 50mm of diameter 50mm respectively solidifies in the testing arrangement, leads to carbon dioxide 2 minutes with the speed that 10l/ divides in sand, thereby obtains mold by means of the gas-solid method.Each mold is measured its compression strength (kg/cm after preparing 24 hours 2) and other character.Specific practice is identical with embodiment 22.The results are shown in Table 2-2.Various bisphenol compounds and other content are all with the explanation among the table 2-1 in table 2-2.
Comparative Examples 8-11
Prepare various molds with the method identical with embodiment 26, different just replace binder composition for mold aqueous solution 2-3 with the mixture (Comparative Examples 10 and 11) of binder composition for mold aqueous solution 2-8 (Comparative Examples 8), binder composition for mold aqueous solution 2-9 (Comparative Examples 9) or binder composition for mold aqueous solution 2-8 and 2-9.Compression strength (the kg/cm of mold after 24 hours that obtains with the method evaluation identical with embodiment 26 2) and other character.The results are shown in Table 2-2.
Table 2-2 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio sand temperature compression strength compression strength
C d (℃) resin 35/10 22.8/13.1 42.5 of the resin of 11 100 parts of (W) Comparative Examples 8 of resin 35/10 21.6/15.6,27.8 Comparative Examples of the resin of the same 2.0 100 35/10 31.8/27.0 of the same 2.0 50 35/10 30.2/25.9 of decline degree (%) embodiment 26 phenol bisphenol-A formaldehyde 2.0 0.400 35/10 27.0/23.7 12.2 embodiment, 27 p-tert-butylphenols 14.2 embodiment, 28 metacresol Bisphenol F 15.1 embodiment 29 phenol bisphenol-A formaldehyde/furfurals=10 100 parts of (W) Comparative Examples 8 of 9/1 2.0 0.400 35/10 25.7/21.8,10.2 Comparative Examples the same 3.0-35/10 23.3/12.5 46.5 Comparative Examples of 8 P-F 1.5-35/10 20.1/17.0,15.4 Comparative Examples 9-bisphenol-As+25 parts of (W) Comparative Examples 9+400 parts of (W) Comparative Examples 9
Embodiment 30-39
In 100 parts of (heavy) refractory particle material quartz sands (sand temperature: 25 ℃), add glycerol triacetate by the amount shown in the table 2-3 and make curing agent.Mix this mixture.A kind of with among ten kinds of the binder aqueous solution 2-1 of the previously prepared mold that adds 1.5 parts (weight) then in each mixture mixes obtaining ten kinds of mixed sand.In the curing testing arrangement of the high 50mm of each mixed sand difference load diameter 50mm, produce mold with this method by means of self-curing.After preparing 24 hours, use the mode identical to measure its compression strength (kg/cm to each mold with embodiment 22 2) and other character.The results are shown in Table 2-3.Compression strength decline degree calculates with following formula: ((compression strength of mold during the compression strength of mold during with the more multiple curing agent-more a spot of curing agent of usefulness)/(compression strength of mold during the more multiple curing agent of usefulness)) * 100.Compression strength decline degree in table 2-4 to 2-6 also is to use this formula to calculate.
Table 2-3 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio curing agent compression strength compression strength
c d ( ) ( ％ ) 30 A 1.0 0.001 0.40/0.25 32.3/30.8 4.631 2.0 0.400 0.40/0.25 40.2/38.1 5.232 5.0 990 0.40/0.25 43.5/39.5 9.233 /=9/1 2.0 50 0.40/0.25 39.2/35.4 9.734 2.0 50 0.40/0.25 35.0/31.9 8.935 F 2.0 100 0.40/0.25 36.0/32.8 8.836 C 2.0 0.9 0.40/0.25 29.8/27.7 7.037 E 2.0 0.9 0.40/0.25 31.8/29.5 7.238 A 2.0 4.0 0.40/0.25 32.5/29.7 8.639 Z 2.0 4.0 0.40/0.25 32.0/29.1 9.1
Comparative Examples 12-15
Prepare various molds with the method identical with embodiment 30, different just replace binder composition for mold aqueous solution 2-1 with the mixture (Comparative Examples 14 and 15) of binder composition for mold aqueous solution 2-4 (Comparative Examples 12), binder composition for mold aqueous solution 2-5 (Comparative Examples 13) or binder composition for mold aqueous solution 2-4 and 2-5.Compression strength (the kg/cm of mold after 24 hours that obtains with the method evaluation identical with embodiment 22 2) and other character.The results are shown in Table 2-4.
Table 2-4 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio curing agent compression strength compression strength
C d, (W) decline degree, (%) Comparative Examples 12 phenol-the same 3.0-0.40/0.25 of formaldehyde 1.5-0.40/0.25 28.2/25.3 10.3 Comparative Examples 13-bisphenol-As 44.0/31.7 28.0 Comparative Examples are 14 100 parts, (W) resin of Comparative Examples 12+25 part, (W) 15 100 parts of resin 0.40/0.25 34.2/29.1 14.9 Comparative Examples of Comparative Examples 13, (W) resin of Comparative Examples 12+400 part, (W) the resin 0.40/0.25 41.2/32.3 21.6 of Comparative Examples 13
Embodiment 40-43
In 100 parts of (weight) refractory particle material quartz sands (sand temperature: 35 ℃), add a kind of among four kinds of 2.0 parts of (weight) previously prepared binder composition for mold aqueous solution 2-2, mix obtaining four kinds of mixed sand.Each mixed sand is put into respectively in the gas-solid testing arrangement of the high 50mm of diameter 50mm, in per 100 parts of (weight) these quartz sands, injects methyl formate by the amount shown in the table 2-5, produces mold by the gas curing.Each mold is measured its compression strength (kg/cm after preparing 24 hours 2) and other character.The results are shown in Table 2-5.Various bis-phenols and other content are all with the explanation among the table 2-1 in table 2-5.
Comparative Examples 16-19
Prepare various molds with the method identical with embodiment 40, different just replace binder composition for mold aqueous solution 2-2 with the mixture (Comparative Examples 18 and 19) of binder composition for mold aqueous solution 2-6 (Comparative Examples 16), binder composition for mold aqueous solution 2-7 (Comparative Examples 17) or binder composition for mold aqueous solution 2-6 and 2-7.Compression strength (the kg/cm of mold after 24 hours that obtains with the method evaluation identical with embodiment 22 2) and other character.The results are shown in Table 2-5.
Table 2-5 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio curing agent compression strength compression strength
The resin 1.2/0.6 40.2/20.5 49.0 of the resin of 19 100 parts of (W) Comparative Examples 16 of resin 1.2/0.6 39.1/26.1 33.2 Comparative Examples of the resin of the same 2.0 100 1.2/0.6 41.2/31.4 of the same 2.0 50 1.2/0.6 38.7/29.9 of c d (W) decline degree (%) embodiment 40 phenol bisphenol-A formaldehyde 2.0 0.400 1.2/0.6 38.5/30.3 21.3 embodiment, 41 p-tert-butylphenols 22.7 embodiment, 42 metacresol Bisphenol F 23.8 embodiment 43 phenol bisphenol-A formaldehyde/furfurals=18 100 parts of (W) Comparative Examples 16 of 9/1 2.0 0.400 1.2/0.6 23.1/18.2,21.2 Comparative Examples the same 3.0-1.2/0.6 43.1/20.0 53.6 Comparative Examples of 16 P-F 1.5-1.2/0.6 35.5/27.0,23.9 Comparative Examples 17-bisphenol-As+25 parts of (W) Comparative Examples 17+400 parts of (W) Comparative Examples 17
Embodiment 44-47
In 100 parts of (weight) refractory particle material quartz sands (sand temperature: 35 ℃), add a kind of among four kinds of 3.0 parts of (weight) previously prepared binder composition for mold aqueous solution 2-3, mix obtaining four kinds of mixed sand.Each mixed sand is put into respectively in the gas-solid testing arrangement of the high 50mm of diameter 50mm, with 101/ minute the speed carbon dioxide of logical different time in sand (shown in the table 2-6), thereby obtains mold by means of the gas-solid method.To the compression strength (kg/cm of each mold after the mode identical with embodiment 22 measured its 24 hours 2) and other character.The results are shown in Table 2-6.Various bis-phenols and other content are all with the explanation among the table 2-2 in table 2-6.
Comparative Examples 20-23
Prepare various molds with the method identical with embodiment 44, different just replace binder composition for mold aqueous solution 2-3 with the mixture (Comparative Examples 22 and 23) of binder composition for mold aqueous solution 2-8 (Comparative Examples 20), binder composition for mold aqueous solution 2-9 (Comparative Examples 21) or binder composition for mold aqueous solution 2-8 and 2-9.Compression strength (the kg/cm of mold after 24 hours that obtains with the method evaluation identical with embodiment 22 2) and other character.The results are shown in Table 2-6.
Table 2-6 embodiment phenolic compounds bis-phenol aldehyde compound mol ratio curing agent compression strength compression strength
The resin 2.0/0.5 22.8/12.2 46.5 of the resin of 23 100 parts of (W) Comparative Examples 20 of resin 2.0/0.5 21.6/14.8 31.5 Comparative Examples of the resin of the same 2.0 100 2.0/0.5 31.8/24.4 of the same 2.0 50 2.0/0.5 30.2/23.4 of c d (W) decline degree (%) embodiment 44 phenol bisphenol-A formaldehyde 2.0 0.400 2.0/0.5 27.0/21.7 19.6 embodiment, 45 p-tert-butylphenols 22.5 embodiment, 46 metacresol Bisphenol F 23.3 embodiment 47 phenol bisphenol-A formaldehyde/furfurals=22 100 parts of (W) Comparative Examples 20 of 9/1 2.0 0.400 2.0/0.5 25.7/20.9,18.7 Comparative Examples the same 3.0-2.0/0.5 23.3/11.8 49.4 Comparative Examples of 20 P-F 1.5-2.0/0.5 20.1/15.5,22.9 Comparative Examples 21-bisphenol-As+25 parts of (W) Comparative Examples 21+400 parts of (W) Comparative Examples 21
The result of table 2-1 and table 2-2 clearly illustrates that, when with three kinds of compounds, when to be the ter-polymers alkalescent phenol resin that obtains of phenolic compounds, bis-phenol and aldehyde compound copolycondensation as the main component of adhesive composition prepared mold, the mold that obtains had higher compression strength than the mixture of the binary polymer fluosite that obtains with formaldehyde and a kind of phenol or a kind of bis-phenol polycondensation or bis-phenol formaldehyde resin or these two kinds of resins as the mold that the main component of adhesive composition prepares.The result shows that also resulting mold is lower because of the low compression strength decline degree that causes of sand temperature drop.Therefore, the mold that obtains of the method by embodiment 22-29 has higher compression strength and the lower compression strength decline degree that causes because of the sand temperature drop is low than the mold that the method by Comparative Examples 4-11 obtains.In addition, table 2-3 clearly illustrates that to the result who shows 2-6, uses the mold of the various binder composition for mold aqueous solution preparations of each embodiment than the mold that the various binder composition for mold aqueous solution with each Comparative Examples prepare lower compression strength decline degree to be arranged.Even when the consumption of curing agent also be like this seldom the time.Therefore, the mold that obtains of the method by embodiment 30-47 has higher compression strength than the mold that the method by Comparative Examples 12-23 obtains.
[preparation of binder composition for mold aqueous solution 3-1]
The amount of determining by the mol ratio of table shown in the 3-1 joins phenolic compounds and polyhydroxy phenol in 50% the potassium hydroxide aqueous solution.Stir this mixture and make wherein each compound dissolving.Amount by the mol ratio shown in the table 3-1 is determined joins aldehyde compound in the above-mentioned solution that maintains 70 ℃ gradually.Be reflected at then and continue under 70 ℃ to carry out, reach 2500 up to weight average molecular weight at this reactant mixture neutral and alkali phenolic resins.Weight average molecular weight reaches time of 2500 and determines by the viscosity of measured reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide aqueous solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the integral molar quantity of phenolic compounds and polyhydroxy phenol.So just obtained the alkaline aqueous solution of alkalescent phenol resin.In per 100 parts of (weight) these alkaline aqueous solutions, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare six kinds of binder composition for mold aqueous solution in above-mentioned mode.The solid content of adhesive composition (alkalescent phenol resin and silane coupling agent) is 50% (weight) in each adhesive composition aqueous solution.
The compression strength of table 3-1 embodiment phenolic compounds polyhydroxy phenol aldehyde compound mol ratio mold
E f embodiment 48 phenol resorcinol formaldehydes 3.0 0.001 6.2 33.2 embodiment 49 the same the same 1.5 0.400 7.2 36.2 embodiment, 50 the same the same 1.5 990 9.2 39.2 embodiment, 51 the same catechol formaldehyde/furfurals=9/1 2.0 50 8.9 35.8 embodiment, 52 metacresol resorcinol formaldehydes, 2.0 50 10.2 37.2 embodiment 53 3 after 24 hours after 0.5 hour, the resin 5.1 26.4 of the resin of 27 100 parts of (W) Comparative Examples 24 of resin 3.9 24.8 Comparative Examples of the resin of the same 2.0 0.600 7.3 35.2 Comparative Examples of 5-xylenol hydroquinones 24 phenol-26 100 parts of (W) Comparative Examples 24 of the same 1.5-9.3 30.2 Comparative Examples of the same 1.5-2.2 20.4 Comparative Examples 25-resorcinols+25 parts of (W) Comparative Examples 25+400 parts of (W) Comparative Examples 25
In table 3-1, e refers to the mole of aldehyde compound and the ratio of the integral molar quantity of phenolic compounds and polyhydroxy phenol, i.e. ((mole of aldehyde compound)/(mole of the mole+polyhydroxy phenol of phenolic compounds)).F refers to the mol ratio of polyhydroxy phenol and phenolic compounds, i.e. ((mole of polyhydroxy phenol)/(mole of phenolic compounds)).E that the back will occur and f definition are the same.
[preparation of binder composition for mold aqueous solution 3-2]
Adopt six kinds of binder composition for mold aqueous solution 3-2 of the method identical preparation with binder composition for mold aqueous solution 3-1, the different just reactions weight average molecular weight that continues to carry out up at reactant mixture neutral and alkali phenolic resins reach 1800.
[preparation of binder composition for mold aqueous solution 3-3]
In the preparation of binder composition for mold aqueous solution 3-2, the alkalescent phenol resin aqueous solution that obtains after per 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Can obtain six kinds of binder composition for mold aqueous solution 3-3 like this.
[preparation of binder composition for mold aqueous solution 3-4]
Phenol joined in 50% the potassium hydroxide aqueous solution and stirring and dissolving.An amount of formaldehyde is joined in the above-mentioned solution that maintains 70 ℃ gradually, and the mol ratio that makes formaldehyde and phenol is 1.5.This is reflected at and continues under 70 ℃ to carry out then, reaches 2500 up to the weight average molecular weight of phenol formaldehyde resin in this reactant mixture.Weight average molecular weight reaches time of 2500 and determines by the viscosity of measured reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide aqueous solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the mole of phenol.So just obtained the alkaline aqueous solution of phenol formaldehyde resin.In per 100 parts of (weight) these aqueous solution, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare a kind of binder composition for mold aqueous solution in this mode.The solid content of adhesive composition (phenol formaldehyde resin and silane coupling agent) is 50% (weight) in this adhesive composition aqueous solution.
[preparation of binder composition for mold aqueous solution 3-5]
Resorcinol joined in 50% the potassium hydroxide aqueous solution and stirring and dissolving.An amount of formaldehyde is joined in the above-mentioned solution that maintains 60 ℃ gradually, and the mol ratio that makes formaldehyde and resorcinol is 1.5.This is reflected at and continues under 60 ℃ to carry out then, reaches 2500 up to the weight average molecular weight of resorcinol formaldehyde resin in this reactant mixture.Weight average molecular weight reaches time of 2500 and determines by the viscosity of measured reaction mixture.After reaction is finished, with this reactant mixture cool to room temperature, and add an amount of 50% potassium hydroxide aqueous solution in this mixture, the mole that makes potassium hydroxide is 0.85 with the ratio of the mole of resorcinol.So just obtained the alkaline aqueous solution of resorcinol formaldehyde resin.In per 100 parts of (weight) these aqueous solution, add 0.5 part of (weight) r-glycidoxypropyltrimewasxysilane.Prepare a kind of binder composition for mold aqueous solution in this mode.The solid content of adhesive composition (resorcinol formaldehyde resin and silane coupling agent) is 50% (weight) in this adhesive composition aqueous solution.
[preparation of binder composition for mold aqueous solution 3-6]
Adopt the method identical to prepare a kind of binder composition for mold aqueous solution 3-6 with binder composition for mold aqueous solution 3-4, the different just reactions weight average molecular weight that continues to carry out up to phenol formaldehyde resin in reactant mixture reach 1800.
[preparation of binder composition for mold aqueous solution 3-7]
Adopt the method identical to prepare a kind of binder composition for mold aqueous solution 3-7 with binder composition for mold aqueous solution 3-5, the different just reactions weight average molecular weight that continues to carry out up to resorcinol formaldehyde resin in reactant mixture reach 1800.
[preparation of binder composition for mold aqueous solution 3-8]
In the preparation of binder composition for mold aqueous solution 3-6, the phenol formaldehyde resin aqueous solution that obtains after per 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Obtain a kind of binder composition for mold aqueous solution 3-8 like this.
[preparation of binder composition for mold aqueous solution 3-9]
In the preparation of binder composition for mold aqueous solution 3-7, the resorcinol formaldehyde resin aqueous solution that obtains after per 25 parts (weight) reaction is finished mixes with the potassium hydroxide of 5 parts of (weight) sodium tetraborate decahydrates and 5 parts of (weight) 50%.Obtain a kind of binder composition for mold aqueous solution 3-9 like this.
Embodiment 48-53
Add 0.3 part of (weight) glycerol triacetate as curing agent at 100 parts of (weight) refractory particle material quartz sands.Mix this mixture.And then add a kind of among six kinds of 1.5 parts of (weight) previously prepared binder composition for mold aqueous solution 3-1, mix obtaining six kinds of mixed sand.Each mixed sand is put into respectively in the testing arrangement of the high 50mm of diameter 50mm, produces mold by the self-curing method.To each mold prepare leave standstill 0.5 hour after (being called " after 0.5 hour " among the 3-1) and 24 at table little back (show to be called among the 3-1 " after 24 hours) measured its compression strength (kg/cm respectively 2).The results are shown in Table 3-1.
Comparative Examples 24-27
With the method identical mold that makes preparations for sowing with embodiment 48, different just replace binder composition for mold aqueous solution 3-1 with the mixture (Comparative Examples 26 and 27) of binder composition for mold aqueous solution 3-4 (Comparative Examples 24), binder composition for mold aqueous solution 3-5 (Comparative Examples 25) or binder composition for mold aqueous solution 3-4 and 3-5.Compression strength (the kg/cm of the mold that obtains with the mode evaluation identical with embodiment 48 2).The results are shown in Table 3-1.
Embodiment 54-59
In 100 parts of (weight) refractory particle material quartz sands, add a kind of among six kinds of 2.0 parts of (weight) previously prepared binder composition for mold aqueous solution 3-2, mix obtaining six kinds of mixed sand.Each mixed sand is put into respectively in the gas-solid testing arrangement of the high 50mm of diameter 50mm, injects 0.8 part of (weight) methyl formate in the quartz sand of per 100 parts (weight), thereby produces mold by means of the gas-solid method.To each mold prepare leave standstill 1 minute after after (being called " after 1 minute " among the 3-2) and 24 hours at table (showing to be called " after 24 hours " among the 3-2) measure its compression strength (kg/cm respectively 2).The results are shown in Table 3-2.Various bisphenol compounds and other content are all with the explanation among the table 3-1 in table 3-2.
Comparative Examples 28-31
Prepare various molds with the method identical with embodiment 54, different just replace binder composition for mold aqueous solution 3-2 with the mixture (Comparative Examples 30 and 31) of binder composition for mold aqueous solution 3-6 (Comparative Examples 28), binder composition for mold aqueous solution 3-7 (Comparative Examples 29) or binder composition for mold aqueous solution 3-6 and 3-7.Compression strength (the kg/cm of the mold that obtains with the method evaluation identical with embodiment 48 2).The results are shown in Table 3-2.
The compression strength of table 3-2 embodiment phenolic compounds polyhydroxy phenol aldehyde compound mol ratio mold
E f embodiment 54 phenol resorcinol formaldehydes 3.0 0.001 40.2 50.8 embodiment 55 the same the same 1.5 0.400 41.1 52.1 embodiment, 56 the same the same 1.5 990 43.5 53.4 embodiment, 57 the same catechol formaldehyde/furfurals=9/1 2.0 50 39.2 49.6 embodiment, 58 metacresol resorcinol formaldehydes, 2.0 50 43.4 53.8 embodiment 59 3 after 24 hours after 1 minute, the resin 36.9 38.7 of the resin of 31 100 parts of (W) Comparative Examples 28 of resin 35.2 38.8 Comparative Examples of the resin of the same 2.0 0.600 38.8 48.2 Comparative Examples of 5-xylenol hydroquinones 28 phenol-30 100 parts of (W) Comparative Examples 28 of the same 1.5-38.1 40.2 Comparative Examples of the same 1.5-33.6 38.3 Comparative Examples 29-resorcinols+25 parts of (W) Comparative Examples 29+400 parts of (W) Comparative Examples 29
Embodiment 60-65
Add a kind of among six kinds of 3.0 parts of (weight) previously prepared binder composition for mold aqueous solution 3-3 in 100 parts of (weight) refractory particle material quartz sand, mix obtaining six kinds of mixed sand.Each mixed sand is put into respectively in the gas-solid testing arrangement of the high 50mm of diameter 50mm, leads to carbon dioxide 2 minutes with the speed that 10l/ divides in sand, thereby obtains mold by means of the gas-solid method.Use the mode identical to measure compression strength (kg/cm to each mold with embodiment 54 2).The results are shown in Table 3-3.Various phenolic compounds and other content are all with the explanation among the table 3-1 in table 3-3.
Comparative Examples 32-35
Prepare various molds with the method identical with embodiment 60, different just replace binder composition for mold aqueous solution 3-3 with the mixture (Comparative Examples 34 and 35) of binder composition for mold aqueous solution 3-8 (Comparative Examples 32), binder composition for mold aqueous solution 3-9 (Comparative Examples 33) or binder composition for mold aqueous solution 3-8 and 3-9.Compression strength (the kg/cm of the mold that obtains with the method evaluation identical with embodiment 48 2).The results are shown in Table 3-3.
The compression strength of table 3-3 embodiment phenolic compounds polyhydroxy phenol aldehyde compound mol ratio mold
E f embodiment 60 phenol resorcinol formaldehydes 3.0 0.001 18.2 30.8 embodiment 61 the same the same 1.5 0.400 20.1 31.4 embodiment, 62 the same the same 1.5 990 23.8 33.7 embodiment, 63 the same catechol formaldehyde/furfurals=9/1 2.0 50 19.2 29.5 embodiment, 64 metacresol resorcinol formaldehydes, 2.0 50 20.2 33.7 embodiment 65 3 after 24 hours after 1 minute, the resin 15.2 21.2 of the resin of 35 100 parts of (W) Comparative Examples 32 of resin 11.1 20.9 Comparative Examples of the resin of the same 2.0 0.600 18.9 28.3 Comparative Examples of 5-xylenol hydroquinones 32 phenol-34 100 parts of (W) Comparative Examples 32 of the same 1.5-18.8 22.3 Comparative Examples of the same 1.5-10.3 20.8 Comparative Examples 33-resorcinols+25 parts of (W) Comparative Examples 33+400 parts of (W) Comparative Examples 33
Table 3-1 clearly illustrates that to the result who shows 3-3 and works as with three kinds of compounds, when to be the ter-polymers alkalescent phenol resin that obtains of phenolic compounds, polyhydroxy phenol and aldehyde compound copolycondensation as the main component of adhesive composition prepare mold, the binary polymer polyhydroxy phenol formaldehyde resin that the mold that obtains obtains than the binary polymer phenol formaldehyde resin that obtains with phenol and formaldehyde, with polyhydroxy phenol and formaldehyde or as the mold that the main component of adhesive composition prepares higher compression strength is arranged with the mixture of these two kinds of resins.Therefore, the initial compression strength of the mold that obtains with the method for embodiment 48-65 and the mold height that the compression strength after certain time interval all obtains than the method with Comparative Examples 24-35.
Embodiment 66
With with prepare mold and prepare the binder composition for mold aqueous solution with the same method of binder aqueous solution 2-1, different just add an amount of isopropyl alcohol therein, the mole that makes isopropyl alcohol is 0.005 with the ratio of the integral molar quantity of phenolic compounds and bis-phenol.
Method by embodiment 1-7 prepares mixed sand with this binder composition for mold aqueous solution, and estimates its flowability and fillibility, and the result shows that they have result preferably.
As mentioned above, when with main component of the present invention being the binder composition for mold of specific alkalescent phenol resin and refractory particle material when being mixed with mixed sand, the mixed sand that obtains has good flowability and model filling capacity.Can fully mix owing to have the mixed sand of excellent fluidity, therefore, adhesive composition can reach even the mixing with the refractory particle material.In addition, this mixed sand can closely be put into model, therefore, can avoid the coarse and surface strength deterioration of mould surface that obtains.Therefore,, will avoid taking place as carry sand, burning secretly, penetrate and casting defect such as serious mouse tail, thereby avoid the decline of casting quality when using when producing foundry goods with the mold of binder composition for mold preparation of the present invention.
In addition, use mold that binder composition for mold of the present invention and refractory particle material be mixed with to contain main component and compare with using, have better compression strength as the mold that traditional adhesive composition of phenol formaldehyde resin and/or bis-phenol formaldehyde resin makes.Therefore, when casting with the mold of binder composition for mold preparation of the present invention, during fusion-cast, mould surface is not easy to be etched, thereby can obtain superior in quality foundry goods.
In addition, use binder composition for mold of the present invention even under the less situation of the temperature of refractory particle material consumption lower or curing agent, also can produce the mold of high compressive strength.So just can save before mold production the step that must heat to the refractory particle material, thereby simplify the production process of mold.In addition, the required energy of refractory particle material of heating can save or reduce.Moreover owing to can reduce used sclerosis dosage, so can reduce the use cost of curing agent.Therefore use binder composition for mold of the present invention can make the mold rationalization of production.
In addition, the mold that uses binder composition for mold of the present invention and refractory particle material to be mixed with is compared with the mold that uses the traditional phenolic resins production as various fluosite, not only improved initial compression strength, and improved through the compression strength after the certain time interval.Therefore, when casting in order to the mold of binder composition for mold preparation of the present invention, mould surface is not easy to be etched during fusion-cast, thereby can obtain superior in quality foundry goods.In addition, binder composition for mold of the present invention even more also can produce the mold of high compressive strength at this adhesive composition consumption.Because the binder dosage in the mold can reduce, so during fusion-cast, the gas that produces because of the existence of adhesive will reduce, thereby can produce the mold of the defective of few induced gas like this.
Abovely the present invention is described in detail, but those skilled in the art are easy to find out, under the situation that does not depart from spiritual essence of the present invention and scope, can carry out variations and modifications with reference to some specific embodiments.

Claims (2)

1. binder composition for mold, it contains the polyhydroxy phenol by the phenolic compounds of formula (1) expression and/or formula (2) expression, the alkyl phenol of formula (3) expression and aldehyde compound carried out under 5-100 ℃ of temperature copolycondensation 1-24 hour and the molecular weight that obtains is the alkalescent phenol resin of 500-800, the mole of wherein said alkyl phenol is 0.01-90 with the ratio of the integral molar quantity of described phenolic compounds and described polyhydroxy phenol compound, and the mole of described aldehyde compound and described phenolic compounds, the ratio of the integral molar quantity of described polyhydroxy phenol compound and described alkyl phenol is 1.0-3.0
Figure C9410392100021
In the formula (1), R 1And R 2Represent hydrogen atom respectively or contain the alkyl of 2 or 2 following carbon atoms;
Figure C9410392100022
In the formula (2), R 3Expression hydrogen atom, hydroxyl or contain the alkyl of 2 or 2 following carbon atoms;
Figure C9410392100023
In the formula (3), R 4Expression contains the aliphatic group or the aryl radical of 3 or 3 above carbon atoms.
2. press the adhesive composition of claim 2, wherein further add an amount of single hydroxyl alcohol that contains 2-10 carbon atom in described copolycondensation is excessive, the mole that makes described alcohol is 0.0001-0.5 with the ratio of the integral molar quantity of described phenolic compounds and described bis-phenol.
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AU2010345651B2 (en) * 2010-02-11 2013-11-28 Jinan Shengquan Group Share-Holding Co., Ltd. Phenolic Resin Adhesive Composition
DE102014106178A1 (en) * 2014-05-02 2015-11-05 Ask Chemicals Gmbh Process for the layered construction of bodies comprising refractory base molding material and resoles and molds or cores produced by this process
WO2017090748A1 (en) * 2015-11-27 2017-06-01 花王株式会社 Kit for forming casting mold

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