CN1117514A - Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold - Google Patents
Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold Download PDFInfo
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- CN1117514A CN1117514A CN94115764.4A CN94115764A CN1117514A CN 1117514 A CN1117514 A CN 1117514A CN 94115764 A CN94115764 A CN 94115764A CN 1117514 A CN1117514 A CN 1117514A
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Abstract
The sand composite contains the binder compound and the curing agent, where the binder compound involves (a) the binder containing the acid-curing resin and (b) at least one curing promoting agent 0.5-63.0% (wt.) of the binder compound. This sand composite can increase the curing rate and provide with the casting pattern with high initial strength.
Description
The present invention relates to water injection molding in manufacturing, that especially uses in die is used for the molded adhesive composition of making, be used to pour into a mould the molded composition of making, said composition comprises adhesive composition and specific curing agent composition, be used for the molded sand composition of making, said composition comprises adhesive composition or binding agent/curing agent composition and uses sand composition to make the method for mould.
According to routine, be that granular refractory material such as silica sand are mixed with the binding agent that comprises acid-cured resin and solidifying agent from the manufacturing of die, mixture is packed in the model, and make adhesive cures.
At the commitment of this technology, generally the phosphoric acid of viscous solution is used as the solidifying agent of acid-cured resin.For example, JP-B-39-1543 (term used herein " JP-B " means " Japanese Patent of having examined is open ") discloses and has used acid-cured resin such as acid cure furane resin as binding agent and the solidifying agent that uses aqueous acid such as phosphoric acid as binding agent.JP-A-47-16324 (term used herein " JP-A " means " not examining disclosed Japanese patent application ") discloses use Vanadium Pentoxide in FLAKES (P
2O
5) as solidifying agent.
But, because the solidification rate of conventional binders is generally all low, so the mould intensity (initial intensity) that obtains in the initial stage is low.That is to say,, cause the utilization ratio step-down of model from being charged to of model by taking out the model time that solidified mould need be grown.
In order to overcome these shortcomings, people attempt to increase the consumption of solidifying agent.But, if repeat molded making, use a large amount of phosphoric acid to make solidifying agent simultaneously, phosphoric acid builds up in reclaimed sand in a large number gradually, usually causes pouring defect such as pin hole.In addition, because reclaimed sand because of the phosphoric acid moisture absorption of accumulation, causes the intensity of watering injection molding to reduce.
In view of these reasons, used to have hyperergy and replace phosphoric acid to make solidifying agent with aromatic sulphonic acid such as Phenylsulfonic acid, toluenesulphonic acids or the xylene monosulfonic acid that increases the acid-cured resin solidification rate.But because the heat of mould material, aromatic sulphonic acid is decomposed, and discharges deleterious degradation production such as sulfurous gas thus.Therefore, using aromatic sulphonic acid to make solidifying agent is deleterious to Working environment.
So people attempt to substitute the curing dose that increases or change solidifying agent with another kind of binding agent itself.For example, the JP-A-56-56753 suggestion is incorporated into the soluble phenolic resin type resinox of essentially no monokaryon phenolic compound, double-core phenolic compound or its hydroxymethyl derivative in the furfuryl alcohol.The soluble phenolic resin type resinox that uses the essentially no low-molecular-weight resin of this class to exist can impel polymer to form the required time decreased of reaction as the part binding agent, thereby has improved the mould intensity of initial period.
, the molded adhesive composition of making that is used for that still needs to make mould that high initial intensity is arranged and do not have above-mentioned shortcoming.
Therefore, an object of the present invention is to provide and be used for the molded novel binders composition of making, said composition comprises traditional binding agent and the mould with high initial intensity is provided.
Second purpose of the present invention provides and is used for the molded adhesive composition of making, and it is minimum that the poison gas that said composition discharges during use reaches.
The 3rd purpose of the present invention provides and is used for the molded adhesive composition of making, and said composition can make reclaimed sand reuse and not cause the defective or the loss of strength of watering injection molding.
The 4th purpose of the present invention provides and is used for molded binding agent/curing agent composition of making, and said composition comprises solidifying agent and this class adhesive composition.
The 5th purpose of the present invention provides and is used for the molded sand composition of making, and said composition comprises sand and this class adhesive composition.
Last purpose of the present invention provides the method that adopts this class sand composition to make mould.
It is obvious that these and other objects of the present invention will become in the following detailed description, discovery by the contriver is achieved, the adhesive composition that promptly contains specific curing catalyst contacts the increase that presents solidification rate with solidifying agent, and the mold that provides has the initial intensity of increase.They find also that this class adhesive composition and specific curing agent composition are combined provides a kind of composition, it has the solidification rate of further increase, avoid a large amount of accumulation of phosphorus in reclaimed sand simultaneously, and suppress the generation of poisonous degradation production such as sulfurous gas.The present invention is based on these discoveries and finishes.
Therefore, provided by the inventionly be used for the molded adhesive composition of making and comprise:
(a) contain acid-cured resin binding agent and
(b) being selected from of 0.5～63.0% (weight) (weight by adhesive composition is calculated) by at least a curing catalyst in the compound of structural formula (1) expression:
(1) X wherein
1, X
2Represent hydrogen atom, methyl or ethyl respectively.
The present invention also provides and has been used for molded binding agent/curing agent composition of making, and it comprises:
(ⅰ) adhesive composition comprises:
(a) binding agent of acid-cured resin is arranged; With
(b) 0.5～63.0% (weight) (by the total of binding agent (a) and curing catalyst (b)) is selected from by at least a curing catalyst in the compound of structural formula (1) expression; With
(ⅱ) curing agent composition, it contains by sulphur atom is the P contained compound and the sulfocompound of a kind of like this weight ratio of 0.01～0.7 to the weight ratio of phosphorus atom and sulphur atom gross weight.
The present invention also provides and has been used for the molded sand composition of making, and said composition contains above-mentioned adhesive composition or binding agent/curing agent composition.
The present invention further provides the method that adopts above-mentioned sand composition to make mould.
Being used for the molded adhesive composition of making (hereinafter referred for adhesive composition) comprises (a) and contains the binding agent of acid-cured resin and (b) curing catalyst.
Curing catalyst (b) is by the compound of structural formula (1) expression or two or more the mixture in structural formula (1) compound.The preferred embodiment of structural formula (1) compound comprises 2, the two hydroxymethylfurans of 5-(hereinafter being referred to as two hydroxymethylfurans sometimes), 2,5-dioxygen methyl furan (hereinafter being referred to as two methoxyl methyl furans sometimes), 2, the two ethoxymethyl furans of 5-(hereinafter being referred to as two ethoxymethyl furans sometimes), 2-methylol-5-methoxyl methyl furans, 2-methylol-5-ethoxymethyl furans and 2-methoxyl methyl-5-ethoxymethyl furans.In these compounds, 2, the two hydroxymethylfurans of 5-are most preferred, this is because this compound is than 2 in the promotion process of the curing reaction of the binding agent that contains acid-cured resin, the two methoxyl methyl furans or 2 of 5-, the 5-pair of easier reactions of ethoxymethyl furans.2, the higher level of reactivity of the two hydroxymethylfurans of 5-is to be caused by the methylol that helps curing reaction.More particularly, 2, two methoxyl methyl furans of 5-or analogue reactive relatively poor, this is because of its alkoxyl group formation methylol that in a single day is hydrolyzed, and just helps curing reaction then.Though it is known in the preparation of furane resin, reaction between furfuryl alcohol and the formaldehyde is accompanied by as 2 of initial condensation product, the formation of the two hydroxymethylfurans of 5-is (referring to KOBUNSHI YAKUZAI NYUMON, by Sanyo ChemicalIndustries, Co., Ltd. publish), but do not know as yet this 2, the two hydroxymethylfurans of 5-play the employed curing catalyst effect that is used for acid-cured resin in the mould manufacturing.The compound of structural formula (1) can prepare by disclosed currently known methods, for example, and Blanksma, Rec.Trav.Chim., 29,403 (1910), Middendorp., Rec.Trav.Chim., 38,1 (1919), Newth and Wiggins, Research (London), 3, Suppln.50-1 (1950), or C.A., 44,6848 (1950).
The preferable amount of curing catalyst (b) is 0.5～63.0% (weight) based on adhesive composition weight, preferably be 1.8～50.0% (weight), more preferably be 2.5～50.0% (weight), being most preferably 5.0～40.0% (weight), further preferably is 10.0～40.0% (weight).If the amount of curing catalyst (b) is lower than 0.5% (weight), then the curing reaction of binding agent (a) does not quicken fully, and the initial intensity of resultant mold can not get gratifying improvement.If surpass 63.0% (weight), then the ratio of binding agent (a) diminishes relatively.Thereby curing catalyst (b) is not easy to be dissolved in the binding agent (a), will deposit in adhesive composition.
Adhesive composition contains the acid-cured resin as binding agent (a), and preferred consumption is calculated as 40～99.5% (weight) by the weight of adhesive composition, more preferably is 50～95% (weight), is most preferably 60～90% (weight).Any common acid-cured resin all can use separately or be used in combination with its two or more.The specific examples of available acid-cured resin comprises furfuryl alcohol, furfuryl alcohol/aldehyde polycondensate, phenol/aldehyde polycondensate, melamine/aldehyde polycondensate, urea/aldehyde polycondensate and its mixture.The cocondensation product of two or more of above-mentioned polycondensate also can be used as acid-cured resin.
With the aldehyde of furfuryl alcohol, phenol, melamine or urea polycondensation be common, the example comprises formaldehyde, oxalic dialdehyde and furfural.In these compounds, formaldehyde is preferred among the present invention.
The molecular-weight average of furfuryl alcohol/aldehyde polycondensate is preferably 200～2000, more preferably is 200～1500.When molecular-weight average is lower than 200, the solidification rate step-down of binding agent.It is lower that the initial intensity of the mold that obtains thus will become.On the other hand, when molecular-weight average was higher than 2000, then the viscosity of adhesive composition increased, and the abrasive characteristic of the sand composition that obtains thus reduces, and caused the mold strength that obtains to descend.
With the phenol of aldehyde polycondensation also be common, the example comprises phenol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, the compound of structural formula as follows (2) expression, compound and its two or more mixtures of structural formula as follows (3) expression:
(2) R wherein
1Expression has the alkyl of 1～10 carbon atom,
(3) R wherein
2And R
3Each represents to have the alkyl of 1～10 carbon atom respectively.
Phenol/aldehyde polycondensate will be preferably by preparing in the phenol monomer filling based on 2～40% (weight) ratio of total monomer weight.Like this, in containing gained phenol/aldehyde polycondensate binding agent, be preferably 2～40% (weight) by the unit of phenol monomer derived.If phenol monomer unit content is lower than 2% (weight), then solidification rate slows down relatively, and the initial intensity of the mold that obtains is reduced.If surpass 40% (weight), the viscosity of adhesive composition increases, and has reduced package stability.
The molecular-weight average of phenol/aldehyde polycondensate is preferably 200～3000, more preferably is 200～2000.When molecular-weight average was lower than 200, the solidification rate of binding agent was slack-off, thereby the initial intensity of the mold that obtains becomes lower.On the other hand, when molecular-weight average was higher than 3000, then the viscosity of adhesive composition increased, and the abrasive characteristic of the sand composition that obtains thus reduces, and caused the mold strength that obtains to reduce.
When using urea/aldehyde condensed polymer as acid-cured resin, preferably, it is ratio in given that urea bond is incorporated on the aldehyde.Promptly in adhesive composition, the preferred urea amount that uses is that will to make the ratio of the nitrogen-atoms in the urea source that exists in adhesive composition be 0.1～6.0% (weight) by the total weight of adhesive composition, especially 0.1～4.5% (weight).Urea/aldehyde polycondensate that use has such nitrogen content can improve the final strength of the mold that obtains, if the such amount that is lower than 0.1% (weight) with nitrogen content is used urea, the tendency of then improving final strength is no longer obvious.If surpass so a large amount of use urea of 6.0% (weight) with nitrogen content, then resulting mold has shortcoming, and this is to water the pour mass that injection molding obtains pouring defect such as pin hole are usually arranged because adopt.When the nitrogen content in urea source relate to be urea/aldehyde polycondensate the time, have same preferred nitrogen content to put on other acid-cured resin.The nitrogen content of adhesive composition can be measured by Ke Yedafa.
The molecular-weight average of urea/aldehyde polycondensate is preferably 100～2000, more preferably is 200～1000.If molecular-weight average is lower than 100, the solidification rate of binding agent is low, and the initial strength of the mold that obtains thus becomes lower.On the other hand, if molecular-weight average is higher than 2000, adhesive composition viscosity increases, and the abrasive characteristic of the sand composition that obtains thus reduces, and causes the intensity of the mold that obtains to reduce.
The molecular-weight average of melamine/aldehyde polycondensate is preferably 200～2000, more preferably is 200～1500.If molecular-weight average is lower than 200, the solidification rate of adhesive composition is low, and the initial strength of the mold that obtains thus becomes lower.On the other hand, if molecular-weight average is higher than 2000, adhesive composition viscosity increases, and the abrasive characteristic of the sand composition that obtains thus reduces, and this can make the strength degradation of the gained mold that obtains.
The preferred water-content of adhesive composition of the present invention is 0.5～30.0% (weight) by the total weight of adhesive composition, more preferably is 0.5～10.0% (weight).The water yield is the viscosity that is used to reduce adhesive composition, so that easy handling.If the water yield is lower than 0.5% (weight), then can not reduce the viscosity of adhesive composition fully.The water yield surpasses the curing reaction that 30% (weight) then can hinder acid-cured resin, causes the initial intensity that is not enough to improve the mold that obtains.The water-content of adhesive composition can pass through Fischer (KarlFischer) method and measure.
Can prepare adhesive composition by acid-cured resin such as furfuryl alcohol are mixed with the curing catalyst (b) that contains structural formula (1) compound.The compound of acid-cured resin such as furfuryl alcohol and structural formula (1) can prepare simultaneously, to obtain to contain the binder compound of acid-cured resin and curing catalyst (b).The above-mentioned preferred water yield can provide by adding water, and the water that is produced in the time of perhaps by the preparation acid-cured resin provides.
In case of necessity, adhesive composition of the present invention can also contain various known properties-correcting agent or additive except component (a) with (b).
That adopts above-mentioned adhesive composition moldedly makes following carrying out usually.Adhesive composition of the present invention and the curing agent composition that is used for the cured binders composition are mixed with granular refractory material, and grind the mixture that obtains, be used for the molded sand composition made from preparation.The interpolation order is unrestricted.For example, add adhesive composition earlier, add curing agent composition then, vice versa, or add adhesive composition and curing agent composition simultaneously.Although without limits, the common adhesive composition that adds of per 100 parts of granular refractory materials and the amount of curing agent composition are respectively about 0.6～5 part of weight (being preferably 0.6～3 part of weight) and about 0.2～3 part of weight (being preferably 0.2～2 part of weight).The curing agent composition that adds can contain general additive curing catalyst as is known in advance.
It is common can be used for granular refractory material of the present invention, and the example comprises fresh sand or reclaimed sand, as silica sand (mainly being made up of quartz), chromite sand, zircon sand, olivine sand, alumina sand, mullite sand and mullite synthesizing sand.Reclaimed sand comprises those that are obtained by machinery regeneration or heat regeneration.Machinery regenerated productive rate height, economic and practical, thereby be preferred.This class reclaimed sand is preferably used for the present invention.
Can comprise general P contained compound (as phosphoric acid, condensed phosphoric acid, phosphoric acid ester (methyl-phosphate) and phosphoric acid salt (calcium phosphate or potassium hydrogen phosphate)) in the curing agent composition that adhesive composition of the present invention is used in combination, common sulfocompound (as sulfoacid compound (methylsulfonic acid, ethyl sulfonic acid, sulfocarbolic acid, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid etc.) and sulfuric acid), with and two or more mixtures.Especially P contained compound or its mixture are preferred.When comparing with the sulfur-bearing curing agent composition, the acidity of phosphorus curing agent composition is low, so solidification rate is low, and but then, the toxic gas that produces when injecting mould material is few, thereby is favourable to Working environment.Though the solidification rate of phosphorus curing agent composition is low, by means of the improvement of the solidification rate of the adhesive composition of the present invention own, it can not bring bigger problem.
Further improve solidification rate if desired, advise that the P contained compound that Working environment is good also can quicken the solidified sulfocompound with high acidity and be used in combination.The curative systems that comprises P contained compound and sulfocompound will be referred to as curing agent composition hereinafter.
The P contained compound example that can be used for curing agent composition of the present invention comprises phosphoric acid, condensed phosphoric acid, phosphoric acid ester (as methyl-phosphate or phosphoric acid ethyl ester) and phosphoric acid salt (as calcium phosphate or potassium hydrogen phosphate) and composition thereof.The sulfocompound example that can be used for curing agent composition of the present invention comprises sulfuric acid, methylsulfonic acid, ethyl sulfonic acid, sulfocarbolic acid, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid and composition thereof.
In curing agent composition, P contained compound and sulfocompound are that such ratio of 0.01～0.7 exists in sulphur atom to the weight ratio of the gross weight of phosphorus atom and sulphur atom preferably.In other words, the weight of sulphur atom is preferably 1/99～7/3 of phosphorus atom weight.If sulphur content is lower than this scope, mean that phosphorus content is higher than this scope, phosphorus is easy to a large amount of accumulation in reclaimed sand, cause pouring defect such as pin hole.In addition, sand is because the phosphorus of accumulation and the moisture absorption significantly causes the curing that hinders acid-cured resin.If sulphur content is higher than this scope, then too a large amount of sulfocompounds are easy to cause the release of poisonous degradation production during pouring mould material into, cause Working environment to worsen.Particularly preferably be sulphur atom is adjusted to the weight ratio of the total amount of phosphorus atom and sulphur atom in 0.03～0.6 the scope.
In order further to improve mould intensity, silane coupling agent can be added in the granular refractory material.The example of silane coupling agent comprises γ-(2-amino) aminopropyl methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan and γ-glycidoxypropyltrimewasxysilane.Can earlier silane coupling agent be added in the adhesive composition.
The molded sand composition of making (hereinafter referred is a sand composition) that is used for of preparation generally can be used for producing from the molded mold of making of hard cast thus.Be about to sand composition and be seated in the predetermined model, the reaction by solidifying agent is solidified adhesive composition, and obtains mold.Adhesive composition of the present invention manifests quite high solidification rate, only uses about 30 minutes to 1 hour so that be charged to from model to take out from model.Produce high-quality pour mass in the injection molding by mould material being poured into thus obtained watering.In the mixing of these materials, molded or solidification process, neither need heating also not need cooling, these all steps can at room temperature be carried out.
To set forth the present invention in more detail referring now to embodiment, but should be clear, the present invention is not limited.All umbers and per-cent are unless otherwise indicated all by weight.
Embodiment
Embodiment 1～12 and comparative example 1～3
(as 2, the two hydroxymethylfurans of 5-are (by " 2,5-furans dihydroxymethyl " of Aldrich fine chemistry company production with the curing catalyst shown in the following table 1 with furfuryl alcohol (acid-cured resin); CAS registration number: 1883-75-6)) amount shown in the table 1 of pressing is mixed and the preparation adhesive composition.Add 1 part of adhesive composition and 0.45 part of solidifying agent (70% the toluenesulphonic acids aqueous solution) in 100 parts of silica sand (" No. 5, Kaketsu Fusen "), grinding mixture obtains sand composition.
The sand composition that obtains is seated in the test block framework of diameter 50mm, high 50mm, kept 1 or 24 hour down at 25 ℃.(term " JIS " means according to JIS Z 2604-1976; Japanese Industrial Standards ") measure the ultimate compression strength of thus obtained mould.Gained the results are shown in the following table 1.
Table 1 embodiment curing catalyst ultimate compression strength
The kind amount is after 1 hour after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 11 pairs of hydroxymethylfurans 20.0 of 1 pair of hydroxymethylfurans of embodiment, 0.5 5.1 32.8 embodiment, 2 pairs of hydroxymethylfurans, 2.5 7.3 33.5 embodiment, 3 pairs of hydroxymethylfurans, 5.0 8.8 34.5 embodiment, 4 pairs of hydroxymethylfurans, 7.5 10.2 36.5 embodiment, 5 pairs of hydroxymethylfurans, 10.0 11.4 38.0 embodiment, 6 pairs of hydroxymethylfurans, 20.0 17.7 42.5 embodiment, 7 pairs of hydroxymethylfurans, 30.0 24.8 48.3 embodiment, 8 pairs of hydroxymethylfurans, 40.0 28.1 51.6 embodiment, 9 pairs of hydroxymethylfurans, 50.0 26.8 51.2 embodiment, 10 pairs of hydroxymethylfurans, 60.0 25.6 46.8 embodiment
+ 18.1 43.2
Bi-methoxy methyl 1.5
12 pairs of hydroxymethylfurans 15.0 of furans embodiment
+ 15.5 40.0
Bi-methoxy methyl 1.0
Furans
Table 1 (continuing) embodiment curing catalyst ultimate compression strength
The kind amount is after 1 hour after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 1 pair of hydroxymethylfurans of Comparative Examples, 0.3 3.2 29.8 Comparative Examples 2 do not have 3 pairs of hydroxymethylfurans of-3.2 29.4 Comparative Examples 65.0 because inhomogeneous survey
Shown in table 1 result, when use contained the adhesive composition of curing catalyst of the present invention, the mould intensity after 1 hour increased, and the mould intensity after 24 hours also increases.When the content of solidifying agent is increased when reaching maximum value 50% (weight) gradually by 0.5% (weight), the intensity of mould also increases gradually.When curing catalyst content further increased, mould intensity descended gradually.If curing catalyst content surpasses 65% (weight), it is inhomogeneous that adhesive composition becomes.When curing catalyst content was lower than 0.5% (weight), the improvement of mould intensity was not too big.
Embodiment 13～24 and comparative example 4～6
Except the mixture of the 70% toluenesulphonic acids aqueous solution that adopts equivalent and 85% phosphate aqueous solution as the curing agent composition, prepare test block by embodiment 1～12 identical mode.Measure by the identical method of embodiment 1 gained test block ultimate compression strength its results are shown in the following table 2.
Table 2 embodiment curing catalyst ultimate compression strength
The kind amount is after 1 hour after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 23 pairs of hydroxymethylfurans 20.0 of 13 pairs of hydroxymethylfurans of embodiment, 0.5 5.4 33.5 embodiment, 14 pairs of hydroxymethylfurans, 2.5 7.7 34.2 embodiment, 15 pairs of hydroxymethylfurans, 5.0 9.2 35.1 embodiment, 16 pairs of hydroxymethylfurans, 7.5 10.6 37.3 embodiment, 17 pairs of hydroxymethylfurans, 10.0 11.9 38.6 embodiment, 18 pairs of hydroxymethylfurans, 20.0 18.1 43.3 embodiment, 19 pairs of hydroxymethylfurans, 30.0 25.5 49.1 embodiment, 20 pairs of hydroxymethylfurans, 40.0 29.0 53.0 embodiment, 21 pairs of hydroxymethylfurans, 50.0 27.2 52.0 embodiment, 22 pairs of hydroxymethylfurans, 60.0 25.8 47.4 embodiment
+ 18.4 43.7
Bi-methoxy methyl 1.5
24 pairs of hydroxymethylfurans 15.0 of furans embodiment
+ 16.0 40.6
Bi-methoxy methyl 1.0
Furans
Table 2 (continuing) embodiment curing catalyst ultimate compression strength
The kind amount is after 1 hour after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 4 pairs of hydroxymethylfurans of Comparative Examples, 0.3 3.3 30.4 Comparative Examples 5 do not have 6 pairs of hydroxymethylfurans of-3.0 30.1 Comparative Examples 65.0 because inhomogeneous survey
Shown in table 2 result, when use contained the adhesive composition of curing catalyst of the present invention, the mould intensity after 1 hour increased, and the mould intensity after 24 hours also increases.When the content of curing catalyst is increased when reaching maximum value 40% (weight) gradually by 0.5% (weight), the intensity of mould also increases gradually.When curing catalyst content further increased, mould intensity descended gradually.If curing catalyst content surpasses 65% (weight), it is inhomogeneous that adhesive composition becomes.When curing catalyst content was lower than 0.5% (weight), the improvement of mould intensity was not too big.
The preparation of adhesive composition 1～15
The mixture of preparation furfuryl alcohol or furfuryl alcohol and the acid-cured resin that is selected from furfuryl alcohol/aldehyde polycondensate, phenol/aldehyde polycondensate, melamine/aldehyde polycondensate and urea/aldehyde polycondensate is as binding agent.Use binding agent and other component as shown in table 3 below to prepare adhesive composition 1～15.In this table, the amount of the binding agent that provides, water, curing catalyst and other component is the weight percent calculating by the gross weight of said composition.The nitrogen content that provides is the weight percent calculating according to the nitrogen-atoms of said composition total atom amount.
Being prepared as follows of binding agent such as furfuryl alcohol/aldehyde polycondensate.
Preparation furfuryl alcohol/aldehyde polycondensate:
The chaff alcohols and aldehydes under acidic conditions, is reacted to the specified time according to a conventional method with preparation furfuryl alcohol/aldehyde polycondensate.
Preparation phenol/aldehyde polycondensate:
Under alkaline condition, reaction reaches specific time according to a conventional method with phenol and aldehyde.After reaction is finished, use, obtain phenol/aldehyde polycondensate a toluenesulphonic acids aqueous solution neutralization reaction mixture.
Preparation melamine/aldehyde polycondensate:
Under alkaline condition, reaction reaches the specified time according to a conventional method with melamine and aldehyde.After reaction is finished,, obtain melamine/aldehyde condensate with right-toluenesulphonic acids aqueous solution neutralization reaction mixture.
Preparation urea/aldehyde condensate:
Under alkaline condition, reaction reaches the specified time according to a conventional method with urea and aldehyde.After reaction is finished,, obtain urea/aldehyde polycondensate with right-toluenesulphonic acids aqueous solution neutralization reaction mixture.
In the present invention who comprises this paper embodiment and comparative example, measure various characteristics as follows.
Furfuryl alcohol and structural formula (1) compound is as 2, the content (ratio) of the two hydroxymethylfurans of 5-:
Under following condition, measure by gas chromatographic analysis:
Chromatographic instrument: GC-14A is made by Shimadzu Corporation
Post: PEG-20M Chromosorb WAW DMCS 10%60/80 sieve aperture,
0.5m×3mmφ
Detector: FID carrier gas: He water-content: measure by Fischer's method.Press the content of the monomeric unit (as phenol) of former amount of monomer phenol.Measure with ultraviolet spectrophotometer.Nitrogen content: measure by Ke Yedafa.
Table 3
Component (wt%) 12345 binding agents: furfuryl alcohol 57.5 50.3 61.7 84.4 35.8 furfuryl alcohols/formaldehyde condensation products 22.0 15.7 8.2 3.7 14.5 urea/formaldehyde condensation products-12.9 12.5 5.5 20.1 phenol/formaldehyde condensation products-----melamine/formaldehyde condensation products-----phenol/furfural condensation polymer-----urea/glyoxal condensation polymer-----other component phenol content-----(according to former amount of monomer) of 5.0 6.0 4.0 1.4 6.2 pairs of hydroxymethylfurans of water content (curing accelerator), 15.5 15.1 13.6 5.0 23.4 nitrogen contents-2.5 2.5 0.9 3.8
Table 3 (continuing)
Component (wt%) 6789 10 binding agents: furfuryl alcohol 35.5 43.6 56.7 53.0 46.8 furfuryl alcohols/formaldehyde condensation products 12.4 18.9 6.6 10.2-urea/formaldehyde condensation products 14.3 1.6 11.9 12.2 8.2 phenol/formaldehyde condensation products--8.1--melamine/formaldehyde condensation products---3.0 phenol/furfural condensation polymer-----urea/glyoxal condensation polymer-----12.6 0.7 4.2 3.8 2.2 pairs of hydroxymethylfurans of water content (curing accelerator), 25.2 35.2 12.5 17.8 42.8 nitrogen contents, 3.0 0.3 2.3 2.5 0.7 other component phenol content--4.5--(according to former amount of monomer)
Table 3 (continuing)
Component (wt%) 11 12 13 14 15 binding agents: furfuryl alcohol 58.9 59.4 100.0 74.4 74.8 furfuryl alcohols/formaldehyde condensation products 10.6--18.8-urea/formaldehyde condensation products---17.2 phenol/formaldehyde condensation products-----melamine/formaldehyde condensation products-----phenol/furfural condensation polymer 9.1----urea/glyoxal condensation polymer-3.8 2.3 0.0 6.2 8.0 pairs of hydroxymethylfurans of 6.0---water content (curing accelerator), 17.6 32.3-0.3-nitrogen content-0.5--3.6 other component phenol content 4.5----(according to former amount of monomer)
Embodiment 25～36 and comparative example 7～9
Except using every kind of adhesive composition 1～15, prepare test block by embodiment 1～13 identical method.The ultimate compression strength of the test block that obtains is shown in the following table 4.
Table 4 embodiment adhesive composition ultimate compression strength
After 1 hour after 24 hours
(kg/cm
2) (kg/cm
2) embodiment 25 1 13.8 35.8 embodiment 26 2 13.2 37.7 embodiment 27 3 12.8 40.2 embodiment 28 4 8.5 36.0 embodiment 29 5 13.2 37.0 embodiment 30 6 9.2 36.6 embodiment 31 7 18.7 35.2 embodiment 32 8 13.0 38.7 embodiment 33 9 15.4 38.2 embodiment 34 10 25.1 48.7 embodiment 35 11 14.7 38.0 embodiment 36 12 24.8 47.2 comparative examples 7 13 3.0 29.4 comparative examples 8 14 3.3 27.8 comparative examples 9 15 3.5 30.2
As shown in table 4, when use contains 2 of specified amount, during the adhesive composition of the two hydroxymethylfurans of 5-, the mold that obtains has than higher initial intensity and intensity after gratifying 24 hours, disperses although present some, and this depends on the kind of binding agent.On the contrary, do not contain or contain indivisible 2 when using, during the adhesive composition of the two hydroxymethylfurans of 5-, the intensity of mould after starting stage or 24 hours is all low, and this kind with binding agent has nothing to do.
Embodiment 37～48 and comparative example 10
By being joined in the furfuryl alcohol/formaldehyde condensation products that contains 0.3% pair of hydroxymethylfurans weight by the amount shown in the table 5, the curing catalyst shown in the following table 5 prepares adhesive composition.Except the adhesive composition that uses preparation thus, press embodiment 1～12 identical method and obtain test block.The ultimate compression strength of the test block that obtains is shown in table 5.
Table 5 embodiment curing catalyst ultimate compression strength
The kind amount is after 1 hour after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 47 pairs of hydroxymethylfurans 22.4 of 37 pairs of hydroxymethylfurans of embodiment, 0.5 5.3 29.6 embodiment, 38 pairs of hydroxymethylfurans, 2.5 7.8 30.0 embodiment, 39 pairs of hydroxymethylfurans, 5.0 9.2 31.1 embodiment, 40 pairs of hydroxymethylfurans, 7.5 10.4 32.9 embodiment, 41 pairs of hydroxymethylfurans, 10.2 11.7 34.3 embodiment, 42 pairs of hydroxymethylfurans, 21.7 18.0 38.3 embodiment, 43 pairs of hydroxymethylfurans, 32.5 25.3 43.5 embodiment, 44 pairs of hydroxymethylfurans, 41.8 28.4 47.4 embodiment, 45 pairs of hydroxymethylfurans, 50.3 27.1 46.2 embodiment, 46 pairs of hydroxymethylfurans, 62.1 25.9 42.2 embodiment
+ 18.3 38.9
48 pairs of hydroxymethylfurans 15.0 of bi-methoxy methyl furan 1.5 embodiment
+ 15.7 36.1
10 pairs of hydroxymethylfurans 0.3 3.4 26.9 of bi-methoxy methyl furan 1.0 comparative examples
Shown in table 5 result, when use contained the adhesive composition of curing catalyst of the present invention, the intensity of the mould that obtains after 1 hour and after 24 hours all increased.When the content of curing catalyst is increased when reaching about 40% (weight) of maximum value gradually by 0.5% (weight), the intensity of mould also increases gradually.When the content of curing catalyst further increased, the intensity of mould descended gradually.When curing catalyst content was lower than 0.5% (weight), the improvement of mould intensity was not too big.
Embodiment 49～60 and comparative example 11～13
Except the phosphate aqueous solution that adopts 85% (weight) is done the solidifying agent, prepare test block by the identical method of embodiment 1～12.Different with embodiment 1～12, in these embodiment and comparative example, measure through after 2 hours and the ultimate compression strength of the sample mold that obtained in 24 hours.Gained the results are shown in table 6.
Table 6 embodiment curing catalyst ultimate compression strength
The kind amount is after 2 hours after 24 hours
(wt%) (kg/cm
2) (kg/cm
2) 59 pairs of hydroxymethylfurans 20.0 of 49 pairs of hydroxymethylfurans of embodiment, 0.5 4.2 32.1 embodiment, 50 pairs of hydroxymethylfurans, 2.5 6.0 32.8 embodiment, 51 pairs of hydroxymethylfurans, 5.0 7.2 33.8 embodiment, 52 pairs of hydroxymethylfurans, 7.5 8.3 35.8 embodiment, 53 pairs of hydroxymethylfurans, 10.0 9.3 37.2 embodiment, 54 pairs of hydroxymethylfurans, 20.0 14.5 41.7 embodiment, 55 pairs of hydroxymethylfurans, 30.0 20.3 47.3 embodiment, 56 pairs of hydroxymethylfurans, 40.0 23.0 51.5 embodiment, 57 pairs of hydroxymethylfurans, 50.0 21.9 50.2 embodiment, 58 pairs of hydroxymethylfurans, 60.0 20.9 45.9 embodiment
+ 14.8 42.3
60 pairs of hydroxymethylfurans 15.0 of bi-methoxy methyl furan 1.5 embodiment
+ 12.7 39.2
13 pairs of hydroxymethylfurans of bi-methoxy methyl furan 1.0 comparative examples 11 pairs of hydroxymethylfurans, 0.3 2.6 29.2 comparative examples 12 pairs of hydroxymethylfurans, 0 2.5 28.8 comparative examples 65.0 are because inhomogeneous survey
As shown in table 6, when use contained the adhesive composition of curing catalyst of the present invention, the intensity of the sample mold that obtains after 2 hours and 24 hours all increased.When the content of curing catalyst is increased when reaching maximum value 40% (weight) gradually by 05% (weight), the intensity of mould also increases gradually.When the content of curing catalyst further increased, mould descended by force gradually.When curing catalyst content surpasses 65% (weight), it is inhomogeneous that adhesive composition becomes.When curing catalyst content was lower than 0.5% (weight), the improvement of mould intensity was not too big.Also can see, compare, use phosphoric acid to make solidifying agent and can cause that initial mould intensity (through the intensity after 1～2 hour) reduces with using toluenesulphonic acids.
Embodiment 61～65 and comparative example 14 and 15
Prepare the adhesive composition shown in the following table 7 by binding agent that contains furfuryl alcohol, furfuryl alcohol/formaldehyde condensation products and urea/formaldehyde condensation products and curing catalyst.With 100 parts furans reclaimed sand,, be used for the molded sand composition made from preparation with 0.8 part of adhesive composition and 0.4 part of solidifying agent (the 60% xylene monosulfonic acid aqueous solution) mixing and grinding of preparation thus.Same procedure by embodiment 1～12 adopts sand composition to prepare test block.The ultimate compression strength of this test block is shown in table 7.
Table 7
Be used for the molded adhesive composition of making
Binding agent embodiment furfuryl alcohol furfuryl alcohol/formaldehyde condensation products urea/formaldehyde condensation products
(wt%) (wt%) (wt%) embodiment 61 55.6 5.9 17.5 embodiment 62 46.5 5.9 17.6 embodiment 63 39.7 2.7 18.6 embodiment 64 42.1 2.7 16.2 embodiment 65 35.8 2.8 16.4 comparative examples 14 56.5 5.9 17.6 comparative examples 15 52.8 2.8 16.4
Table 7 (continuing)
Be used for the molded adhesive composition of making
The two hydroxymethylfurans water-contents of curing catalyst ultimate compression strength embodiment number are after 1 hour after 24 hours
(wt%) (wt%) (kg/cm
2) (kg/cm
2) embodiment 61 5.0 16.0 11.8 42.0 embodiment 62 10.0 20.0 10.2 40.1 embodiment 63 15.0 24.0 10.7 38.5 embodiment 64 15.0 24.0 10.9 37.5 embodiment 65 17.0 28.0 8.8 34.2 comparative examples 14 0.0 20.0 3.2 37.3 comparative examples 15 0.0 28.0 0.8 31.6
As shown in table 7, when use contained the adhesive composition of curing catalyst of the present invention, the intensity of the mould that obtains after 1 hour or 24 hours all increased.
Embodiment 66～77 and comparative example 16～18
Preparation contains the curing agent composition of 11.3% sulfuric acid and 38.8% Vanadium Pentoxide in FLAKES.Find that [sulphur/(phosphorus+sulphur)] weight ratio is 0.178.With the amount shown in furfuryl alcohol (acid-cured resin) according to the form below 8 respectively with curing catalyst as 2, the two hydroxymethylfurans of 5-(" 2,5-furans dihydroxymethyl " that produce by Aldrich fine chemistry company; CAS registration number: 1883-75-6) mix, with the preparation adhesive composition.In 100 parts of silica sand, add 0.33 part of curing composition, to wherein adding 0.65 part of adhesive composition, grind the mixture that obtains then, to obtain sand composition.Sand composition is molded in the mould, and the mould that employing obtains obtains pour mass by the weight ratio of mould/molten metal 2.5.Broken then mould, the sand that reclaims is broken in crusher, and in the M type rotation revivifier of making by Nippon Chuzo company limited, regenerate to obtain reclaimed sand.
95 parts of reclaimed sands and 5 parts of fresh sands are mixed, and to the curing agent composition and the adhesive composition of the same amount that wherein adds above-mentioned use, with the preparation sand composition.Repeat 20 apotype manufacturings, cast, recovery and regenerated circulation.Measure the sulfurous gas (SO in the interior Working environment of pouring into a mould of time that circulates 20 times
2) concentration.
The sand composition that adopts 20 regenerated sand by above-mentioned same procedure preparation is seated in is used for the molded model of making, measure from charging through obtaining the ultimate compression strength of mould after 0.5 hour, 1 hour and 24 hours.What obtain the results are shown in table 8.
Table 8
Curing catalyst ultimate compression strength embodiment kind amount is after 0.5 hour after 1 hour after 24 hours
(wt%) (wt%) (kg/cm
2) (kg/cm
2) (kg/cm
2) 76 pairs of hydroxymethylfurans 20.0 of 66 pairs of hydroxymethylfurans of embodiment, 0.5 1.5 5.3 32.8 embodiment, 67 pairs of hydroxymethylfurans, 2.5 2.2 7.6 33.9 embodiment, 68 pairs of hydroxymethylfurans, 5.0 3.8 9.0 34.7 embodiment, 69 pairs of hydroxymethylfurans, 7.5 4.5 9.8 37.0 embodiment, 70 pairs of hydroxymethylfurans, 10.0 4.9 10.6 38.5 embodiment, 71 pairs of hydroxymethylfurans, 20.0 6.2 16.8 43.1 embodiment, 72 pairs of hydroxymethylfurans, 30.0 7.0 23.7 48.6 embodiment, 73 pairs of hydroxymethylfurans, 40.0 9.3 27.6 52.3 embodiment, 74 pairs of hydroxymethylfurans, 50.0 7.1 25.3 50.2 embodiment, 75 pairs of hydroxymethylfurans, 60.0 6.8 23.2 46.8 embodiment
+ 5.7 16.5 43.1
Bi-methoxy methyl 1.0
77 pairs of hydroxymethylfurans 15.0 of furans embodiment
+ 5.0 15.2 40.0
Bi-methoxy methyl 1.0
Furans
Table 8 (continuing)
Curing catalyst ultimate compression strength embodiment kind amount is after 0.5 hour after 1 hour after 24 hours
(wt%) (wt%) (kg/cm
2) (kg/cm
2) (kg/cm
2) 18 pairs of hydroxymethylfurans of 16 pairs of hydroxymethylfurans of comparative example, 0.3 0 2.8 30.2 comparative examples 17--0,2.5 29.8 comparative examples 65.0 are owing to inhomogeneously survey
As shown in table 8, when use contained the adhesive composition of curing catalyst of the present invention, the intensity of the sample mold that obtains after 0.5 hour, 1 hour or 24 hours all increased.When the content of curing catalyst is increased when reaching maximum value 40% (weight) gradually by 0.5% (weight), the intensity of mould also increases gradually.When curing catalyst content further increased, mould intensity descended gradually.When curing catalyst content surpassed 65% (weight), it is inhomogeneous that adhesive composition becomes.When curing catalyst content was lower than 0.5% (weight), the improvement of mould intensity was not too big.
Embodiment 78～83 and reference example 1 and 2
As shown in table 9 below, prepare curing agent composition by sulfocompound and P2O5 as P contained compound.In table 9, watering balance sulfocompound and P contained compound.The sulphur content of curing agent composition, phosphorus content and sulphur also are shown in Table 9 the weight ratio of (sulphur+phosphorus).
Table 9
Contain the S Compound P curing agent composition embodiment number
2O
5Content S content P content S/ (S+P)
(wt%) (wt%) (wt%) for kind content (wt%)
(wt%) embodiment 78 methylsulfonic acids 2.7 15.3 13.95 6.7 0.676
Toluenesulphonic acids 25.0
Sulfuric acid 20.0 embodiment 79 ethyl sulfonic acids 2.0 15.3 3.9 6.7 0.368
Sulfocarbolic acid 14.5
Phenylsulfonic acid 3.2 embodiment 80 sulfocarbolic acids 6.8 30.7 9.25 13.4 0.408
Toluenesulphonic acids 38.6
Xylene monosulfonic acid 4.8 embodiment 81 xylene monosulfonic acids 8.5 30.7 2.9 13.4 0.178
Sulfocarbolic acid 7.8 embodiment 82 Phenylsulfonic acids 19.5 42.4 5.8 18.5 0.239
Sulfuric acid 7.5 embodiment 83 Phenylsulfonic acids 1.0 36.6 0.6 16.0 0.036
Toluenesulphonic acids 2.1
Table 9 (continuing)
Contain the S Compound P curing agent composition embodiment number
2O
5Content S content P content S/ (S+P)
(wt%) (wt%) (wt%) for kind content (wt%)
(wt%) reference example 1 toluenesulphonic acids 0.5 39.9 0.12 17.42 0.007
Sulfuric acid 0.1 reference example 2 Phenylsulfonic acids 48.5 6.1 16.74 2.68 0.862
Toluenesulphonic acids 5.2
Sulfuric acid 18.2
Separately preparation contains two hydroxymethylfurans with the furane resin that nitrogen content is 2.5% (weight) (acid-cured resin) and 15.0% (weight) adhesive composition as curing accelerator.
Except the various curing agent compositions that use table 9, repeat molded being equipped with and the regeneration of sand by the same procedure of embodiment 66～77, the same procedure of press embodiment 66～77 is in 5 ℃ and 35 ℃ final ultimate compression strength of the mould of acquisition of mensuration down.By making 20 regenerated sand after leaving standstill 24 hours under 25 ℃, the environment of 90%RH, the humidity of measuring reclaimed sand absorbs, and measures the moisture content that absorbs in this sand then.In addition, under following stringent condition, measure the SO when molded 20 times
2Generation.
Measure SO
2Generation
Be of a size of in 620mm * 770mm * 530mmh mould and the weight ratio of mould/molten metal is after 2.5 in that mould material is poured into, cover this mould with the wooden case that is of a size of 900mm * 900mm * 900mmh immediately, behind casting complete, in the time of 5 minutes, measure SO with the sensor tube that is arranged on the wooden case top
2Concentration.
Gained the results are shown in following table 10.
Table 10
Ultimate compression strength (kg/cm
2) embodiment humidity absorption SO
2Generation was measured temperature in 0.5 hour 1.0 hours 24 hours
(%
*), (ppm), (℃) embodiment 78 0.21 72.0 3.0 8.9 40.2 5 embodiment 79 0.25 21.0 4.8 9.2 39.3 35 embodiment 80 0.23 47.8 3.2 8.3 40.9 5 embodiment 81 0.27 16.0 5.2 9.9 37.1 35 embodiment 82 0.26 28.0 4.9 9.8 39.5 5 embodiment 83 0.28 3.5 5.2 9.1 38.1 35 reference examples 1 0.45 1.5 0 0.6 11.5 35 reference examples 2 0.18 95.0 2.1 8.0 37.3 5 notes: *: based on sand
Table 9 and table 10 have disclosed when the weight ratio of S/ in the curing agent composition (S+P) is lower than 0.01, and the humidity of reclaimed sand absorbs high, and the ultimate compression strength of the mould that obtains reduces.Surpass 0.7 if also proved the weight ratio of S/ (S+P), Working environment suffers severe exacerbation.
On the other hand, when using the curing agent composition of embodiment 78～83, the humidity of reclaimed sand absorbs little, and the intensity of the mould that obtains increases, and Working environment also is gratifying.
Embodiment 84～95 and comparative example 19～21
Adopt among various adhesive compositions 1～15 and the embodiment 78～83 curing agent composition that uses to prepare test block by the same procedure of embodiment 78～83.The ultimate compression strength of the test block that obtains is shown in the following table 11.
Table 11 ultimate compression strength embodiment adhesive composition 0.5 hour 1 hour 24 hours
(kg/cm
2) (kg/cm
2) (kg/cm
2) embodiment 84 1 4.8 11.3 34.4 embodiment 85 2 4.5 10.8 36.2 embodiment 86 3 4.2 10.5 36.8 embodiment 87 4 3.8 7.0 34.6 embodiment 88 5 4.3 10.8 35.5 embodiment 89 6 4.0 7.5 35.1 embodiment 90 7 5.8 15.3 33.8 embodiment 91 8 4.5 10.6 37.1 embodiment 92 9 5.1 12.7 36.7 embodiment 93 10 6.5 19.8 46.5 embodiment 94 11 4.8 12.1 36.5 embodiment 95 12 6.4 19.6 45.3 comparative examples 19 13 0 3.0 28.2 comparative examples 20 14 0 3.3 26.7 comparative examples 21 15 0 3.5 29.0
As can be seen from Table 11, when use contains 2 of specified amount, during the adhesive composition of the two hydroxymethylfurans of 5-, the initial intensity of the mould that obtains is quite high.Intensity after 24 hours is satisfactory, disperses although show some, and this depends on the acid-cured resin as binding agent.On the contrary, do not contain or contain indivisible 2 using, in the adhesive composition of the two hydroxymethylfurans of 5-, the intensity after the starting stage of mould or 24 hours is low.The kind of this and binding agent is irrelevant.
Adhesive composition of the present invention comprises the compound of structural formula (1) of specified amount as 2, and the two hydroxymethylfurans of 5-are made curing catalyst.2, the methylol groups of the two hydroxymethylfurans of 5-has high reactivity, when contacting with solidifying agent such as phosphoric acid, stands condensation reaction with the methylol groups of binding agent etc., promotes the curing reaction of binding agent thus.In addition, 2,5-bi-methoxy methyl furan or 2, the methoxy group of the two ethoxyl methyl furans of 5-or oxyethyl group group are hydrolyzed to hydroxyl when contacting with solidifying agent such as phosphoric acid, so the hydroxyl that forms promotes the curing reaction of binding agent by above-mentioned identical mode.
The molded solidification rate that has increased binding agent of making that uses adhesive composition of the present invention and carry out makes mold have improved initial intensity.Therefore, after with the sand composition filling model that contains adhesive composition, can from model, take out mould at short notice.This means that being used for the molded model of making can effectively utilize, to obtain improved productivity.In addition, but because by changing the composition accelerated rates of cure of adhesive composition itself, so need not increase the consumption of solidifying agent or use the solidifying agent of a large amount of peracidities.Thereby can in gratifying Working environment, carry out molded making.
The present invention is used for the molded curing agent composition of making and contains sulfocompound and P contained compound by specific sulphur and phosphorus weight ratio, and this is specific for the weight ratio of may command in order to the sulfocompound that improves the solidification rate effect.In molded making, when adhesive composition of the present invention and curing agent composition of the present invention are used in combination with granular refractory material, even also can guarantee the high solidification rate of binding agent when in curing agent composition, using the sulfocompound of reduction, this is because adhesive composition contains curing catalyst.Along with the minimizing of sulfocompound, it is minimum that toxic gas that produces during molded making such as sulfurous gas reach, and avoids aggravating working environment.Compare with independent use P contained compound, P contained compound and sulfocompound are used in combination the necessary amounts that causes reducing P contained compound.The result can avoid in multiple reclaimed sand the accumulation of a large amount of phosphorus, thereby can prevent that reclaimed sand from absorbing a large amount of moisture content, has fundamentally got rid of the possibility that the mould intensity that obtained by reclaimed sand may be lowered.Also can stop in watering injection molding the pouring defect that the existence owing to a large amount of accumulation phosphorus cause such as the development of pin hole.
Although the present invention describes in detail by means of embodiment, for those skilled in the art, under the situation that does not deviate from spirit and scope of the invention, carry out various changes and modification is obvious.
Claims (26)
1, be used for the molded adhesive composition of making, comprise:
(a) contain acid-cured resin binding agent and
(b) based at least a curing catalyst of 0.5～63.0% (weight) of adhesive composition, this curing catalyst is selected from the compound by structural formula (1) expression:
(1) X wherein
1, X
2Each represents hydrogen atom, methyl or ethyl respectively.
2, adhesive composition as claimed in claim 1, the consumption of wherein said curing catalyst are 1.8～50.0% (weight).
3, adhesive composition as claimed in claim 1, wherein said acid-cured resin are to be selected from following a kind of compound at least: furfuryl alcohol, furfuryl alcohol/aldehyde polycondensate, phenol/aldehyde polycondensate, melamine/aldehyde polycondensate and urea/aldehyde polycondensate or be selected from the cocondensation compound of at least two kinds of above-mentioned compounds.
4, the adhesive composition of claim 3, wherein said aldehyde is selected from formaldehyde, oxalic dialdehyde and furfural.
5, the adhesive composition of claim 3, wherein said phenol is selected from: phenol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, by the compound of structural formula (2) expression:
(2) (R wherein
1Representative has the alkyl of 1～10 carbon atom) and by the compound of structural formula (3) expression:
(3) (R wherein
2And R
3Each represents the alkyl with 1～10 carbon atom respectively).
6, the adhesive composition of claim 1, the nitrogen content of wherein said adhesive composition are 0.1～6.0% (weight) based on adhesive composition weight.
7, the adhesive composition of claim 3, wherein said acid-cured resin are by aldehyde and the phenol/aldehyde polycondensate that obtains in the phenol monomer condenses of 2～40% (weight) (based on aldehyde and the monomeric gross weight of phenol) ratio.
8, the adhesive composition of claim 1, the water content of wherein said adhesive composition are based on adhesive composition 0.5～30% (weight).
9, the adhesive composition of claim 1, wherein said curing catalyst is 2, the two hydroxymethylfurans of 5-.
10, being used to pour into a mould molded binding agent/curing agent composition of making comprises:
(ⅰ) adhesive composition comprises:
(a) contain acid-cured resin binding agent and
(b) by at least a curing catalyst that is selected from by the compound of structural formula (1) expression of 0.5～63.0% (weight) of binding agent (a) and curing catalyst (b) gross weight:
(1) X wherein
1, X
2Each represents hydrogen atom, methyl or ethyl respectively; With
(ⅱ) curing agent composition, it contains by sulphur atom is the P contained compound and the sulfocompound of a kind of like this weight ratio of 0.01～0.7 to the weight ratio of phosphorus atom and sulphur atom gross weight.
11, the binding agent/curing agent composition of claim 10, wherein said P contained compound are to be selected from phosphoric acid, phosphoric acid condenses, phosphoric acid ester and phosphatic a kind of compound at least.
12, the binding agent/curing agent composition of claim 10, wherein said sulphur atom is 0.03～0.6 to the weight ratio of the gross weight of phosphorus atom and sulphur atom.
13, the binding agent/curing agent composition of claim 10, the amount of wherein said curing catalyst (b) are 1.8～50.0% (weight) based on binding agent (a) and curing catalyst (b) gross weight.
14, the binding agent/curing agent composition of claim 10, wherein said acid-cured resin are the cocondensation compounds that is selected from a kind of compound of furfuryl alcohol, furfuryl alcohol/aldehyde polycondensate, phenol/aldehyde polycondensate, melamine/aldehyde polycondensate and urea/aldehyde polycondensate at least or is selected from described two kinds of compounds at least.
15, the binding agent/curing agent composition of claim 14, wherein said aldehyde is selected from formaldehyde, oxalic dialdehyde and furfural.
16, the binding agent/curing agent composition of claim 14, wherein said phenol be selected from phenol, Resorcinol, dihydroxyphenyl propane, Bisphenol F, by the compound of structural formula (2) expression:
(2) (R wherein
1Representative has the alkyl of 1～10 carbon atom) and by the compound of structural formula (3) representative:
(3) (R wherein
2And R
3Each represents the alkyl with 1～10 carbon atom respectively).
17, the binding agent/curing agent composition of claim 10, the nitrogen content of wherein said binding agent/curing agent composition are 0.1～6.0% (weight) based on the gross weight of binding agent (a) and curing catalyst (b).
18, the binding agent/curing agent composition of claim 14, wherein said acid-cured resin be by aldehyde with in the phenol/aldehyde polycondensate that obtains based on the phenol monomer condenses of the ratio of 2～40% (weight) of aldehyde and the monomeric gross weight of phenol.
19, the binding agent/curing agent composition of claim 15, the water-content of wherein said binding agent/curing agent composition are 0.5～30% (weight) based on the gross weight of binding agent (a) and curing catalyst (b).
20, the binding agent/curing agent composition of claim 10, wherein said curing catalyst is 2, the two hydroxymethylfurans of 5-.
21, be used for the molded sand composition of making, it comprises granular refractory material, the adhesive composition of claim 1 and the solidifying agent that is used for the cured binders composition.
22, the sand composition of claim 21, wherein said solidifying agent are mixture, P contained compound and vitriolic mixture or P contained compound, sulfoacid compound and the vitriolic mixtures of P contained compound, P contained compound and sulfoacid compound.
23, the sand composition of claim 21, wherein said solidifying agent are to be selected from phosphoric acid, phosphoric acid condenses, phosphoric acid ester and phosphoric acid salt.
24, be used for the molded sand composition of making, it comprises the binding agent/curing agent composition of granular refractory material and claim 10.
25, make the method for mould, comprising:
With the sand composition filling model of claim 21,
Make adhesive cures contained in the sand composition.
26, make the method for mould, comprising:
With the sand composition filling model of claim 24,
Make adhesive cures contained in the sand composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5352173A JP2826588B2 (en) | 1993-12-27 | 1993-12-27 | Binder-curing agent composition for mold molding |
| CN94115764.4A CN1117514A (en) | 1993-12-27 | 1994-08-22 | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5352173A JP2826588B2 (en) | 1993-12-27 | 1993-12-27 | Binder-curing agent composition for mold molding |
| CN94115764.4A CN1117514A (en) | 1993-12-27 | 1994-08-22 | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1117514A true CN1117514A (en) | 1996-02-28 |
Family
ID=37076172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115764.4A Pending CN1117514A (en) | 1993-12-27 | 1994-08-22 | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2826588B2 (en) |
| CN (1) | CN1117514A (en) |
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| CN1052928C (en) * | 1997-10-22 | 2000-05-31 | 沈阳汇亚通铸造材料有限责任公司 | Self-hardening sand curing agent for casting and its preparation |
| CN102470423A (en) * | 2009-07-24 | 2012-05-23 | 哈特尼斯·艾伯特斯法国公司 | Method for producing a body made from a granular mixture |
| CN102665960A (en) * | 2009-12-25 | 2012-09-12 | 花王株式会社 | Binder composition for the formation of self-curing molds |
| CN103237614A (en) * | 2010-12-27 | 2013-08-07 | 花王株式会社 | Binder composition for mold molding |
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| CN108884370A (en) * | 2016-04-01 | 2018-11-23 | 米其林集团总公司 | Aqueous adhesive composition comprising thermosetting resin |
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| JP4672401B2 (en) * | 2005-03-11 | 2011-04-20 | 花王株式会社 | Mold manufacturing method |
| JP5986457B2 (en) * | 2011-08-31 | 2016-09-06 | 花王株式会社 | Self-hardening binder composition for mold making |
-
1993
- 1993-12-27 JP JP5352173A patent/JP2826588B2/en not_active Expired - Lifetime
-
1994
- 1994-08-22 CN CN94115764.4A patent/CN1117514A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1052928C (en) * | 1997-10-22 | 2000-05-31 | 沈阳汇亚通铸造材料有限责任公司 | Self-hardening sand curing agent for casting and its preparation |
| CN102470423A (en) * | 2009-07-24 | 2012-05-23 | 哈特尼斯·艾伯特斯法国公司 | Method for producing a body made from a granular mixture |
| CN102470423B (en) * | 2009-07-24 | 2014-06-18 | 哈特尼斯·艾伯特斯法国公司 | Method for producing a body made from a granular mixture |
| CN102665960B (en) * | 2009-12-25 | 2015-11-25 | 花王株式会社 | Self-curing making molds adhesive composition |
| CN102665960A (en) * | 2009-12-25 | 2012-09-12 | 花王株式会社 | Binder composition for the formation of self-curing molds |
| US8822568B2 (en) | 2009-12-25 | 2014-09-02 | Kao Corporation | Binder composition for self-curing mold formation |
| CN103379971A (en) * | 2010-12-16 | 2013-10-30 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Low-emission cold-setting binder for the foundry industry |
| CN103379971B (en) * | 2010-12-16 | 2015-09-30 | 胡坦斯·阿尔伯图斯化学厂有限公司 | For the low transmitting cold setting adhesive of foundary industry |
| CN103237614A (en) * | 2010-12-27 | 2013-08-07 | 花王株式会社 | Binder composition for mold molding |
| CN103237614B (en) * | 2010-12-27 | 2015-10-14 | 花王株式会社 | Making molds adhesive composition |
| CN103351455A (en) * | 2013-07-16 | 2013-10-16 | 沈阳化工大学 | Low furfuralcohol furan resin preparation method |
| CN105848805A (en) * | 2013-12-25 | 2016-08-10 | 花王株式会社 | Composition for forming mold, method for producing self-curing mold, and kit for forming self-curing mold |
| CN105848805B (en) * | 2013-12-25 | 2018-02-16 | 花王株式会社 | Making molds with composition, from the manufacture method of solidity casting mold and from solidity making molds external member |
| CN108348986A (en) * | 2015-11-27 | 2018-07-31 | 花王株式会社 | Making molds external member |
| CN108884370A (en) * | 2016-04-01 | 2018-11-23 | 米其林集团总公司 | Aqueous adhesive composition comprising thermosetting resin |
| CN109689245A (en) * | 2016-09-08 | 2019-04-26 | 旭有机材株式会社 | Shell mold resin combination and the coated sand obtained using it |
| CN109689245B (en) * | 2016-09-08 | 2020-09-25 | 旭有机材株式会社 | Resin composition for shell mold and resin-coated sand obtained using same |
| CN106734860A (en) * | 2016-12-02 | 2017-05-31 | 陈佩珊 | One kind is based on phosphatic organic casting binder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07185732A (en) | 1995-07-25 |
| JP2826588B2 (en) | 1998-11-18 |
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