WO2010013629A1 - Composition de liant pour formation de moule de coulée et procédé pour produire un moule de coulée utilisant la composition de liant pour formation de moule de coulée - Google Patents

Composition de liant pour formation de moule de coulée et procédé pour produire un moule de coulée utilisant la composition de liant pour formation de moule de coulée Download PDF

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WO2010013629A1
WO2010013629A1 PCT/JP2009/063132 JP2009063132W WO2010013629A1 WO 2010013629 A1 WO2010013629 A1 WO 2010013629A1 JP 2009063132 W JP2009063132 W JP 2009063132W WO 2010013629 A1 WO2010013629 A1 WO 2010013629A1
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Prior art keywords
mass
binder composition
mold
parts
sand
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PCT/JP2009/063132
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English (en)
Japanese (ja)
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康弘 永井
正司 吉村
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群栄化学工業株式会社
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Priority to CN2009801294457A priority Critical patent/CN102105241A/zh
Publication of WO2010013629A1 publication Critical patent/WO2010013629A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/224—Furan polymers

Definitions

  • the present invention relates to a mold forming binder composition capable of improving the strength of a mold, and a mold production method using the mold forming binder composition.
  • a self-hardening mold is known as one of casting molds.
  • the self-hardening mold is obtained by adding and kneading a binder mainly composed of an acid curable resin and a curing agent such as xylene sulfonic acid or phosphoric acid to a refractory granular material such as silica sand. It is manufactured by a method in which sand is filled into a mold and the binder is cured.
  • the acid curable resin is generally a resin mainly composed of furfuryl alcohol, urea, phenol, formaldehyde or the like, and is cured by polycondensation while dehydrating with an acid.
  • the progress of curing of such an acid curable resin is affected by water generated by a dehydration reaction. That is, the surface portion that comes into contact with air tends to undergo a dehydration reaction and tends to harden. Accordingly, the self-hardening mold using the binder mainly composed of the acid curable resin has a difference in the degree of cure between the inside and the surface, and the strength is insufficient.
  • a method of improving the strength of the mold without using sulfuric acid there is a method of blending a chloride such as calcium chloride in a refractory granular material (see Patent Document 1).
  • a chloride such as calcium chloride is used in a powder form to absorb moisture.
  • hydrochloric acid having a curing catalytic action is generated from chloride to promote curing.
  • Patent Document 1 it is necessary to mix the refractory granular material and the chloride in advance using a hopper or the like separately from the production line for obtaining the kneaded sand in order to mix the chloride powder.
  • the manufacturing process has become complicated.
  • the chloride powder has a property of easily absorbing moisture. Therefore, there is a problem that it is difficult to manage in the factory in a powder state, and since it becomes a lump when it absorbs moisture, it is difficult to uniformly mix it in the refractory granular material.
  • the manufacturing method of Patent Document 1 has many inconveniences in manufacturing and is not practical, and has hardly been implemented.
  • Patent Document 1 when using powdered metal chloride, it takes time to generate hydrochloric acid exhibiting a hardening promoting action, thereby improving the initial strength of the mold. I found it difficult to do. Therefore, in order to improve the initial strength of the mold, it is necessary to add the metal chloride to a certain amount or more. However, when the amount of the metal chloride added is large, the amount of hydrochloric acid produced increases, and a decomposition reaction may occur due to excess hydrochloric acid after curing, and the final strength of the mold tends to decrease.
  • hydrochloric acid In order to increase the curing speed, a method of directly adding hydrochloric acid having a curing catalytic action is also conceivable, but hydrochloric acid generates corrosive hydrogen chloride, which is difficult to store in a mold manufacturing factory, and is realistic. It wasn't.
  • the present invention has been made in view of the above circumstances, and is capable of obtaining a mold having a sufficient strength without complicating the production process, and a caking additive for mold making. It aims at obtaining the manufacturing method of the casting_mold
  • the binder composition for mold making of the present invention contains an acid curable resin, water, and a metal chloride, and the acid curable resin is selected from the group consisting of furfuryl alcohol, phenols, and urea. 1 type or 2 types or more and 1 type or 2 types or more of a condensate or a cocondensate of aldehydes, and furfuryl alcohol (IUPAC name: 2-furanomethanol),
  • the said metal is alkaline-earth It is a metal and / or zinc group element.
  • the method for producing a mold of the present invention comprises a step of mixing a binder composition for mold making, a refractory granular material and a curing agent to obtain kneaded sand, filling the kneaded sand into a mold for mold making, It has the process of hardening the binder composition for molding.
  • a refractory granular material is an alumina sand.
  • the strength of the mold can be improved without complicating the process of the mold.
  • a mold having improved mold strength, particularly initial strength can be obtained.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 1 and 2 and Comparative Examples 1 to 4 over time.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 3 to 6 and Comparative Example 1 over time.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 7 to 11 and Comparative Example 1 over time.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 12 to 16 and Comparative Example 3 over time.
  • 6 is a bar graph showing the compressive strength of the test pieces obtained in Examples 17 to 20 and Comparative Example 5 over time.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 21 to 24 and Comparative Example 6 over time.
  • 3 is a bar graph showing the compressive strength of the test pieces obtained in Examples 25 to 28 and Comparative Example 7 over time.
  • binder composition for mold making The binder composition for mold making of the present invention (hereinafter referred to as “binder composition”) is used as a binder when producing a mold, and includes an acid curable resin, water, And containing metal chlorides.
  • An acid curable resin is a substance that is cured by polycondensation with an acid.
  • the acid curable resin one or more of a condensate or a cocondensate of one or two or more selected from the group consisting of furfuryl alcohol, phenols and urea and an aldehyde, and Use one containing furfuryl alcohol.
  • aldehydes examples include formaldehyde, glyoxal, and furfural. You may use these in combination of 2 or more type. However, depending on the type of condensate, when glyoxal or furfural is used alone as an aldehyde, acid curing may not proceed. In such a case, at least formaldehyde may be used as the aldehyde.
  • phenols examples include phenol, cresol, resorcinol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, and bisphenol Z. You may use these in combination of 2 or more type.
  • aldehyde When producing a condensate of furfuryl alcohol and aldehydes, it is preferable to use 0.1 to 1 mol of aldehyde per 1 mol of furfuryl alcohol. If the amount of aldehyde used is 0.1 mol or more, it becomes a condensate with a low degree of polymerization, so that the pot life can be easily set, and if it is 1 mol or less, it becomes a condensate with a high degree of polymerization. The final template strength is improved.
  • the content of nitrogen atoms derived from urea or the like is preferably in the range of 0.1 to 6% by mass per 100% by mass of the total of the acid curable resin and water, and is preferably 0.1 to 4%. More preferably, it is 5 mass%.
  • the nitrogen atom content affects the initial strength and final strength of the template. When the nitrogen atom content is low, the initial strength of the template tends to be high, and when the nitrogen atom content is high, the template is high. The final strength of the steel tends to increase. Accordingly, it is preferable to appropriately adjust the nitrogen atom content as necessary. If the nitrogen atom content is within the above range, a template having a favorable initial strength and final strength can be obtained.
  • the (co) condensate in the following means a condensate and / or a cocondensate.
  • the acid curable resin is in such a form of i) to iv) because a binder composition that can easily set the pot life and can improve the mold strength can be obtained.
  • the ratio of the (co) condensate obtained by condensing urea, furfuryl alcohol and aldehydes in the acid curable resin is preferably 15 to 45% by mass, and preferably 25 to 35% by mass. Is more preferable.
  • the ratio of furfuryl alcohol is preferably 55 to 85% by mass, and more preferably 65 to 75% by mass.
  • the ratio of the condensate of urea and aldehydes in the acid curable resin is preferably 3.5 to 20% by mass, and more preferably 6.9 to 13.5% by mass.
  • the ratio of furfuryl alcohol is preferably 80 to 96.5% by mass, and more preferably 86.5 to 93.1% by mass.
  • the ratio of the (co) condensate obtained by condensing urea, furfuryl alcohol and aldehydes in the acid curable resin is preferably 7.5 to 22.5% by mass, More preferably, the content is 5 to 17.5% by mass.
  • the ratio of the condensate of phenol and aldehyde is preferably 7.5 to 22.5% by mass, and more preferably 12.5 to 17.5% by mass.
  • the ratio of furfuryl alcohol is preferably 55 to 85% by mass, and more preferably 65 to 75% by mass.
  • the ratio of the condensate of phenol and aldehyde in the acid curable resin is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass.
  • the ratio of furfuryl alcohol is preferably 60 to 90% by mass, and more preferably 70 to 80% by mass.
  • the content of the acid curable resin in the binder composition is preferably 2 to 98% by mass, more preferably 70 to 98% by mass, and 81.5 to 94.5% by mass. More preferably it is.
  • the content of the acid curable resin in the binder composition is 2% by mass or more, it is easy to set the pot life and the initial strength of the mold tends to be improved. On the other hand, if it is 98% by mass or less, the final strength of the mold tends to be improved.
  • the binder composition of the present invention contains water.
  • the water includes water derived from the combined water of metal chlorides, water derived from condensed water produced when synthesizing each (co) condensate such as a condensate of urea and aldehydes, an aqueous raw material (for example, All water supplied by formalin, etc.) and any water added separately as needed.
  • the water content in the binder composition is preferably 1 to 25% by mass, and more preferably 3 to 15% by mass. When the content of water in the binder composition is 1% by mass or more, the strength of the mold tends to be easily developed. On the other hand, when it is 25% by mass or less, a significant cost increase of the binder composition can be suppressed.
  • the metal chloride an alkaline earth metal chloride and / or a zinc group element chloride is used. Specific examples include calcium chloride, magnesium chloride, barium chloride, and zinc chloride, and one or more of these are used. Of these, calcium chloride is preferably used because of its low cost and excellent solubility.
  • the content of the metal chloride in the binder composition is preferably 1 to 5% by mass, more preferably 2.5 to 3.5% by mass in terms of anhydride. When the content of the metal chloride is within the above range, both the initial strength and final strength of the mold can be improved. On the other hand, when the content of the metal chloride in the binder composition is less than 1% by mass, it tends to be difficult to obtain the initial strength of the mold. If it exceeds 5% by mass, the initial strength of the mold can be obtained, but the final strength of the mold cannot be maintained. This is presumably because a decomposition reaction occurs in the mold due to excessively generated hydrochloric acid.
  • a silane coupling agent such as N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane may be added for the purpose of improving the strength of the obtained template.
  • the silane coupling agent can be contained in an amount of 0.01 to 3% by mass, and more preferably 0.1 to 1% by mass. When 0.01% by mass or more of the silane coupling agent is contained, the strength of the mold can be improved, and if it is 3% by mass or less, a significant cost increase can be suppressed.
  • the binder composition may contain urea, resorcinol, pyrogallol and the like for the purpose of reducing formaldehyde generated during casting pouring.
  • the total content of these in the binder composition is preferably 0.1 to 3% by mass, and more preferably 0.5 to 1% by mass. If these total content is 0.1 mass% or more, it becomes a binder composition excellent in reduction of formaldehyde, and if it is 3 mass% or less, a significant cost increase can be suppressed.
  • the binder composition of the present invention can be obtained by a general production method.
  • An example of the method for producing the binder composition of the present invention is shown below.
  • a part of the raw material of acid curable resin furfuryl alcohol, aldehydes, urea, phenols, etc.
  • an aqueous sodium hydroxide solution to make it alkaline
  • the temperature is raised to produce a (co) condensate.
  • it is acidified using hydrochloric acid or the like, and after a reaction such as a condensate of urea and aldehyde is allowed to proceed, it is rendered alkaline again, and the remaining acid curable resin raw materials are mixed to obtain an acid curable resin.
  • the binder composition of the present invention contains a metal chloride already dissolved. Therefore, it is not necessary to control the humidity at the mold manufacturing site so that the metal chloride does not absorb moisture. Moreover, it is not necessary to complicate the process for obtaining the kneaded sand.
  • the method for producing a mold according to the present invention comprises a step of mixing a binder composition, a refractory granular material and a curing agent to obtain kneaded sand, filling the kneaded sand into a mold for mold making, A step of curing the binder composition;
  • refractory granular material conventionally known materials such as silica sand, chromite sand, zircon sand, olivine sand, alumina sand, mullite sand, and synthetic mullite sand can be used. Recycled ones can also be used. In particular, it is preferable to use chromite sand, zircon sand, and alumina sand for a portion that requires fire resistance, and among them, it is preferable to use alumina sand that does not cost and has no problem with disposal.
  • the curing agent one or more conventionally known compounds such as sulfonic acid compounds such as xylene sulfonic acid, phosphoric acid compounds, and sulfuric acid can be used.
  • sulfonic acid compounds such as xylene sulfonic acid, phosphoric acid compounds, and sulfuric acid
  • curing agent are mixed.
  • chlorine liberated in the water in the binder composition and a part of the curing agent react to produce hydrochloric acid having a curing catalytic action.
  • the curing rate tends to be higher in the order of hydrochloric acid, sulfuric acid, phosphoric acid compound, and sulfonic acid compound.
  • the curing strength is obtained in the order of sulfonic acid compound, phosphoric acid compound, sulfuric acid and hydrochloric acid. Therefore, in the present invention, it is preferable to use an appropriate curing agent in consideration of the balance between the initial strength and final strength of the mold.
  • the mixing ratio of the refractory granular material, the binder composition and the curing agent in the kneaded sand can be set as appropriate, but the mixing ratio of the binder composition is 0.3 to 2 with respect to 100 parts by mass of the refractory granular material.
  • the amount is preferably 0.5 to 1.5 parts by mass.
  • the mixing ratio of the curing agent is preferably 0.045 to 1.2 parts by mass, and more preferably 0.075 to 0.9 parts by mass. With such a mixing ratio, it is easy to obtain a mold having sufficient strength.
  • the mixing method is not particularly limited as long as it is a general mixing method, and for example, a stirrer or the like can be used.
  • the content of the metal chloride in the kneaded sand having the above mixing ratio is preferably 0.003 to 0.2% by mass, more preferably 0.005 to 0.15% by mass, It is preferable that it is 05 mass% or less.
  • a sufficiently strong mold can be easily obtained, and particularly when it is 0.05% by mass or less, the hydrochloric acid generated by the metal chloride is almost completely cured. All tend to evaporate and tend not to affect the final strength of the mold.
  • the mixing ratio of the binder composition to 100 parts by mass of the refractory granular material is 1 part by mass and the mixing ratio of the curing agent is 0.4 parts by mass
  • the content of metal chloride in the kneaded sand is In order to make it 0.05 mass% or less, what is necessary is just to use the binder composition which contains a metal chloride 5 mass% or less in conversion of an anhydride as a binder composition.
  • a mold is produced from the obtained kneaded sand.
  • a self-hardening mold making method can be employed. That is, when the kneaded sand is filled in a predetermined mold for mold making, the binder composition in the kneaded sand is cured by the action of the curing agent. As a result, a template can be obtained.
  • a binder composition in which metal chlorides are uniformly mixed and dissolved in advance is used.
  • the metal chloride is easily dispersed uniformly throughout the kneaded sand, and the hydrochloric acid generated from the metal chloride improves not only the surface of the mold but also the internal hardening, thereby further improving the strength of the mold. .
  • the metal chloride is in a powder form, it cannot exhibit a curing promoting action, but can be dissolved in water or the like and further contacted with an acid to produce hydrochloric acid to exhibit a curing action.
  • the metal chloride is previously dissolved in the binder composition together with water. Therefore, when a curing agent is added, hydrochloric acid having a reaction for curing can be obtained immediately. For this reason, it is not necessary to add a certain amount or more of metal chloride as in the case of mixing powdered metal chloride. Rather, the initial strength of the mold is reduced while minimizing the addition amount. Can be improved. That is, excessive hydrochloric acid is hardly generated and the final strength tends to be improved.
  • template which improved both initial strength and final strength can also be obtained.
  • the binder composition of the present invention can improve the initial strength of the mold and the strength after a long period of time while improving not only the surface of the mold but also the internal curing. Even when a refractory granular material such as large alumina sand is used, a mold strength equivalent to that obtained when conventional silica sand is used can be obtained. Therefore, even a refractory granular material having a high heat capacity such as alumina sand can be produced.
  • hydrochloric acid having a curing catalytic action is generated in the mold manufacturing process. Therefore, it is possible to reduce the use amount of the curing agent, and it is possible to suppress the use amount of sulfuric acid. If the amount of sulfuric acid used can be reduced in this way, the amount of sulfurous acid gas generated can be greatly reduced, and a better working environment can be obtained. At the same time, the rate of occurrence of hindered spheroidization due to sulfur in the sulfurous acid gas Can also be reduced.
  • composition of the binder composition used in each Example and Comparative Example and each physical property of the obtained mold (test piece) were measured by the following methods.
  • Water content The water content was determined by the moisture test method for chemical products of JIS K 0068.
  • the nitrogen atom content was determined by the titration method of the factory wastewater test method of JIS K 0102.
  • the bulk density of the test pieces obtained in each Example and Comparative Example was determined by the following general formula (I).
  • METLER PM 4000 manufactured by Nippon Shibel Hegner Co., Ltd. was used as an electronic balance used for mass measurement. The bulk density is measured to confirm that the wooden mold is filled with approximately the same mass of kneaded sand.
  • Test piece bulk density (g / cm 3 ) Test piece mass (g) / Test piece volume (cm 3 ) (I)
  • Example 1 Binder composition 859.2 parts by mass of furfuryl alcohol, 47.05 parts by mass of urea, 65.9 parts by mass of paraformaldehyde of 92% by mass, and 2.0 parts by mass of a 15% by mass aqueous sodium hydroxide solution. The mixture was placed in a four-necked flask equipped with a stirrer and allowed to react at 80 ° C. for 1 hour. Then, 3.0 parts by mass of 10% by mass hydrochloric acid was added, and further reacted for 3 hours. Thereafter, 2.0 parts by mass of a 15% by mass aqueous sodium hydroxide solution and 28.84 parts by mass of urea were added and reacted for another 30 minutes.
  • a silane coupling agent N- ⁇ (aminoethyl) ⁇ - 2 parts of aminopropylmethyldimethoxysilane
  • a binder composition (A) comprising (co) condensate obtained by condensing urea, furfuryl alcohol and aldehydes, free furfuryl alcohol and water. 1010 parts by mass were obtained.
  • the water content in 1010 parts by mass of the binder composition (A) was 4.5% by mass, and the nitrogen atom content with respect to the total amount of the acid curable resin and water was 3.5% by mass. It was.
  • binder composition (A) To 96.03 parts by mass of the obtained binder composition (A), 3.97 parts by mass of calcium chloride dihydrate (CaCl 2 .2H 2 O) was mixed and dissolved to obtain a binder composition (B). 100 parts by mass (containing 3% by mass of calcium chloride in terms of anhydride) was obtained.
  • test piece preparation wooden mold having a mold with an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 30 ° C. and a humidity of 35%. After 30 minutes, the test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 1.
  • Example 1 A part of the kneaded sand obtained was filled into a test piece production wooden mold under the same conditions as in Example 1 and cured, and the test piece was taken out after 30 minutes from the start of curing (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 1.
  • Example 2 A test piece was prepared in the same manner as in Example 1 except that alumina sand (Alsand 350 # new sand, manufactured by Cosmo Co., Ltd.) was used instead of silica sand, and 30 minutes from the start of curing in the same manner as in Example 1. The compressive strength and bulk density after 1 hour, 3 hours and 24 hours were measured. The results are shown in Table 1.
  • alumina sand Alsand 350 # new sand, manufactured by Cosmo Co., Ltd.
  • Comparative Example 3 A test piece was prepared in the same manner as in Comparative Example 1 except that alumina sand was used instead of silica sand, and the compressive strength and bulk density after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 1.
  • Comparative Example 4 Test pieces were produced in the same manner as in Comparative Example 2 except that alumina sand was used instead of silica sand, and the compressive strength and bulk density after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 1.
  • Example 1, Comparative Example 1 and Comparative Example 2 using the same silica sand as the refractory granular material are compared.
  • the compression strength after 30 minutes in Comparative Example 2 in which calcium chloride was mixed with silica sand was higher than that in Comparative Example 1 in which no calcium chloride was used, but was not as high as in Example 1. From Table 1 and FIG.
  • Example 2 Comparative Example 3
  • Comparative Example 4 using the same alumina sand as the refractory granular material are compared.
  • the compressive strength after 30 minutes and the compressive strength after 24 hours in Example 2 in which calcium chloride was contained in the binder composition were clearly higher than those of Comparative Example 3 in which no calcium chloride was used. It can be said that the effect of improving the strength is obtained.
  • the compressive strength after 30 minutes and the compressive strength after 24 hours in Comparative Example 4 in which calcium chloride was mixed with alumina sand showed higher values than Comparative Example 3 in which no calcium chloride was used. It was not about two.
  • Example 1 0.03 mass% of calcium chloride is contained in kneaded sand.
  • Comparative Examples 2 and 4 contain 0.03% by mass of calcium chloride in the kneaded sand. That is, the calcium chloride content in the kneaded sand of Examples 1 and 2 and Comparative Examples 2 and 4 is the same. Nevertheless, the compressive strength after 30 minutes and the compressive strength after 24 hours in Examples 1 and 2 are clearly superior to Comparative Examples 2 and 4, respectively. This is because, in Examples 1 and 2, since calcium chloride was previously dissolved in the binder composition, it could react with acid immediately to form hydrochloric acid, and it was easy to obtain compressive strength after 30 minutes. It is thought that.
  • Example 1 it is considered that the compressive strength after 24 hours was easily obtained because calcium chloride in the kneaded sand was easily dispersed uniformly. Furthermore, the compressive strength after 30 minutes in Example 2 is superior to the compressive strength after 30 minutes of Comparative Example 1. That is, when the binder composition of the present invention is used, even when alumina sand having a large heat capacity is used, an initial strength equal to or higher than that obtained when silica sand having a small heat capacity is used by a normal method is obtained. Can be said.
  • Examples 3 to 6 1 part by mass of each of the following binder compositions and 0.4 part by mass of a curing agent (75% by mass aqueous solution containing 67% by mass of xylene sulfonic acid and 8% by mass of sulfuric acid) with respect to 100 parts by mass of silica sand.
  • the kneaded sand of each example was obtained by adding and kneading with a Shinagawa universal stirrer.
  • Example 3 Binder composition (B) (containing 3% by mass of calcium chloride in terms of anhydride).
  • Example 4 Binding agent composition (A) 93.6 parts by mass, 6.4 parts by mass of magnesium chloride hexahydrate (MgCl 2 .6H 2 O) was mixed and dissolved to give 100 parts by mass.
  • Agent composition (C) (containing 3% by mass of magnesium chloride in terms of anhydride).
  • Example 5 Baking agent composition (A): 96.48 parts by mass of 3.52 parts by mass of barium chloride dihydrate (BaCl 2 .2H 2 O) was mixed and dissolved to give 100 parts by mass.
  • Agent composition (D) (containing 3% by mass of barium chloride in terms of anhydride).
  • Example 6 Binder composition (E) (chlorinated) which was prepared by mixing and dissolving 3.0 parts by mass of zinc chloride (ZnCl 2 ) in 97.0 parts by mass of the binder composition (A). Containing 3% by weight of zinc).
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 2.
  • Examples 7 to 11 1 part by mass of each of the following binder compositions and 0.4 part by mass of a curing agent (75% by mass aqueous solution containing 67% by mass of xylene sulfonic acid and 8% by mass of sulfuric acid) with respect to 100 parts by mass of silica sand.
  • the kneaded sand of each example was obtained by adding and kneading with a Shinagawa universal stirrer.
  • Example 7 Binder composition (F) (chlorinated) which was prepared by mixing and dissolving 1.32 parts by mass of calcium chloride dihydrate in 98.68 parts by mass of binder composition (A). 1% by mass of calcium in terms of anhydride).
  • Example 8 Binder composition (G) (100% by mass) by mixing and dissolving 3.97 parts by mass of calcium chloride dihydrate in 96.03 parts by mass of binder composition (A) 3% by mass of calcium in terms of anhydride).
  • Example 9 Binder composition (H) (chlorinated) made by mixing and dissolving 6.62 parts by mass of calcium chloride dihydrate in 93.38 parts by mass of binder composition (A). 5% by mass of calcium in terms of anhydride).
  • Example 10 Binder composition (I) (salt chloride) prepared by mixing and dissolving 10.6 parts by mass of calcium chloride dihydrate in 89.4 parts by mass of binder composition (A). 8% by mass of calcium in terms of anhydride).
  • Example 11 Binder composition (J) (chlorinated) obtained by mixing and dissolving 13.25 parts by mass of calcium chloride dihydrate in 86.75 parts by mass of binder composition (A). 10% by mass of calcium in terms of anhydride).
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 3.
  • Example 12 to 16 Each kneaded sand was obtained in the same manner as in Examples 7 to 11 except that alumina sand was used instead of silica sand. Further, a part of each kneaded sand obtained was filled in a wooden piece for test piece preparation under the same conditions as in Examples 7 to 11 and cured, and each test piece was taken out after 30 minutes from the start of curing (die cutting). 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 4.
  • Example 17 (Binder composition) 47.0 parts by mass of urea, 121.1 parts by mass of a 50% by mass aqueous formaldehyde solution, and 1.2 parts by mass of a 15% by mass aqueous sodium hydroxide solution having a 0.5 liter capacity equipped with a thermometer, a cooler and a stirrer The mixture was placed in a four-necked flask and allowed to react at 80 ° C. for 1 hour, and then 2.5 parts by mass of 10% by mass hydrochloric acid was added and further reacted for 3 hours.
  • the water content in the binder composition (K) 501.35 parts by mass is 10.5% by mass, and the nitrogen atom content with respect to the total amount of the acid curable resin and water is 3.5% by mass. Met.
  • To 96.03 parts by mass of the obtained binder composition (K) 3.97 parts by mass of calcium chloride dihydrate (CaCl 2 .2H 2 O) was mixed and dissolved to obtain a binder composition (L). 100 parts by mass (containing 3% by mass of calcium chloride in terms of anhydride) was obtained.
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compression strength and bulk density of the obtained test pieces were measured after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing. The results are shown in Table 5.
  • Examples 18 to 20 1 part by mass of each of the following binder compositions and 0.4 part by mass of a curing agent (75% by mass aqueous solution containing 67% by mass of xylene sulfonic acid and 8% by mass of sulfuric acid) with respect to 100 parts by mass of silica sand.
  • the kneaded sand of each example was obtained by adding and kneading with a Shinagawa universal stirrer.
  • Example 18 Bonding to 100 parts by mass by mixing and dissolving 6.4 parts by mass of magnesium chloride hexahydrate (MgCl 2 .6H 2 O) in 93.6 parts by mass of the binder composition (K).
  • Agent composition (M) (containing 3% by mass of magnesium chloride in terms of anhydride).
  • Example 19 caking was made by mixing and dissolving 3.52 parts by mass of barium chloride dihydrate (BaCl 2 .2H 2 O) in 96.48 parts by mass of the binder composition (K).
  • Agent composition (N) (containing 3% by mass of barium chloride in terms of anhydride).
  • Example 20 Binder composition (O) (chlorinated) which was prepared by mixing and dissolving 3.0 parts by mass of zinc chloride (ZnCl 2 ) in 97.0 parts by mass of binder composition (K). Containing 3% by weight of zinc).
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 5.
  • Comparative Example 5 and Examples 17 to 20 urea and formaldehyde condensate and furfuryl alcohol are used as the acid curable resin.
  • Table 5 and FIG. 5 in Examples 17 to 20 using the binder composition mixed with metal chloride, the compressive strength after 30 minutes and the compressive strength after 24 hours are both It is clearly higher than Comparative Example 5 using a binder composition in which a metal chloride is not mixed, and it can be said that an effect of improving the strength of the mold is obtained.
  • Table 2 and FIG. 2 described above in which furfuryl alcohol, a condensate of urea and formaldehyde, and furfuryl alcohol are used as the acid curable resin. Therefore, even when urea-formaldehyde condensate and furfuryl alcohol are used as the acid curable resin, it can be said that the effect of improving the initial strength and final strength of the mold can be obtained by adding metal chloride.
  • Example 21 (Binder composition) 861.2 parts by mass of furfuryl alcohol, 47.05 parts by mass of urea, 65.9 parts by mass of paraformaldehyde of 92% by mass, and 2.0 parts by mass of a 15% by mass aqueous sodium hydroxide solution, The mixture was placed in a four-necked flask equipped with a stirrer and allowed to react at 80 ° C. for 1 hour.
  • the content of water in the mixture of 974.1 parts by mass of the phenol / formaldehyde condensate, furfuryl alcohol and water was 4.5% by mass.
  • a binder composition comprising 898.2 parts by mass of a mixture of a product, furfuryl alcohol and water and 3.6 parts by mass of a silane coupling agent (N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane) (P) 1800 parts by mass were obtained.
  • the water content in 1800 parts by mass of the binder composition (P) was 4.5% by mass, and the nitrogen atom content with respect to the total amount of the acid curable resin and water was 1.85% by mass. It was.
  • To 96.03 parts by mass of the obtained binder composition (P) 3.97 parts by mass of calcium chloride dihydrate (CaCl 2 .2H 2 O) was mixed and dissolved, and the binder composition (Q) was dissolved. 100 parts by mass (containing 3% by mass of calcium chloride in terms of anhydride) was obtained.
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 6.
  • Examples 22 to 24 1 part by mass of each of the following binder compositions and 0.4 part by mass of a curing agent (75% by mass aqueous solution containing 67% by mass of xylene sulfonic acid and 8% by mass of sulfuric acid) with respect to 100 parts by mass of silica sand.
  • the kneaded sand of each example was obtained by adding and kneading with a Shinagawa universal stirrer.
  • Example 22 Binding of 100 parts by mass by mixing and dissolving 6.4 parts by mass of magnesium chloride hexahydrate (MgCl 2 .6H 2 O) in 93.6 parts by mass of the binder composition (P).
  • Agent composition (R) (containing 3% by mass of magnesium chloride in terms of anhydride).
  • Example 23 binder composition (P) 96.48 parts by weight of barium chloride dihydrate (BaCl 2 ⁇ 2H 2 O) 3.52 parts by mass were mixed and dissolved, and 100 parts by mass caking Agent composition (S) (containing 3% by mass of barium chloride in terms of anhydride).
  • Example 24 Binder composition (T) (chlorinated) which was prepared by mixing and dissolving 3.0 parts by mass of zinc chloride (ZnCl 2 ) in 97.0 parts by mass of the binder composition (P). Containing 3% by weight of zinc).
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 6.
  • Example 25 (Binder composition) 297.2 parts by mass of furfuryl alcohol, 8.0 parts by mass of urea, 20.64 parts by mass of a 50% by mass aqueous formaldehyde solution, and 0.7 parts by mass of a 15% by mass aqueous sodium hydroxide solution, The mixture was placed in a four-necked flask equipped with a stirrer and allowed to react at 80 ° C. for 1 hour. Then, 1.3 parts by mass of 10% by mass hydrochloric acid was added and further reacted for 3 hours.
  • the content of water in the binder composition (U) 334.4 parts by mass is 4.0% by mass, and the nitrogen atom content with respect to the total amount of the acid curable resin and water is 1.8% by mass. Met.
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 7.
  • Examples 26 to 28 1 part by mass of each of the following binder compositions and 0.4 part by mass of a curing agent (75% by mass aqueous solution containing 67% by mass of xylene sulfonic acid and 8% by mass of sulfuric acid) with respect to 100 parts by mass of silica sand.
  • the kneaded sand of each example was obtained by adding and kneading with a Shinagawa universal stirrer.
  • Example 26 binder composition (U) 93.6 parts by mass of magnesium chloride hexahydrate (MgCl 2 ⁇ 6H 2 O) by mixing and dissolving 6.4 parts by weight was 100 parts by caking Agent composition (W) (containing 3% by mass of magnesium chloride in terms of anhydride).
  • Agent composition (X) (containing 3% by mass of barium chloride in terms of anhydride).
  • Example 28 Binder composition (Y) (chlorinated) which was prepared by mixing and dissolving 3.0 parts by mass of zinc chloride (ZnCl 2 ) in 97.0 parts by mass of binder composition (U). Containing 3% by weight of zinc).
  • each kneaded sand thus obtained is immediately filled into a test piece-manufacturing wood mold with a mold having an inner diameter of 50 mm and a height of 50 mm under the conditions of a temperature of 25 ° C. and a humidity of 55%, and curing is started. 30 minutes later, each test piece was taken out (molding time 30 minutes). Therefore, the compressive strength and bulk density of the obtained test pieces after 30 minutes, 1 hour, 3 hours and 24 hours from the start of curing were measured. The results are shown in Table 7.
  • Comparative Example 7 and Examples 25 to 28 a binder composition having a nitrogen atom content of 1.8% by mass with respect to the total amount of the acid curable resin and water is used.
  • the compressive strength after 30 minutes and the compressive strength after 24 hours in Examples 25 to 28 using the binder composition mixed with metal chloride are both metal It is clearly higher than Comparative Example 7 using a binder composition in which no chloride is mixed, and it can be said that the effect of improving the strength of the mold is obtained. Therefore, even when the nitrogen atom content relative to the total amount of the acid curable resin and water is 1.8% by mass, the effect of improving the initial strength and final strength of the mold can be obtained by using the binder composition of the present invention. It can be said.
  • the compressive strength (initial strength) after 30 minutes is the nitrogen atom content Examples 25 to 28 in Table 7 tended to be higher, and the compressive strength after 24 hours tended to be higher in Examples 3 to 6 in Table 2 having a higher nitrogen atom content.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention porte sur une composition de liant pour formation de moule de coulée, qui peut donner un moule de coulée ayant une résistance suffisante sans compliquer l'étape de production ; et sur un procédé pour produire un moule de coulée utilisant la composition de liant pour formation de moule de coulée. La composition de liant pour formation de moule de coulée est caractérisée en ce qu'elle comprend une résine durcissable aux acides, de l'eau et le chlorure d'un métal. La composition est en outre caractérisée en ce que la résine durcissable aux acides comprend de l'alcool furfurylique et un ou plusieurs produits de la condensation ou de la co-condensation de l'un ou de plusieurs des éléments choisis dans un groupe constitué par l'alcool furfurylique, les phénols et l'urée, avec un aldéhyde, et en ce que le métal est un métal alcalino-terreux et/ou un élément de la famille du zinc.
PCT/JP2009/063132 2008-07-29 2009-07-22 Composition de liant pour formation de moule de coulée et procédé pour produire un moule de coulée utilisant la composition de liant pour formation de moule de coulée WO2010013629A1 (fr)

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JP2012255129A (ja) * 2010-10-25 2012-12-27 Sekisui Chem Co Ltd フルフリルアルコール−ホルムアルデヒド共重合体の製造方法
EP2832790A4 (fr) * 2012-03-26 2015-11-18 Sekisui Chemical Co Ltd Composition de résine furannique thermodurcissable et stratifié de résine furannique l'utilisant
EP3085724B1 (fr) 2015-04-24 2019-06-05 Cavenaghi SPA Système de liant de fonderie avec une faible teneur en formaldéhyde et son procédé d'obtention

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JP5755911B2 (ja) 2010-03-18 2015-07-29 花王株式会社 鋳型造型用粘結剤組成物
JP5563875B2 (ja) * 2010-04-16 2014-07-30 花王株式会社 鋳型用組成物を製造するためのキット
JP5717978B2 (ja) * 2010-04-16 2015-05-13 花王株式会社 鋳型造型用粘結剤組成物
JP2011224639A (ja) * 2010-04-22 2011-11-10 Kao Corp 鋳型用組成物
CN101856716A (zh) * 2010-05-07 2010-10-13 牛兰锋 精铸整体中空陶瓷型壳及生产方法
JP5581114B2 (ja) * 2010-05-21 2014-08-27 花王株式会社 鋳型造型用粘結剤組成物
JP5986457B2 (ja) * 2011-08-31 2016-09-06 花王株式会社 自硬性鋳型造型用粘結剤組成物
JP5876737B2 (ja) * 2012-02-06 2016-03-02 旭有機材工業株式会社 鋳型用有機粘結剤及びそれを用いた鋳物砂組成物の製造方法並びに鋳型の製造方法
CN104093508B (zh) * 2012-02-06 2016-12-14 旭有机材工业株式会社 铸型用有机粘结剂、使用其得到的型砂组合物以及铸型
EP2828325B1 (fr) * 2012-03-23 2020-04-15 Kao Corporation Composition de liant pour la fabrication de moules de fonderie
CN102806316A (zh) * 2012-08-27 2012-12-05 林柏崧 一种预成型陶瓷型芯金属铸造制程及其方法

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JP2012255129A (ja) * 2010-10-25 2012-12-27 Sekisui Chem Co Ltd フルフリルアルコール−ホルムアルデヒド共重合体の製造方法
EP2832790A4 (fr) * 2012-03-26 2015-11-18 Sekisui Chemical Co Ltd Composition de résine furannique thermodurcissable et stratifié de résine furannique l'utilisant
US9376543B2 (en) 2012-03-26 2016-06-28 Sekisui Chemical Co., Ltd. Thermosetting furan resin composition and furan resin laminated body using the same
EP3085724B1 (fr) 2015-04-24 2019-06-05 Cavenaghi SPA Système de liant de fonderie avec une faible teneur en formaldéhyde et son procédé d'obtention

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