Composition for mold

Abstract: A binder resin composition, a curing agent composition, a caking additive composition, a kit, a casting mold composition and a process for manufacturing a casting mold, wherein a metallic compound containing a metallic element belonging to Group IB to VIII of the Periodic Table is utilized. The compositions are useful for the production of a sand mold for casting having an excellent strength from reclaimed sand in a self-hardening or gas-hardening mold process. The casting mold, which is manufactured in the presence of a metallic compound containing a metallic element belonging to Group IB to VIII of the Periodic Table, so that it has excellent strength.

Description: Background of the Invention Field of the Invention The present invention relates to a binder resin composition, a caking additive composition and a casting mold composition for a self-hardening or gas-hardening mold process. More particularly, the present invention relates to a binder resin composition, a caking additive composition and a casting mold composition which are useful in a process for the production of a sand mold for casting by molding a refractory granular material with a water-soluble phenolic resin as a binder and an organic ester as a curing agent and which can remarkably improve the reusability of the refractory granular material. The present invention also contemplates a sand mold for casting produced by using one of the above-mentioned compositions and a process for the production of a sand mold for casting comprising the use of one of the above-mentioned compositions. Description of the Related Art The self-hardening molding process, the Cold Box process and the Croning process (i.e., the Shell process) have been known as processes for producing a mold such as a master mold or core by the use of an organic binder. Particularly from the standpoint of productivity, quality of castings, safety and hygiene, the self-hardening or self-curing molding process using an organic binder instead of an inorganic binder has already become a general-purpose molding process, mainly in the field of machinery castings. Meanwhile, the Croning process of thermally curing a granular refractory coated with a phenolic resin, i.e., a so-called coated sand, has been also widely used as a process for producing a mold at a medium or high rate. However, the employment of the Cold Box process of conducting the curing or hardening of a mold with a gas or an aerosol at ordinary temperatures instead of the Croning process has been attempted in earnest for the purpose of saving the energy which would otherwise be consumed in the production of a mold and improving the production rate of a mold and the qualities of a mold and a casting. Recently, compositions for a molding sand comprising a water-soluble phenolic resin as a binder and an organic ester as a curing agent have been reported in U.S. RE Nos. 32812 (published on December 27, 1988; Borden UK Limited) and 32720 (published on July 26, 1988; Borden UK Limited) as compositions which are suitably used in the self-hardening or gas-hardening molding process and which can improve the quality of a casting and the working atmosphere. The molding process using such a composition is advantageous in that the working atmosphere is not polluted by the sulfur dioxide gas evolved in pouring and that the obtained casting has few faults due to sulfur and nitrogen, because the composition does not contain sulfur or nitrogen, unlike the acid-curing type binder composition of the prior art. However, it is well known that the employment of the above-mentioned process, i.e., a process using such a composition comprising a water-soluble phenolic resin and an organic ester, has a limitation due to the low reclaimability of molding sand. Accordingly, the improvement of the process in these respects has been much expected. Further, the amount of the water-soluble phenolic resin or the composition comprising the same to be used must be increased in order to attain the necessary mold strength because the obtained mold is poor in strength when such a composition is employed. Additionally, the use of a composition comprising a water-soluble phenolic resin and an organic ester has the disadvantage that an increasing amount of the resin must be added to the sand when the amount of sand recovered for reuse or reclaimed after repeated use is large, because the production of a mold having a desirable strength becomes more difficult when the sand recovered for reuse or reclaimed after repeated use is employed. What is worse, such an increase in the resin content of a mold leads to an increase in the amount of thermal decomposition gas evolved in pouring, which introduces gas faults into the casting and adversely affects the working atmosphere. In order to alleviate these disadvantages even a little, for example, a method of subjecting the used sand to severe mechanical abrasion to remove the organic substance and/or alkali remaining on the surface of the sand in preparing the sand for reuse and increasing the amount of fresh sand used or the method of using sand only once and then throwing it away is now generally employed. Accordingly, the rate of reclamation of sand, i.e., the rate of the used sand based on the entire sand, in the case of using the above-mentioned composition was at most about 85% ("Modern sand binders - a review; Liquid catalyst cold setting processes, Liquid ester cured alkaline phenolic binders Alphaset", Foundry Trade Journal, 8/22, P.924, December 1989, by BRITISH CASTING IRON RESEARCH ASSOCIATION). This specialty in sand reclaimability in the case of using a composition comprising a water-soluble phenolic resin and an organic ester is made more apparent in comparison with the case of using an acid-curing furan resin binder which is generally used as a binder for molding the sand. That is, in the case of using an acid-curing furan resin binder, the mold strength attained by using reclaimed sand is generally higher than that attained by using fresh sand, so that the amount of the binder to be added to reclaimed sand can be slightly reduced as compared with that to be added to fresh sand. Further, severe mechanical abrasion is unnecessary for the reclamation of sand, so that the rate of reclamation of sand is about 95% or above. In the production of a mold and/or a core from the sand recovered for reuse, in which sand is bound with a binder after curing, the method for reclamation of sand and the rate of reclamation of sand are economically important factors. The reclamation of sand from a mold and/or a core is generally conducted by taking a casting from the mold, breaking the mold and the core into pieces by mechanical oscillation or similar treatment for breaking up the mold and the core, crushing the lumps and agglomerate and recovering the sand. The recovered sand is generally subjected to a reclamation treatment in order to remove the binder remaining on the surface of the sand in an unburnt state. There are known three processes for reclaiming sand (i.e., mechanical, wet and thermal processes). The wet process is relatively unfavorable because of the problematic disposal of washings and the high energy cost for drying the sand. Further, the thermal reclamation process is also relatively unfavorable because of its high energy cost. The mechanical reclamation process is most economical, so that it is most generally employed and its use is spreading in the casting industry. In the case of using the sand thus reclaimed, however, there is the aforementioned disadvantage inherent in this process that a binder system comprising a step of curing a water-soluble phenolic resin with an organic ester cannot provide a mold having a sufficiently high strength. This phenomenon is far from different from the current case using an acid-curing furan resin. Accordingly, an improvement of the above-mentioned disadvantage has been earnestly expected. Japanese Patent Laid-Open No. 261815/1990 (October 24, 1990) and the corresponding European Patent Application - A No. 389 082 (September 26, 1990) discloses the use of specific modified benzylic ether resole resins as the binder for foundry cores and molds to thereby attain higher tensile strength of molds and cores. The modified benzylic ether resole resins are prepared by partial reaction of aldehyde and phenol in the presence of a divalent metal ion catalyst followed by completion of the reaction under alkaline conditions. However, this prior art does not show a sufficiently high strength of molds and cores in the case where the reclaimed sand is used. As processes for improving the strength of a mold produced by the use of reclaimed sand, a process of lowering the content of solid, i.e., resin, contained in the binder composition is disclosed in Japanese Patent Laid-Open No. 262042/1989 (October 18, 1989) and the corresponding European Patent Publication-A No. 336534 (October 11, 1989) and a process of preliminarily treating reclaimed sand with a silane solution is disclosed in Japanese Patent Laid-Open No. 262043/1989 (October 18, 1989) and the corresponding European Patent Publication-A No. 336533 (October 11, 1989). However, these processes do not impart a satisfactory strength to a mold made from reclaimed sand, though they sometimes slightly enhance the strength of such a mold. EP-A-0 465 919 discloses a process for producing a casting mold from sand, which comprises the steps of blending with one another sand, a binder comprising a water-soluble phenolic resin, a hardening agent comprising an organic ester compound and one or more additives containing therein a metal of the Groups I to VIII and molding and curing the mixture into a casting mold. EP-A-0 376 432 discloses curable binder compositions comprising a phenol formaldehyde resol resin, an ester-functional curing agent and a lithium ion-generating alkalizing agent. Furthermore, a binder-aggregate material is disclosed comprising the above curable binder composition and a particulate aggregate material and furthermore, at least one additive which may be selected from iron oxide, silicon dioxide, aluminum powder, magnesium powder, silicon powder, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide and mixtures thereof. EP-A-202 004 discloses a pouring tube being prepared from a self-set, foamed, refractory composition which comprises a particulate refractory material and a binder system comprising an alkali-stabilized phenol-formaldehyde resol resin, a setting agent and a sinter aid selected from sodium borate, calcium tetraborate, powdered glass and ball clay. Disclosure of the Invention Summary of the Invention The present inventors have extensively studied in order to solve the above-described problem and have found that the strength of a mold produced from a refractory granular material, particularly a reclaimed refractory granular material (hereinafter referred to as "reclaimed sand"), with a composition comprising a water-soluble phenolic resin as a binder and an organic ester as a curing agent can be remarkably enhanced by incorporating a specified amount of a specified metal element into the composition. The present invention has been accomplished on the basis of this finding. Namely, the present invention provides a process for preparing a binder resin composition consisting essentially of a water-soluble phenolic resin and a compound containing a metallic element, wherein the metallic element is selected from the group consisting of elements belonging to Groups IB to VIII of the Periodic Table, wherein said composition contains said compound containing said metallic element in an amount of from 0.0005 to 5% by weight in terms of the metallic element based on the weight of the water-soluble phenolic resin and optionally a silane coupling agent, characterized in that said compound containing said metallic element is mixed with a phenol and an aldehyde, and the phenol is polycondensed with the aldehyde in the presence of the metallic compound, or said compound containing said metallic element is added in the step where the polycondensation of the phenol with the aldehyde has proceeded to some extent. The present invention further provides a binder resin composition being obtainable by the above process. The present invention provides a caking additive composition consisting essentially of the above binder resin composition and an organic ester compound. The present invention provides a kit consisting essentially of the above-described caking additive composition, wherein said kit consists essentilly of package (A) containing said binder resin composition and package (B) containing said organic ester compound. The present invention provides a casting mold composition consisting essentially of the aforementioned caking additive composition and a refractory granular material. Detailed Description of the Invention The compound containing a specified metallic element according to the present invention contains therein at least one metal element selected from the group consisting of elements belonging to Group IB to VIII of the Periodic Table, namely, metal elements except for alkaline metals (IA) and metalloids. For example, the compound comprises one or more metallic element(s) selected from among Cu and Ag (Group 1B), Mg, Ca, Sr and Ba (Group IIA), Zn and Cd (Group IIB), Sc and Y (Group IIIA), Al, Ga, In and Tl (Group IIIB), Ti, Zr and Hf (Group IVA), Sn and Pb (Group IVB), V, Nb and Ta (Group VA), Sb and Bi (Group VB), Cr, Mo and W (Group VIA), Po (Group VIB), Mn, Tc and Re (Group VIIA) and Fe, Co and Ni (Group VIII). The compounds containing the metallic element to be used in the present invention may take any form selected from among powdered metal (in which the metal is a simple substance or a metal alloy), metal oxide, metal hydroxide, metal salt of an inorganic acid, metal salt of an organic acid, a metal complex and so on. That is, in the present invention, the form of the compound containing the metallic element (hereinafter referred to simply as "the metallic compound" ) is not limited at all. Specific examples of the metallic compounds will now be described, though the metallic compounds are not limited to those which will be mentioned. In the case where the metallic compound according to the present invention is used in a powdery form, i.e., in the form of a powdered metal, as the metallic element contained in the metallic compound, Cu and Ag (Group IB), Mg, Ca, Sr, Ba, Zn and Cd (Group II), Al, Sc and Ga (Group III), Ti, Zr and Sn (Group IV), Sb and Bi (Group V), Cr and Mo (Group VI), Mn and Tc (Group VII) and Fe, Co and Ni (Group VIII) are cited. Elements called metalloids such as B, Si, As and Te are undesirable. Further, the metal alloy to be used in a powdery form includes duralumin, magnalium and ferromanganese. Representative forms of the metallic compound according to the present invention include salts, double salts, hydroxides, oxides, organometallic compounds wherein the metal atom is bonded to a hydrocarbon group such as an alkyl group and an aryl group, nitrides, alkoxides, hydrides, carbides, metal imides, peroxides, sulfides, phosphides, nitrites, anilides, phenolates, hexaammine complexes (hexaammoniates), ferrocene and its analogues, dibenzenechromium and its analogues, inorganic heteropolymers, metal carbonyl, metal-containing enzymes, clathrate compounds, metal chelates and metal chelate polymers. The double salt includes alums and its analogies represented by the general formula (I): (M³⁺)₂(SO₄)₃·(M¹⁺)₂SO₄·24H₂O wherein the trivalent metal corresponding to M³⁺ includes Al, V, Mn and Fe and the monovalent metal corresponding to M¹⁺ includes Na and K. Examples of the double salt include potassium alum and ammonium alum. A representative structure of the salts, hydroxides and oxides containing one or more of metallic elements belonging to Group IB to VIII of the Periodic Table is represented by the following general formula (II): M a X b wherein M represents a metallic element selected from the group consisting of elements belonging to Group IB to VIII of the Periodic Table; X represents an oxygen atom, a hydroxyl group, or an anionic atomic group of an inorganic or organic acid or an acid having a sequestering property; and a and b are each an integer of 1 or above. Examples of M in general formula (II) include, as in the case of the powdered metal, Cu and Ag (Group IB), Mg, Ca, Sr, Ba, Zn and Cd (Group II), Al, Sc and Ga (Group III), Ti, Zr and Sn (Group IV), Sb and Bi (Group V), Cr and Mo (Group VI), Mn and Tc (Group VII) and Fe, Co and Ni (Group VIII), but elements called metalloids such as B, Si, As and Te are undesirable. Specific examples of X in general formula (II) include an oxygen atom, a hydroxyl group, an anionic atomic group of an inorganic acid, such as halides (F⁻, Cl⁻ and Br⁻), SO₄²⁻, SO₃²⁻, S₂O₃²⁻, S₂O₆²⁻, SiF₆²⁻, MoO₄²⁻, MnO₄²⁻, NO₃⁻, NO₂⁻, ClO₃⁻, ClO⁻, CO₃²⁻, HCO₃⁻, CrO₄²⁻, IO₃⁻, PO₃⁻, PO₄³⁻, HPO₃²⁻, HPO₄²⁻, H₂PO₄⁻, P₂O₇⁴⁻, H₂PO₂⁻, SiO₃²⁻, BO₂⁻, BO₃³⁻, B₄O₇²⁻, Al(OH)₆³⁻ and Fe(CN)₆⁴⁻, and an anionic atomic group of an organic acid, such as anionic atomic groups of carboxylic acids, e.g., formic acid, acetic acid, oxalic acid, tartaric acid and benzoic acid; anionic atomic groups of organic sulfonic acids, e.g., sulfamic acid, xylenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid and alkylbenzenesulfonic acid; and anionic atomic groups of organic phosphoric acids, e.g., methylphosphoric acid and ethylphosphoric acid. Representative examples of the salts, hydroxides and oxides to be used in the present invention are as follows: Examples of the salts include calcium chloride, magnesium chloride, barium chloride, copper chloride, zinc chloride, calcium bromide, aluminum fluoride, vanadium chloride, molybdenum chloride, manganese chloride, iron chloride, nickel chloride, calcium sulfate, calcium carbonate, magnesium phosphate, calcium phosphate, aluminum chloride, tin chloride, calcium formate, magnesium oxalate, calcium toluenesulfonate, magnesium acetate, zinc acetate, aluminum acetate and magnesium aluminate. Examples of the hydroxides include aluminum hydroxide, calcium hydroxide, magnesium hydroxide and zinc hydroxide. The oxides includes magnesium oxide, calcium oxide, barium oxide, zinc oxide and aluminum oxide. Further, double compounds comprising two or more of these oxides or those comprising one of the oxides and an oxide or salt of other element can also be favorably used in the present invention. The double compounds to be used in the present invention will now be described in detail. Representative examples thereof include cements such as hydraulic lime, Roman cement, natural cement, Portland cement, alumina cement, Portland blast-furnace slag cement, silica cement, fly ash cement, masonry cement, expansive cement and special cement; and blast furnace slags such as steelmaking slag, magnesium smelting slag, ferrochrome slag and bentonite. Chemical structures of representative double compounds are represented by; mCaO·nSiO₂, mCaO·nAl₂O₃, mBaO·nAl₂O₃, CaO·mAl₂O₃·nSiO₂, CaO·mMgO·nSiO₂, mCaCO₃·nMgCO₃, or mCaO·nFe₂O₃·ℓCaO·mAl₂O₃·nFe₂O₃ (wherein ℓ, m and n are each 0 or an integer of 1 or above). The oxides or double compounds to be used in the present invention further include other clayish materials, iron oxide materials and other mineral materials. When such an oxide is used, it is preferable that the oxide have a particle diameter as small as possible. That is, the mean particle diameter thereof is generally 200 µm or below, preferably 50 µm or below. The organometallic compounds in which a metal atom belonging to Group IB to VIII of the Periodic Table is bonded to a hydrocarbon group such as an alkyl group and an aryl group include Al(CH₃)₃, Al(C₂H₅)₃, Al(C₆H₅)₃, (C₂H₅)₂AlI, (C₂H₅)₂AlH, (C₂H₅)₂AlCN, Al(i-C₄H₉)₃, (CH₂=CH)₃Al, Zn(C₆H₅)₂, (CH₂=CH)₂Zn, Ca(C₂H₅)₂ and Grignard reagents represented by the formula: R-Mg-X (wherein R is an alkyl group or an aryl group and X is a halogen atom). The alkoxides containing a metallic element belonging to Group LB to VIII of the Periodic Table include Al[OCH(CH₃)₂]₃ and Zn(OCH₃)₂. The hydrides containing a metallic element belonging to Group IB to VIII of the Periodic Table include AlH₃, CaH₂ and BaH₂. The carbides containing a metallic element belonging to Group IB to VIII of the Periodic Table include Al₄C₃ and CaC₂. The metal imides containing a metallic element belonging to Group IB to VIII of the Periodic Table include Ca(NH₂)₂. The peroxides containing a metallic element belonging to Group IB to VIII of the Periodic Table include CaO₂, BaO₂ and BaO₄. The sulfides containing a metallic element belonging to Group IB to VIII of the Periodic Table include ZnS, Cu₂S and CuS. The phosphides containing a metallic element belonging to Group IB to VIII of the Periodic Table include AlP. The nitrites containing a metallic element belonging to Group IB to VIII of the Periodic Table include CuNO₂. The anilides containing a metallic element belonging to Group IB to VIII of the Periodic Table include Al(NHPh)₃. The phenolates containing a metallic element belonging to Group IB to VIII of the Periodic Table include aluminum phenolate, zinc phenolate and calcium phenolate. The hexaammine complexes, i.e., hexaammoniates, containing a metallic element belonging to Group IB to VIII of the Periodic Table include Ca(NH₃)₆. The ferrocenes and its analogues containing a metallic element belonging to Group IB to VIII of the Periodic Table include ferrocene, i.e., Fe(C₅H₅)₂, Zn(C₅H₅)₂, Ni(C₅H₅)₂, Mn(C₅H₅)₂ and V(C₅H₅)₂. The dibenzenechromium and its analogues containing a metallic element belonging to Group IB to VIII of the Periodic Table include Cr(C₆H₆)₂, Mo(C₆H₆)₂ and V(C₆H₆)₂. The inorganic heteropolymers containing a metallic element belonging to Group IB to VIII of the Periodic Table include inorganic hydride heteropolymers such as beryllium hydride polymer, magnesium hydride polymer and aluminum hydride polymer; and inorganic polymers such as aluminum nitride containing Al-N bonds. The inorganic compounds containing a metallic element belonging to Group IB to VIII of the Periodic Table include aluminosilicates such as zeolite, analcite and natrolite; layer silicates such as mica; and aluminum phosphate and hydrotalcite. The clathrate compounds containing a metallic element belonging to Group IB to VIII of the Periodic Table include complexes of these metallic elements with cyclic polyethers (crown ethers), cyclic polyamines (azacrown compounds), cyclic polythia ethers (thiacrown compounds), composite donor crown compounds, heterocyclic crown compounds (cryptand), polymeric crown compounds, cyclic phenolic resin (calixarene) and cyclodextrin derivatives, for example, Ca²⁺ complex of dibenzo-18-crown-6 and Ca²⁺ complex of cryptand [2·2·2]. The metal complexs containing a metallic element belonging to Group IB to VIII of the Periodic Table include complexes each of which has a coordination number of 2 to 8 and comprises the metallic element and a ligand selected from among anionic ligands such as Cl⁻, CN⁻, NCS⁻, SO₄²⁻, NO²⁻, NO₃⁻, CH₃COO⁻, C₂O₄²⁻, CO₃²⁻, OH⁻, H₂N·CH₂COO⁻, F⁻, Br⁻, ONO⁻, I⁻, NH²⁻ and SCN⁻; neutral ligands such as H₂N·CH₂CH₂·NH₂, C₆H₅N, NH₃ and H₂O; and cationic ligands such as H₂N·NH₃⁺ and H₂N·CH₂CH₂·NH₃⁺ and . Specific examples thereof include [Al(C₂O₄)₃]Cl₃ and [Zn(NH₃)₆]Cl₂. Further, the compounds containing a metallic element belonging to Group IB to VIII of the Periodic Table include metal carbonyls such as Ni(CO)₄ and Mn₂(CO)₁₀; metal-containing enzymes such as carboxypeptidase A and thermolysin; and zircoaluminum compounds. Further, a metal chelate (or a sequestering compound) comprising a metallic element belonging to Group IN to VIII of the Periodic Table and a chelating agent (or a sequestering agent) may be used in the present invention. Representative examples of the chelating agent include aminoacetic acids and salts thereof such as ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid (NTA) and its salts, trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA) and its salts, diethylenetriaminepentaacetic acid (DTPA) and its salts, triethylenetetraminehexaacetic acid (TTHA) and its salts, glycol ether diaminetetraacetic acid (GEDTA) and its salts, iminodiacetic acid (IDA) and its salts, polyalkylenediaminetetraacetic acid and its salts and N-hydroxyalkyleneiminodiacetic acid and its salts; phenylaminocarboxylic acids and salts thereof such as 2-oxyphenyliminodiacetic acid and its salts, phenyliminodiacetic acid and its salts, 2-oxybenzyliminodiacetic acid and its salts, benzyliminodiacetic acid and its salts and N,N'-ethylenebis-[2-(o-hydroxyphenyl)]glycine and its salts; mercapto-containing aminocarboxylic acids and salts thereof such as β-mercaptoethyliminodiacetic acid and its salts; ether linkage-containing aminocarboxylic acids and salts thereof such as ethyl ether diaminetetraacetic acid and its salts; thio ether linkage-containing aminocarboxylic acids and salts thereof such as ethyl thio ether diaminetetraacetic acid and its salts; aminocarboxylic acids having a sulfonic acid group and salts thereof represented by β-aminoethylsulfonic acid-N,N-diacetic acid and its salts; aminocarboxylic acids having a phosphonic acid group and salts thereof such as nitrilodiacetic acid-methylenephosphonic acid and its salts; peptide linkage-containing aminocarboxylic acids and salts thereof such as N,N'-diglycylethylenediamine-N',N'',N''',N''''-tetraacetic acid and its salts; hydroxycarboxylic acids and salts thereof such as gluconic acid and its salts, citric acid and its salts, and tartaric acid and its salts; phosphorus acids and salts thereof such as tripolyphosphoric acid and its salts, hydroxyethanediphosphonic acid (HEDP) and its salt, and nitrilotristyrenephosphonic acid (NTP) and its salts; and acetylacetone. Further, a metal chelate polymer comprising a metallic element belonging to Group IB to VIII of the Periodic Table and a coordination polymer may be used in the present invention. Representative examples of the coordination polymer include polymers containing at least one member selected from among an amino group, a nitrogenous heteroring, a Schiff base, an alcohol, a carboxylic acid, a ketone, an ester, an amide, an aminocarboxylic acid, a phosphonic acid, a phosphinic acid and a thiol in the molecule. Among the metallic compounds described above, a compound comprising a metallic element belonging to Group II to VIII of the Periodic Table is desirable, a compound comprising a metallic element belonging to Group II and III of the Periodic Table is more desirable, and a compound comprising a metallic element selected from the group consisting of Zn, Ca, Mg and Al, especially Al, is most desirable. The water-soluble phenolic resin, that is an alkaline phenolic resin, to be used in the present invention can be cured with an organic ester compound. The water-soluble phenolic resin is prepared, for example, by reacting a phenol such as phenol, cresol, resorcinol, 3,5-xylenol, bisphenol A and other substituted phenols with an aldehyde such as formaldehyde, acetaldehyde, furylaldehyde or a mixture of them in a large amount of an aqueous solution of an alkaline substance. Therefore, the water-soluble phenolic resin contains a phenolate portion in the molecule. In the preparation of the water-soluble phenolic resin, other monomer(s) which is condensable with formaldehyde, such as urea, melamine and cyclohexanone may be condensed with the components described above in such an amount that these monomer(s) are not the main constituent. The resin may have either a methylene linkage type structure or a benzyl ether type structure. A suitable alkaline substance, that is an alkaline catalyst, to be used in the preparation of such a water-soluble phenolic resin includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and mixtures thereof, among which potassium hydroxide is most desirable. The organic ester compound to be used in the present invention includes lactones and organic esters which are obtained by reacting a monohydric or polyhydric alcohol having 1 to 10 carbon atoms with an organic carboxylic acid having 1 to 10 carbon atoms, which may be used either alone or as a mixture. In a self-hardening mold process, the use of γ-butyrolactone, propiolactone, ε-caprolactone, propylene carbonate, ethyl formate, ethylene glycol diacetate, ethylene glycol monoacetate or triacetin is desirable, while in a gas-hardening mold process, the use of methyl formate is desirable. The binder resin composition contains the metallic compound in an amount from 0.0005 to 5% by weight, preferably 0.001 to 3% by weight in terms of the metallic element, and based on the weight of the water-soluble phenolic resin. If the content of the metallic compound is lower than 0.0005% by weight, the effect of the present invention will not be exhibited sufficiently, while if it exceeds 5% by weight, no additional effect will be attained. The binder resin composition generally shows a solid content of from 40 to 50 % by weight. In binder resin composition, the solid content shows the amount of the water-soluble phenolic resin only or the total amount of the water-soluble phenolic resin and a silane coupling agent, substantially. The metallic compound is, for example, dissolved, dispersed or emulsified in the binder resin composition. The metal-containing water-soluble phenolic resin is prepared by adding the metallic compound in any step of the preparation of the water-soluble phenolic resin. Namely, the metal-containing water-soluble phenolic resin can be prepared by mixing the metallic compound with a phenol and an aldehyde and polycondensing the phenol with the aldehyde in the presence of the metallic compound and a large amount of an alkaline substance, or by adding the metallic compound in the step where the polycondensation of the phenol with the aldehyde proceeds to some extent. The present invention provides a process for preparing the binder resin composition, wherein the above-described metallic compound is added to a raw material composition which is used for synthesizing the above-described water-soluble phenolic resin. The binder resin composition of the present invention may contain a conventional silane coupling agent. Preferred specific examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane. The present invention provides a caking additive composition comprising the above-described binder resin composition and an organic ester compound. The content of the metallic compound in the caking additive composition is from 0.0005 to 5% by weight, preferably 0.001 to 3% by weight in terms of metallic element, based on the weight of the water-soluble phenolic resin, or, preferably from 5 to 200000 ppm, still preferably from 20 to 100000 ppm in terms of the metallic element, and based on the weight of the organic ester compound. The content of the organic ester compound in the caking additive composition is preferably from 0.6 to 5000 parts by weight, still preferably 4 to 2000 parts by weight based on 100 parts by weight of the water-soluble phenolic resin. The caking additive composition of the present invention may contain a conventional silane coupling agent. Preferred specific examples of the silane coupling agent include those which are described according to the binder resin composition. The caking additive composition is used for a self-hardening mold process or a gas-hardening mold process in which the setting or curing step is conducted at ordinary temperature. Therefore, the caking additive composition is genarally provided as a kit comprising two or more of packages each of which contains a different component. The present invention provides a kit comprising the above-described caking additive composition, wherein said kit comprises package (A) containing the above-described binder resin composition and package (B) containing the above-described organic ester compound, When such a kit is used for a self-hardening mold process, package (A) and package (B) are mixed with each other. When such a kit is used for a gas-hardening mold process, package (B) is used in the state of an aerosol. In the production of a sand mold for casting with the binder resin composition, the caking additive composition or the kit according to the present invention in a self-hardening mold process or a gas-hardening mold process, any conventional process may be employed. In the manufacture of a casting mold, it has not been known at all that the strength of the casting mold comprising reclaimed sand can be remarkably enhanced by using the above-described metallic compound, i.e., by using the above-described binder resin composition, the above-described caking additive composition or the above-described kit according to the present invention. Meanwhile, it has been known that some metal ions are useful as a catalyst for forming a benzyl ether linkage between the phenolic nuclei of phenols at the o-position. For example, U.S. Patent No. 3485797 (published on December 23, 1969; ASHLAND OIL INC.) and Japanese Patent Publication Nos. 15797/1979 (published on June 18, 1979; COR TECH RESEARCH LTD.) and 23769/1985 (published on June 10, 1985; SUMITOMO BAKELITE K.K.) disclosed Group II elements and transition elements as such metal ions. According to these known techniques, however, the metallic elements are used as a catalyst for causing the reaction of forming a resol or benzyl ether and the obtained resol resin is one which should fall into the category of thermosetting solid resol resins, being far different from the water-soluble phenolic resin according to the present invention with respect to the field of application and curing mechanism. That is, in the present invention, an organic ester compound used as a curing agent is hydrolyzed in a caking additive composition exhibiting strong alkalinity to thereby cure the water-soluble phenolic resin, which is far different from the curing mechanism of the solid resol resin described above. In fact, when an organic ester compound is added to the resins described in the above Patent documents, no curing occurs due to poor alkalinity. Accordingly, the techniques described above have no reference to the present invention. The present invention further provides a casting mold composition comprising the aforementioned caking additive composition and a refractory granular material. The refractory granular material to be used in the present invention includes silica sand comprising quartz as a main component, chromite sand, zircon sand, olivine sand and alumina sand. Although the refractory granular material to be used in the present invention may be either a fresh one or a recovered (or reclaimed) one, the effect of enhancing the mold strength according to the present invention is remarkable, particularly when a recovered or reclaimed sand is used. Therefore, it is preferable that a refractory granular material mainly comprising a recovered or reclaimed sand for reuse is employed. When recovered or reclaimed sand is used, the reclamation process is not particularly limited though a molding sand is generally reclaimed by abrasion or roasting. The casting mold composition according to the present invention comprises preferably from 0.2 to 7.5 parts by weight, still preferably from 0.3 to 2.5 parts by weight, based on 100 parts by weight of the refractory granular material, of said water-soluble phenolic resin; preferably from 0.05 to 9 parts by weight, still preferably from 0.1 to 5.0 parts by weight, based on 100 parts by weight of the refractory granular material, of said organic ester compound; preferably from 0.0001 to 10 parts by weight, still preferably from 0.0001 to 3 parts by weight (in terms of the metallic element), based on 100 parts by weight of the refractory granular material, of said metallic compound; and water. The casting mold composition according to the present invention comprises preferably from 0.001 to 1 parts by weight, still preferably from 0.002 to 0.5 parts by weight, based on 100 parts by weight of the refractory granular material, of a silane coupling agent. The present invention provides a casting mold comprising a cured resin which is obtained by curing the water-soluble phenolic resin in the above-mentioned binder resin composition with the above-mentioned organic ester compound in the presence of a refractory granular material. As the refractory granular material, the employment of those which mainly comprises a recovered (or reclaimed) sand for reuse is advantageous because the effect of enhancing the mold strength according to the present invention is remarkable particularly when a recovered or reclaimed sand is used. The cured resin is obtained by curing the water-soluble phenolic resin in the above mentioned binder resin composition including the above mentioned metallic compound with the above-mentioned organic ester compound. Therefore, the term "cured resin" means those which comprise the specified resin and the metallic element constituting the metallic compound. The cured resin is present on the surface of the refractory granular material. The present invention provides a process for manufacturing a casting mold by curing the water-soluble phenolic resin in the above mentioned binder resin composition including the above mentioned metallic compound with the above-mentioned organic ester compound in the presence of the above-mentioned refractory granular material. In the process for molding a refractory granular material into a sand mold for casting, the strength of such a mold made from reclaimed sand can be remarkably improved by using the binder resin composition, the caking additive composition, the kit, the casting mold composition or the process for manufacturing a casting mold according to the present invention. Example The present invention will now be described in detail by referring to the following Examples, though the present invention is not limited to them. Synthesis Example 1 (Preparation Example 1 of a binder resin composition) 255 parts by weight of water, 267 parts by weight of phenol and 34 parts by weight of magnesium ethylenediaminetetraacetate were fed into a four-necked flask fitted with a stirrer, a reflux condenser and a thermometer, heated on a water bath under stirring, and maintained at 85°C for 30 minutes. 282 parts by weight of 48 wt.% potassium hydroxide aq. soln. was added into the flask, followed by the addition of 158 parts by weight of 92 % (purity) paraformaldehyde in one hour. The reaction was continued at the same temperature. When the viscosity of the resin solution reached 100 cps at 25°C, the reaction mixture was cooled, followed by the addition of 4.0 g of γ-aminopropyltriethoxysilane. A resin solution, i.e., a binder resin composition, containing 1931 ppm of elementary magnesium (solid content: 49 wt.%, weight-average molecular weight of the synthesized resin: 2300) was obtained. Synthesis Example 2 (Preparation Example 2 of a binder resin composition) 263 parts by weight of water, 275.5 parts by weight of phenol and 291 parts by weight of 48 wt.% potassium hydroxide aq. soln. were fed into a four-necked flask fitted with a stirrer, a reflux condenser and a thermometer, heated on a water bath under stirring, and maintained at 85°C. 163 parts by weight of 92 % (purity) paraformaldehyde was added into the flask in one hour. The reaction was continued at the same temperature. When the viscosity of the resin solution reached 100 cps at 25°C, the reaction mixture was cooled, followed by the addition of 3.5 parts by weight of zinc chloride and 4 parts by weight of γ-aminopropyltriethoxysilane. A resin solution containing 1983 ppm of elementary zinc (solid content: 49 wt.%, weight-average molecular weight of the synthesized resin: 2300) was obtained. Synthesis Example 3 (Preparation Example 3 of a binder resin composition) 264 parts by weight of water, 277 parts by weight of phenol and 292 parts by weight of 48 wt.% potassium hydroxide aq. soln. were fed into a four-necked flask fitted with a stirrer, a reflux condenser and a thermometer, heated on a water bath under stirring, and maintained at 85°C. 163 parts by weight of 92% (purity) paraformaldehyde was added into the flask in one hour. The reaction was continued at the same temperature. When the viscosity of the resin solution reached 100 cps at 25°C, the reaction mixture was cooled, followed by the addition of 4 parts by weight of γ-aminopropyl-triethoxysilane. A resin solution (solid content: 49 wt.%, weight-average molecular weight of the synthesized resin: 2300) was obtained. The determination of the content of the metallic compound, in terms of the metallic element, in the above-described binder resin compositions was conducted as follows: A binder resin composition was sufficiently mixed by stirring and 0.5 to 0.8 g of the composition was weighed onto a 100-ml platinum dish. 10 ml of concentrated nitric acid was added thereto to conduct acid decomposition, followed by weak thermal decomposition. 10 ml of concentrated perchloric acid was added to the decomposition mixture and the obtained mixture was subjected to white fuming treatment to reduce the amount of the mixture to 3 ml. The resulting mixture was cooled by allowing to stand, followed by the addition of 10 ml of HCl (1 + 1) and 10 ml of H₂O, i.e., HCl 5 ml + H₂O 15 ml. The obtained mixture was heated to conduct dissolution. The resulting mixture was filtered through a filter paper No. 5C and the filter cake was washed with dilute hydrochloric acid and hot water. The residue remaining on the filter was ashed at 900 to 1000°C in a 30-ml platinum crucible and cooled by allowing to stand. 2 g of potassium pyrosulfate was added to the ash to conduct acid melting at 800°C. To the obtained melt, 15 ml of water was added and the resultant mixture was heated to solve. Then, the obtained solution was combined with the filtrate recovered above, followed by the adjustment of the total volume to 100 ml with water with a measuring flask. The amount of the metal in the obtained solution was determined by the ICP (inductively coupled plasma emission spectrochemical analysis) method. The determination of the weight-average molecular weight of the synthesized resins in the above-described binder resin compositions was conducted as follows: (a) A sample was dissolved in suitable amount of water, followed by neutralized with diluted sulfuric acid. The resulting mixture containing a precipitation was filtered, and the filter cake was washed with water and then dried. The resulting solid was dissolved in tetrahydrofuran to use as a sample for gel permeation chromatography. (b) Column (manufactured by Shimadzu Seisakusho Co. Ltd.) Guard Column: Shim-pack GPC-800P (4.6 mmΦ × 1.0 cm) Column for determination: Shim-pack GPC-801, GPC-802 and GPC-804 (8.0 mmΦ × 30 cm) Connection: Guard Column, Shim-pack GPC-804, GPC-802 and GPC-804 were connected in this order from injection part side to the other side. (c) Reference material polystyrene (manufactured by Tohsoh Co. Ltd.) (d) Eluate tetrahydrofuran, flow rate: 1 ml/min (pressure: 40 to 70 kg/cm²) (e) Column temperature 40°C (f) Detection RI (g) Share method for calculation of molecular weight time sharing (10 sec) Examples 1 to 20 In a similar manner to that of the Synthesis Example 1, metal-containing resin solutions, i.e., binder resin compositions, were prepared with the proviso that the metallic compounds listed in Table 1 were used in stead of magnesium ethylenediaminetetraacetate in such amounts that the metal contents (in terms of metallic element) of the resin solutions were to be as described in Table 1. Examples 21 to 34 In a similar manner to that of the Synthesis Example 2, metal-containing resin solutions were prepared with the proviso that the metallic compounds listed in Table 2 were used instead of zinc chloride in such amounts that the metal contents (in terms of metallic element) of the resin solutions were to be as described in Table 2. Comparative Example 1 In a similar manner to that of the Synthesis Example 3, a resin solution was prepared. Comparative Example 2 In a similar manner to that of the Example of Japanese Patent Laid-Open No. 262042/1989, a water-soluble phenolic resin solution (solid content: 40 wt.%) was prepared. Namely, to the water-soluble phenolic resin ALpHASET TPA-30 (a product of Borden Inc.), water was added in such an amount that the solid content was to be 40 wt.%. Comparative Example 3 In a similar manner to that of the Synthesis Example 3, a resin solution was prepared. Further, as a refractory granular material, treated sand (See the Example of Japanese Patent Laid-Open No. 262043/1989) was used. Test pieces for pressure test were prepared by the use of the above-described resin solutions, triacetin as a curing agent and reclaimed sands described below, and were examined with respect to their change of pressure resistance with time. A process for the preparation of reclaimed sand-1 (for Examples 1 to 34 and Comparative Examples 1 and 2) FC-250 (Sand/Metal=3.5) was cast with a mold produced from a mixture comprising 100 parts by weight of new Freemantle silica sand, 0.375 part by weight of triacetin as a curing agent and 1.5 parts by weight of a water-soluble phenolic resin solution (solid content: 49 wt.%, weight-average molecular weight of the phenolic resin: 2300) containing 0.5% by weight (based on the phenolic resin) of γ-aminopropyltriethoxysilane. The sand was recovered from the mold, crushed and reclaimed with an M-type rotary claimer (mfd. by Japan Casting Co., Ltd.) (A reclamation, two passes). The reclaimed sand obtained by repeating these steps five times was used in the above determination of mold strength. A Process for the preparation of reclaimed sand-2 (for Comparative Example 3) Reclaimed sand, which was obtained in process for the preparation of reclaimed sand-1, was treated in a similar manner to that of the Example of Japanese Patent Laid-Open No. 262043/1989. Specifically, 100 parts by weight of reclaimed sand was treated with 0.024 part by weight of a 40 wt.% aqueous solution of γ-aminopropyltriethoxysilane at 25°C. Methods for preparing test piece for pressure test and for the determination of mold strength A mixture comprising 100 parts by weight of reclaimed sand described above, 0.375 part by weight of triacetin and 1.5 parts by weight of each of the water-soluble phenolic resin solutions (solid content: 49 wt.%, weight-average molecular weight of the phenolic resin: 2300) prepared in the Examples and the Comparative Examples was poured into a mold for the test piece having a size of 50 mm × 50 mmh. From immediately after the mixture was poured into the mold to 24 hours thereafter, the obtained test piece was examined for changes of pressure resistance with time. The sand temperature was 25°C, and the humidity was 60%RH. The pressure resistances determined at 24 hours after each mixture was poured into the mold are given in Tables 1 and 2. Metallic compound Metal content (ppm) Pressure resistance (kg/cm²) sand temp.: 25°C, humidity: 60%RH after 24 hrs. Example 1 CuCl₂·2H₂O 2,000 13.2 2 MgCl₂ 1,000 32.1 3 EDTA·Na₂Mg 10,000 31.5 4 C₂H₅MgBr 250 30.7 5 calcium acetate 6,000 33.4 6 calcium gluconate 1,500 30.2 7 BaCl₂ 3,000 18.6 8 ZnCl₂ 50 30.2 9 NTA·NaZn 200 33.3 10 AlCl₃ 10 35.5 11 Al₂(SO₄)₃ 100 34.8 12 Al(O-iPr)₃ 500 36.5 13 tetraisopropylbis(dioctylphosphite) titanate 500 12.4 14 SnCl₂ 2,000 11.8 15 VCl₃ 8,000 12.7 16 MoCl₂ 20,000 13.6 17 MnCl₂ 1,000 15.1 18 nickel acetate 500 21.3 19 EDTA·Na₂Ni 2,000 26.5 20 powdered aluminum 1,000 32.4 Comparative Example 1 none 0 6.6 2 none - 5.9 3 none - 7.0 Metallic compound Metal content (ppm) Pressure resistance (kg/cm²) sand temp.: 25°C, humidity: 60%RH after 24 hrs. Example 21 DTA·Na₂Cu 500 14.1 22 magnesium acetate 5,000 33.2 23 Mg(OH) 100 29.2 24 CaCl₂ 5,000 30.0 25 nitrilotris (methylene calcium phosphonate) 1,500 28.5 26 Zn(OH)₂ 10,000 32.4 27 zinc acetate 100 31.5 28 (C₅H₅)₂Zn 50 29.8 29 aluminum acetate 250 34.3 30 aluminum oleate 100 30.7 31 DTA·Na₂V 5,000 15.3 32 DTA·Na₂Mn 500 11.9 33 NiCl₂ 1,000 21.1 34 (CH₅H₅)₂Fe 2,000 18.2

Claims: A process for preparing a binder resin composition consisting essentially of a water-soluble phenolic resin and a compound containing a metallic element, wherein said metallic element is selected from the group consisting of elements belonging to Groups IB to VIII of the Periodic Table, wherein said composition contains said compound containing said metallic element in an amount of from 0.0005 to 5% by weight in terms of the metallic element based on the weight of the water-soluble phenolic resin and optionally a silane coupling agent, characterized in that said compound containing said metallic element is mixed with a phenol and an aldehyde, and the phenol is polycondensed with the aldehyde in the presence of the metallic compound, or said compound containing said metallic element is added in the step where the polycondensation of the phenol with the aldehyde has proceeded to some extent. The process as set forth in claim 1, wherein said composition contains said compound containing said metallic element in an amount of from 0.001 to 3% by weight in terms of the metallic element based on the weight of the water-soluble phenolic resin. The process as set forth in claim 1, wherein said metallic element is selected from the group consisting of elements belonging to Groups II to VIII of the Periodic Table. The process as set forth in claim 1, wherein said metallic element is selected from the group consisting of elements belonging to Groups II and III of the Periodic Table. The process as set forth in claim 1, wherein said metallic element is selected from the group consisting of Zn, Ca, Mg and Al. The process as set forth in claim 1, wherein said metallic element is Al. The process as set forth in claim 1, wherein the form of said compound containing said metallic element is selected from the group consisting of powdered metals, metal oxides, metal hydroxides, metal salts of inorganic acids, metal salts of organic acids and metal complexes. The process as set forth in claim 1, wherein said binder resin composition further comprises a silane coupling agent. The process as set forth in claim 8, wherein said silane coupling agent is selected from the group consisting of γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane. A binder resin composition being obtainable by a process as defined in any of the claims 1 to 9. A caking additive composition consisting essentially of a binder resin composition as defined in claim 10 and an organic ester compound. The caking additive composition as set forth in claim 11, wherein said composition contains said compound containing said metallic element in an amount of from 5 to 200,000 ppm in terms of the metallic element based on the weight of the organic ester compound. A kit comprising the caking additive composition as set forth in claim 11 or 12, wherein said kit essentially consists of package (A) containing said binder resin composition and package (B) containing said organic ester compound. A casting mold composition comprising said caking additive composition as set forth in claim 11 or 12 and a refractory granular material. The casting mold composition as set forth in claim 14, wherein said refractory granular material mainly comprises recovered or reclaimed sand for reuse. A process for manufacturing a casting mold by curing the water-soluble phenolic resin included in the binder resin composition as defined in claim 10 with an organic ester compound. The process as set forth in claim 16, wherein a caking additive composition comprising said binder resin composition and said organic ester compound is used. The process as set forth in claim 16, wherein said refractory granular material mainly comprises recovered or reclaimed sand for reuse.

Inventors: FUNADA HITOSHI, KIUCHI KAZUHIKO, KYOCHIKA NAOKI, MAMBA AKIO, YOSHIDA AKIRA, FUNADA, HITOSHI, KIUCHI, KAZUHIKO, KYOCHIKA, NAOKI, MAMBA, AKIO, YOSHIDA, AKIRA
Applicants: KAO CORP, KAO CORPORATION
Application year: 1992
Main classification: B22C1
IPC codes: C08G8, C04B26, C08K3, B22C1