Patent Publication Number: US-2003236345-A1

Title: Binder for granulation molding of powder particles and granulated moldings

Description:
BACKGROUND OF THE INVENTION  
       [0001] 1) Field of the Invention  
       [0002] The present invention relates to a binder used in granulation molding of powder particles of a metal, a metal oxide or a mineral, or a mixture of two or more thereof, and to granulated moldings obtained by granulation molding by using the binder.  
       [0003] 2) Description of the Related Art  
       [0004] Various steps such as refining and melting are carried out to obtain a desired metal from ores, but at these steps, powder particles are inevitably generated. Reutilization of these powder particles is desired-for effective use of resources, and usually these powder particles are reutilized after granulation molding to a certain size for convenience of handling and in consideration of working atmosphere.  
       [0005] For granulation molding, incorporation of a binder is proposed to improve granulation, shape retention and crushing strength. The binder for granulation molding of powder particles includes inorganic materials such as cement and bentonite, polyvinyl alcohol, carboxymethyl cellulose, starch, tar, pitch, and polybasic acids such as dimer acid and trimer acid (disclosed in JP-A No. 2-270920, JP-A No. 3-6334 and JP-A No. 6-200332, respectively).  
       [0006] However, water should be added to inorganic materials such as cement or polyvinyl alcohol and carboxymethyl cellulose, and starch, poor in water resistance, absorbs moisture, and then they react with water in aluminum residues to generate a hydrogen gas and ammonia, and therefore use of such binders is inconvenient.  
       [0007] When a polybasic acid such as dimer acid or trimer acid is used in materials such as aluminum residues, aluminum nitride, aluminum chloride and aluminum carbide contained therein causes chemical reaction from the start of molding, to ignite and burn granulated moldings, thus causing oxidation of aluminum as a reducing component and depriving it of a reducing ability, and thus there is a problem of a deterioration in the commodity value thereof as an additive.  
       [0008] When a polybasic acid such as dimer acid or trimer acid is used not only in aluminum residues but also in other materials, granulated moldings are poor in shape retention, and therefore the amount of fragments after molding is increased thus decreasing the yield of granulation, and the proportion of the additive compounded in powder particles is so high that when granulated moldings are used as an additive in metal refining, the concentration of the refined metal is decreased.  
       [0009] When tar and pitch are used not only in aluminum residues but also in other materials, a large amount of black smoke is generated at the time of addition to melt steel thus deteriorating the working atmosphere.  
       [0010] Phenol-based resin and polyurethane resin are also proposed as the resins (JP-A No. 3-6334), but the phenol-based resin is poor in shape retention, while the polyurethane resin is expensive and should be heated at 180 to 200° C. to exhibit its binder effect, thus requiring a special expensive device for heating.  
       [0011] Accordingly, any of these binders have advantages and disadvantages, and at present, they are used by compromise in consideration of its use and costs.  
       [0012] Typical inorganic powder particles utilized effectively as a flux material for making steel at present are aluminum residues consisting of aluminum dross, aluminum ash or aluminum mineral residues (melt residues) generated at an aluminum refining, secondary refining or melting step, and used as an additive for de-oxidation and desulfurization of melt pig iron, melt steel or steel ingot, residue formation, reduction of FeO in slag, an improvement in fluidity and heat-retention of slag, in procedures of manufacturing pig iron in a blast furnace, in procedures of steel maiking or casting in an electrical furnace, or in casting procedures, but except for addition by injection, they are subjected to granulation molding with a binder for the convenience of handling. When a water-soluble binder is used, an ammonia gas and hydrogen gas is generated because of the reaction of water with aluminum nitride and metal aluminum contained in aluminum residues, and thus a water-soluble binder based on polybasic acid such as dimer acid is used, but this suffers from a problem of heat evolution.  
       SUMMARY OF THE INVENTION  
       [0013] It is an object of the present invention to provide a binder for granulation molding of powder particles that can be used to produce granulated moldings relatively inexpensively without the problems described above and with broader applicability than the conventional one.  
       [0014] It is object of the present invention to provide a binder for granulation molding of aluminum residues that is suitable particularly for granulation molding of aluminum residues, and that can be utilized effectively as an additive for molten pig iron and melt steel to which the granulated moldings are mainly applied at present.  
       [0015] It is still other object of the present invention to effectively reutilize wastes disposed of at present.  
       [0016] The present invention provides:  
       [0017] 1. A binder for granulation molding of powder particles, which is compounded with a resin having a softening point suitable as a binder resin for toners.  
       [0018] 2. The binder for granulation molding of powder particles may be compounded with a resin softened by heat generated upon friction compression at the time of granulation molding.  
       [0019] 3. The softening point of the binder for granulation molding may be 100° C. or less.  
       [0020] 4. The softening point of the binder for granulation molding may be 60° C. or less.  
       [0021] 5. The resin may be in the form of finely divided particles.  
       [0022] 6. The maximum particle diameter of the resin may be 50 μm or less.  
       [0023] 7. The maximum particle diameter of the resin may be 12 μm or less.  
       [0024] 8. The maximum particle diameter of the resin may be 5 μm or less.  
       [0025] 9. The binder for granulation molding of powder particles may comprise at least one resin selected from the group consisting of polyol resin, polyester resin, a homopolymer of styrene, a homopolymer of a substituted derivative of styrene, a styrene-based copolymer, acrylic resin, methacrylate resin, polyethylene, polypropylene, epoxy resin, silicone resin, polyamide resin, furan resin, xylene resin, polyvinyl butyral, terpene resin, chroman indene resin, diene-based resin, maleic acid resin, polyvinyl chloride, polyvinyl acetate, polyethylene-vinyl acetate resin, and petroleum-based resin.  
       [0026] 10. The binder for granulation molding of powder particles may comprise at least one resin selected from the group consisting of polyol resin, styrene-acrylic copolymer, and polyester resin.  
       [0027] 11. The binder for granulation molding of powder particles may comprise waste toners as the resin.  
       [0028] 12. The binder for granulation molding of powder particles may be used in granulation molding of aluminum powder particles comprising at least one kind of aluminum residues consisting of aluminum dross, aluminum ash or aluminum mineral residues used as a steel-making flux material and generated at an aluminum refining, secondary refining or melting step.  
       [0029] 13. A Granulated molding compriseing 1 to 20% by weight of the binder for granulation molding of powder particles according to above item 1 compounded with composite powder particles based on aluminum residues, minerals, or metals.  
       [0030] The other objects, features and advantages of the present invention are specifically set forth in or will become apparent from the following detailed descriptions of the invention when read in conjunction.  
       DETAILED DESCRIPTIONS  
       [0031] The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that when powder particles are granulated and molded adding a binder which includes a particular resin, the obtained granulated moldings have excellent performance of granulation, shape retention and crushing strength, and the granulated moldings do not cause excess heating by chemical reaction. In addition-, the present inventors have found that waste toners which are scrapped at present are favorable as the resin, and then applying the waste toners makes the cost of granulation molding inexpensive. Then, the present inventors have succeeded in developing a binder with broader applicability.  
       [0032] Hereinafter, embodiments of the present invention are described.  
       [0033] (1) Binder for Granulation Molding  
       [0034] The binder of the present invention is a resin having a softening point suitable as a binder resin-for toners. The toners are used widely in electrophotography, electrostatic printing, electrostatic recording and the like, and the binder resin therefor is required to exhibit a good fixing ability, that is, good heat fusion under fixing heating, to render itself low viscous. In fixing, there is a difference in the system, that is, contact fixing and non-contact fixing, and the fixing temperature in the former is lower, and thus the softening point of the binder resin used is lower, but in the present invention, the resin is used as binder for granulation molding of powder particles, that is, the resin is used under compression, and therefore, any binder resins can be used to give preferable results.  
       [0035] At the time of granulation molding, the binder is subjected to friction compression and thus inevitably evolves heat. The resin is preferably the one to be softened by this heat because the necessity for separately arranging a heating unit can be eliminated.  
       [0036] From the viewpoint described above, a resin having a softening point of preferably 100° C. or less, more preferably 60° C. or less is compounded, because the resin is heated to about 60° C. upon friction compression.  
       [0037] When the resin is in the form of finely divided particles, the surface area of the resin, relative to the total volume, is large. Accordingly, the frictional area is increased thereby increasing the efficiency of friction compression, to improve thermal conductivity and fluidity, resulting in an increase in binder reactivity, and therefore, the finely divided particles are preferably used.  
       [0038] From the viewpoint described above, a resin having a maximum particle diameter of 50 μm or less is preferably compounded, and a smaller diameter is more preferable.  
       [0039] The binder may be compounded with other components in such an extent that the function of the binder is not deteriorated, and in a usual mode, the content of the resin is 50% or more by weight.  
       [0040] Examples of the resin which can satisfy the above conditions include polyol resin, styrene-acrylic copolymer, polyester resin, styrene resin and epoxy resin.  
       [0041] More preferable examples of the resin are polyol resin, styrene-acrylic copolymer and polyester resin. Hereinafter, these 3 types of resins are described in more detail.  
       [0042] The polyol resin is a resin produced by modifying epoxy resin, and various known polyol resins can be used.  
       [0043] By way of example, the polyol resin (1) includes compounds obtained by reacting epoxy resin, a divalent phenol-alkylene oxide adduct or a glycidyl ether thereof, and a compound having, in the molecule, 2 or more active hydrogens reacting with epoxy groups.  
       [0044] The epoxy resin includes, for example, products obtained by condensating bisphenol such as bisphenol A and bisphenol F with epichlorohydrin.  
       [0045] The divalent phenol-alkylene oxide adduct includes reaction products of alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide or a mixture thereof with a divalent phenol, for example bisphenol such as bisphenol A or bisphenol F. The glycidyl ether includes, for example, products produced by glycidylating the adduct with epichlorohydrin or β-methyl epichlorohydrin. Preferable examples include diglycidyl ethers of bisphenol A-alkylene oxide adducts represented by the formula:  
                 
 
       [0046] wherein R represents either one of  
       —CH 2 —CH 2 —                 
 —CH 2 —CH 2 —CH 2 — 
       [0047] each of n and m is 1 or more and each represents the number of repeating units, and satisfies the equation n+m=2 to 6.  
       [0048] The compound having, in the molecule, 2 or more active hydrogens reacting with epoxy groups includes, for example, phenols, polyvalent phenols and polycarboxylic acids. The divalent phenols include bisphenols such as bisphenol A and bisphenol F; the polyvalent phenols include o-cresol novolaks, phenol novolaks, tris(4-hydroxydiphenyl) methane and 1-[α-methyl-α-(4-hydroxydiphenyl)ethyl]benzene; and the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid and trimellitic anhydride.  
       [0049] The polyol resin (1)′ includes those obtained by inactivating the terminals of polyol resin by reacting a compound having 1 active hydrogen reacting with an epoxy group (for example, monovalent phenols such as phenol, cresol, isopropyl phenol, amyl phenol, nonyl phenol, dodecyl phenol, xylenol and p-cumyl phenol, secondary amines such as diethylamine, dipropylamine, dibutylamine, N-methyl(ethyl)piperazine and piperidine, and carboxylic acids such as propionic acid and caproic acid) allowed to be present during the reaction of the epoxy resin and the like or by adding and reacting the compound after the reaction.  
       [0050] Examples of other polyol resin (2) include those obtained by esterifying a secondary hydroxyl group of epoxy resin.  
       [0051] The esterifying agent used includes C 3-25  monocarboxylic acids (for example, C 6-20  monocarboxylic acids such as propionic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, oleic acid, margarine acid, arachic acid, linolic acid, linoleic acid, castor oil fatty acid, and toll oil fatty acid), monovalent carboxylate derivatives (for example, lower alkyl carboxylates such as methyl and ethyl carboxylates), lactones (for example, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone and γ-valerolactone).  
       [0052] Further, the polyol resin (2)′ includes those whose terminals have been inactivated by reacting a compound having 1 active hydrogen reacting with an epoxy group (for example, C 6-40  monovalent phenols such as phenol, cresol, isopropyl phenol, amyl phenol, nonyl phenol, dodecyl phenol, xylenol and p-cumyl phenol and C 6-25  monovalent carboxylic acids such as acetic acid, propionic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, oleic acid, margarine acid, arachic acid, linolic acid, linoleic acid, castor oil fatty acid, and toll oil fatty acid).  
       [0053] The styrene-acrylic copolymer is obtained by copolymerizing or partially crosslinking a styrene monomer with acrylate or methacrylate, and various known styrene-acrylic copolymers can be used.  
       [0054] The styrene monomer includes, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,4-dimethylstyrene and the like.  
       [0055] The acrylate includes, for example, ethyl acrylate, methyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, ethyl methacrylate, methyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate.  
       [0056] The styrene-acrylic copolymer includes, for example, a styrene-acrylic copolymer, styrene-methyl methacrylate copolymer, styrene-n-butyl acrylate copolymer, styrene-butyl methacrylate copolymer, styrene-diethylaminoethyl methacrylate copolymer, styrene-methyl methacrylate-n-butyl acrylate copolymer, styrene-methyl methacrylate-butyl acrylate-N-(ethoxymethyl) acrylamide copolymer, styrene-glycidyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-diethylaminoethyl methacrylate copolymer, styrene-butadiene-acrylate copolymer, styrene-butadiene copolymer, styrene-butadiene-chlorinated paraffin copolymer, styrene-butadiene-dimethylaminoethyl methacrylate copolymer, styrene-acrylate-maleate copolymer, styrene-n-butyl acrylate-2-ethylhexyl acrylate copolymer, styrene-methyl methacrylate-2-ethylhexyl acrylate copolymer, styrene-n-butyl acrylate-ethylglycol methacrylate copolymer, and styrene-n-butyl methacrylate-acrylic acid copolymer.  
       [0057] As the polyester resin, various known polyester resins obtained by polycondensation reaction of an alcohol with an acid can be used.  
       [0058] The alcohol includes, for example, diols such as polyethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol and 1,4-butene diol, etherified bisphenols such as 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylene bisphenol A, polyoxypropylene bisphenol A, divalent alcohol monomers derived from these bisphenols by substitution with C 3-22  saturated or unsaturated hydrocarbon groups, other divalent alcohol monomers, and polyvalent (trivalent or more) alcohol monomers such as sorbitol, 1,2,3,6-hexatetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzne.  
       [0059] The carboxylic acid includes, for example, monocarboxylic acids such as palmitic acid, stearic acid and oleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, terephthalic acid, cyclohexane dicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, divalent organic acid monomers derived from these acids by substitution with C 3-22  saturated or unsaturated hydrocarbon groups, acid anhydrides thereof, a dimer of lower alkyl ester and linoleic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene carboxypropane, tetra(methylenecarboxyl) methane, 1,2,7,8-octanetracarboxylic acid, and polyvalent (trivalent or more) acid monomer such as anhydrides thereof.  
       [0060] As the polyester resin, various known polyester resins obtained by polycondensation reaction of a polyol with a polycarboxylic acid can also be used.  
       [0061] The polyol includes, for example, ethylene glycol, propyelene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, bisphenol A-ethylene oxide adduct, and bisphenol A-propylene oxide adduct.  
       [0062] The polyester resin includes crystalline polyester having a crosslinked structure by an unsaturated site (unsaturated bonds), that is, crosslinked crystalline polyester. The crosslinked crystalline polyester has an unsaturated site of unsaturated double bonds and is obtained by condensation reaction of a mixture of a divalent or more unsaturated carboxylic acid and a divalent or more saturated carboxylic acid with a divalent or more alcohol.  
       [0063] In addition, the polyester resin includes a non-linear polyester resin comprising 3 to 15 mol-% polyvalent (trivalent or more) carboxylic acid monomer unit, 5 to 30 mol-% polyvalent carboxylic acid monomer unit and/or polyvalent alcohol monomer unit (soft segment component) having a C 5-30  saturated or unsaturated aliphatic hydrocarbon group, the balance being a divalent acid component, a divalent alcohol component and the like.  
       [0064] Further preferably used are resins conventionally used as binder resin for toners, for example homopolymers of styrene and substituted derivatives, such as polystyrene, poly-p-chlorostyrene and polyvinyl toluene, polystyrene-based copolymers other than those described above, for example styrene-butadiene copolymer, styrene-acrylonitrile copolymer and styrene-maleic anhydride copolymer, and acrylic resin, methacrylate resin, polyethylene, polypropylene, epoxy resin, silicone resin, polyamide resin, furan resin, xylene resin, polyvinyl butyral, terpene resin, chroman indene resin, diene-based resin, maleic acid resin, polyvinyl chloride, polyvinyl acetate, polyethylene-vinyl acetate resin, and petroleum-based resin.  
       [0065] Any of these resins are positively used as binder resin for toners in electrophotography, electrostatic printing, electrostatic recording and the like.  
       [0066] At present, electrophotographic products and the like are recovered by manufactures, and toners contained in the products are also recovered. Accordingly, the used toners conventionally disposed of after recovery are also preferable as the resin to be incorporated into the binder of the present invention.  
       [0067] The toners are composed inherently of finely divided particles, and the maximum particle diameter of toners from any manufactures is about 12 μm. However, the used toners wear out by impact and friction in products during use, and thus have smaller diameters by about several μm than those of initially used toners. Accordingly, the recovered waste toners have improvements in thermal conductivity and fluidity, and are thus more preferable as the resin to be incorporated into the binder of the present invention.  
       [0068] Other than the above, toners discharged from factories can be utilized as the resin to be incorporated into the binder of the present invention.  
       [0069] In electrophotography, the electrophotographic process consisting of various steps such as electrification, light exposure, development, transfer, separation and fixation is complicated, and a too small toner diameter causes drawbacks in the process and brings about problems in products. To improve the process, toners having a particle diameter of 5 μm or less, produced in factories, are not marketed. Conventionally, such unused toners discharged from factories are disposed of. There is no necessity for disposal of toners having a maximum particle diameter of 12 μm or more because their diameter can be reduced by means such as milling in factories that is a major step in the process of producing toners.  
       [0070] Accordingly, it can be said that waste toners discharged from factories have smaller particle diameters than those of usual toners and are thus very excellent in thermal conductivity and in fluidity and most preferable as the resin to be incorporated into the binder of the present invention.  
       [0071] Accordingly, utilization of the waste toners as the binder is advantageous because pretreatment such as milling is not necessary before granulation molding.  
       [0072] A coloring matter and other additives contained in the toners will not deteriorate the function of the toners as the binder of the present invention.  
       [0073] (2) Powder Particles for Granulation Molding  
       [0074] The powder particles in the present invention are intended to be those of a metal, metal oxide or mineral generated at various steps such as refining and melting carried out to obtain a desired metal from ores, but the powder particles in this invention are not limited thereto, and encompasses powder particles milled for reutilization of wastes.  
       [0075] The binder of the present invention does not react with metal aluminum or aluminum compounds such as aluminum nitride, aluminum chloride and aluminum carbide, is excellent in moldability, and unlike tar or pitch, does not deteriorate the working atmosphere after addition to melt pig iron or melt steel, and the present binder is thus preferable in granulation molding using, as steel-making flux, aluminum-based powder particles containing aluminum residues consisting of aluminum dross, aluminum ash or aluminum mineral residues generated at the aluminum refining, secondary refining and melting steps.  
       [0076] Recently, composite flux having components (MgO.CaO.SiO 2 .Al 2 O 3 ) and basicity (CaO/SiO 2 ) regulated by compounding minerals such as lime, silicate carbide, fluorite, dolomite and lightly burned magnesia with aluminum residues is also produced as steel-making flux for complex chemical reactions, and as a matter of course, the binder of the present invention is suitable for granulation molding of such composite flux.  
       [0077] (3) Amount of the Binder Compounded  
       [0078] The binder is compounded preferably in an amount of 1 to 20% by weight (in terms of solids content) relative to the total amount (100% by weight) of powder particles and the binder. This is because if the amount is less than 1% by weight, a satisfactory binder effect is not demonstrated, but given 20% by weight or less, a sufficient binder effect can be achieved.  
       [0079] (4) Granulation Molding Method  
       [0080] Granulated moldings are obtained in a usual manner in any forms such as particles, pellets and briquettes, depending on use.  
       [0081] To prepare flux for manufacture of pig iron or steel, the binder and powder particles are kneaded, granulated and molded with a pelletizer or a low-pressure briquetting machine for wet manufacture of steel or with a high-pressure briquetting machine or a rotary press machine for dry molding, among which the high-pressure briquetting machine or the rotary press machine for dry molding are used preferably for preventing a loss of metal aluminum due to the reaction of water with metal aluminum as a reducing component in steel-making flux and for preventing evolution of ammonia gas due to the reaction of water with aluminum nitride contained in aluminum residues. The high-pressure briquetting machine can achieve higher productivity than by the rotary press machine, and can control production costs, and therefore, the high-pressure briquetting machine is used in many cases in actual operation.  
       [0082] In usual operation, the roll pressure in the high-pressure briquetting machine is 10 to 20 tons/cm 2 , and thus the roll temperature is raised to 60 to 80° C. even if a special heating device is not arranged. The resin of the present invention is confirmed to achieve a binding effect at 30° C. or more and a practical binding effect at 60° C. or more at the above-mentioned pressure. Accordingly, subsequent heat treatment can be omitted by utilizing the molding heat at the time of molding.  
       [0083] When a heating device is used, the upper limit of the temperature is predetermined at 200° C. or less to prevent gasification of the resin. 
     
    
    
     EXAMPLES  
     [0084] Hereinafter, the present invention is described in more detail with reference to the Examples.  
     Example 1  
     [0085] Confirmation of Binder Effect at Different Heating Temperatures  
     [0086] Aluminum ash (metal aluminum: 50% by weight) generated in secondary refining of aluminum was used as the inorganic powder particles.  
     [0087] As the binder for granulation molding, a mixture of 100 g bisphenol A type liquid epoxy resin, 45.26 g bisphenol A, 30.9 g p-cumyl phenol and 20 g xylene was heated to 70° C. in a nitrogen atmosphere, and lithium chloride, 0.032 g/H 2 O, was added thereto, and the mixture was reacted at 150 to 180° C. for 4 to 7 hours, to give a modified epoxy polyol resin having a softening point of 100° C. and a Tg of 56° C. This product was finely pulverized such that the maximum particle diameter was reduced to 12 μm or less, in order to improve the reactivity thereof as the binder.  
     [0088] The binder was incorporated in various proportions into the aluminum ash, granulated and molded into cylindrical samples (diameter, 28 mm; thickness, 8 mm) by a hand press machine [SSP-10A (not evolving molding heat), manufactured by Shimadzu Corporation], heated to a predetermined temperature in an electrical furnace, then removed, left and cooled.  
     [0089] There was a difference in the granulating ability between the aluminum ash with or without at least 1% by weight binder, and the aluminum ash with at least 1% by weight binder was excellent in releasability from the molding, thus confirming its lubricant effect.  
     [0090] Further, the sample just after cooled to room temperature was measured for crushing strength by a tensile compression testing machine [SV-2000-0 (Imai Seisakusho Co., Ltd.)]. The results are shown in Table 1. From these results, it was confirmed that the crushing strength is significantly increased by heating, and the molding heat generated in dry high-pressure molding can be utilized.  
               TABLE 1                          Measurement results of crushing strength at different heating temperatures                 (Kgf)                         Temperature           Heating temperature in electrical furnace           (each sample was measured after being heated to a predetermined       Compounding   temperature, immediately removed, left and cooled.)                                                 ratio   30° C.   40° C.   50° C.   60° C.   80° C.   100° C.   140° C.   180° C.                                                         Not added   4   4   4   4   4   4   4   4       Added at 1%   41   48   53   59   89   107   109   118       Added at 5%   65   83   107   127   167   191   ≧200   ≧200       Added at 10%   98   134   151   180   ≧200   ≧200   ≧200   ≧200                  
 
     Example 2  
     [0091] Confirmation of Granulating Ability and Binder Effect by the Resin Added in Different Amounts  
     [0092] To confirm the granulating ability and binder effect adapted to an actual production process with a machine, the same aluminum ash and binder as in the Example 1 were granulated and molded with a small testing machine ([briquetting machine BSC-25 (not evolving molding heat), manufactured by Shintokogio, Ltd.), to form granulated moldings in a hard-tack form of 20 mm in width, 25 mm in length and 25 mm in thickness.  
     [0093] The granulated moldings were sifted with a screen having a 3 mm mesh size, and as a result, there was a difference in the granulated molding and powder particle distribution ratio among the aluminum ashes with or without the resin compound, thus confirming an improvement in the granulating ability.  
     [0094] The crushing strength was measured in the same manner as in the Example 1. The measured strength was higher in proportion to the amount of the binder added and the heating temperature, thus confirming its binder effect.  
               TABLE 2                          Measurement results of granulation yield and crushing strength by the resin       added in different amounts                 (Kgf)                         Measurements                                 Crushing strength (Kgf)                                                 Granulation yield   at time                           Compounding   (%)   of                                                 ratio   +3 mm   −3 mm   molding   30° C.   40° C.   50° C.   60° C.   100° C.                                                         Not added   65   35   35.2   36.5   35.8   35.5   36.1   34.2       Added at 1%   85   15   50.7   60.4   67.8   67.1   68.5   71.2       Added at 3%   93   7   68.4   69.7   70.8   80.7   95.2   156.8       Added at 5%   95   5   70.8   78.1   81.4   85.3   110.8   177.2       Added at 10%   98   2   75.8   90.6   100.4   150.2   189.4   ≧200                  
 
     Example 3  
     [0095] Confirmation of Binder Effect in a Machine  
     [0096] To confirm the binder effect in a machine, the same aluminum ash as in the Example 1 and various binders (the same polyol resin as in the Example 1, styrene-acrylic copolymer, polyester resin (obtained by polycondensation of polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl) propanol and fumaric acid) were compounded such that the ratio of the binder was 5% by weight, and then granulated and molded in production facilities having material-receiving hoppers (10 m 3 ×5), a mixing machine (10 m 3 ), a mixed material-storing hopper (5 m 3 ) and a molding machine (high-pressure briquetting machine that can granulate at a ratio of 3 to 5 tons/hour, manufactured by Shintokogio, Ltd.) arranged in line, to prepare 12 ton products in total (1 flexible container bag/ton).  
     [0097] In the case of a granulating machine in production line, the temperature of the molding roll was varied depending on molding pressure, but was usually in the temperature range of 60 to 100° C., and the temperature just after molding of granulated moldings was 40 to 80° C.  
     [0098] The granulating ability and crushing strength were measured in the same manner as in the Example 2. Both the measured granulating ability and crushing strength were higher in proportion to the amount of the binder added, to confirm its binder effect also excellent in a change with time.  
     [0099] The crushing strength in Table 3 is the average of 100 samples sampled at random from an upper part of 12 flexible container bags. The crushing strength in Table 4 is the average of 100 samples different from those in Table 3 and sampled at random from an upper part of 12 flexible container bags.  
               TABLE 3                          Measurement results of granulation yield and crushing       strength of each resin                         Measurements                             Granulation yield (%)   Crushing                                 +3 mm   −3 mm   strength           (granulated   (recycle starting   (Kgf)       Resin   material)   material)   [Average]                                     No additive   83.8   16.2   35.2       Polyol resin   98.3   1.7   96.8       (compounded at 5%)       Styrene acrylic resin   98.1   1.9   97.1       (compounded at 5%)       Polyester resin   98.5   1.5   96.4       (compounded at 5%)                  
 
     [0100]               TABLE 4                          Measurement results of crushing strength with time                         Measurements (10N)           Elapsed time (hour) · Crushing strength (Kgf) [Each resin compounded at 5%]                                                     At time of                                   Resin   production   6 h   12 h   24 h   48 h   72 h   120 h   168 h                                                         No additive   36.4   30.2   25.8   5.6   Collapsed   Collapsed   Collapsed   Collapsed       Polyol resin   102.3   101.4   102.3   98.4   95.6   90.2   86.4   77.3       Styrene acrylic   104.5   104.1   103.5   99.7   94.2   90.7   86.1   77.1       resin       Polyester resin   101.3   102.8   101.5   98.5   95.7   90.6   88.2   76.9                    
     Example 4  
     [0101] Confirmation of Evaluation of Steel-Making Flux by Using a Production Line  
     [0102] For confirmation of evaluation of steel-making flux by using a production line, the following compounding materials were prepared.  
     [0103] Starting composition A: 70% by weight of aluminum ash (5,600 kg) containing 50% by weight of metal aluminum, 25% by weight of lightly burned magnesia (2,000 kg), and 5% by weight of a styrene-acrylic copolymer (400 kg) pulverized to an average particle diameter of 10 μm or less were mixed and compounded in a ratio of 8 tons/lot.  
     [0104] Starting composition B: 70% by weight of aluminum ash (5,600 kg) containing 50% by weight of metal aluminum, 22% by weight of lightly burned magnesia (1,760 kg), 5% by weight of a commercially available briquetting binder (400 kg) pulverized to an average particle diameter of 10 μm or less, using a polybasic acid such as dimer acid, trimer acid, acrylated fatty acid and maleated fatty acid, and 3% by weight of slaked lime (240 kg) to be compounded according to manufacture&#39;s instructions were mixed and compounded in a ratio of 8 tons/lot.  
     [0105] Starting composition C: 75% by weight of aluminum ash (6,000 kg) containing 50% by weight of metal aluminum and 25% by weight of lightly burned magnesia (2,000 kg) were mixed and compounded in a ratio of 8 tons/lot.  
     [0106] Each composition was granulated and molded in a briquetting machine in a dry high-pressure molding system at a material-feed rate of 2 tons/hour. The roll molding temperature was 80° C., and the temperature just after molding of granulated moldings was 60° C.  
     [0107] The output (per hour) of 10 mm or more granulated moldings to be formed into granulated articles and the amount of the articles produced were an output of 1,950 kg/hour and articles of 7,900 kg [98.75% by weight] for the starting composition A, an output of 1,900 kg/hour and articles of 7,800 kg [97.50% by weight] for the starting composition B, and an output of 1,800 kg/hour and articles of 7,300 kg [91.25% by weight] for the starting composition C, thus confirming its binder effect effective in productivity.  
     [0108] In the reaction with time of granulated moldings, there are a few cases that a briquetting binder comprising a polybasic acid such as dimer acid, trimer acid, acrylated fatty acid and maleated fatty acid, used generally in manufactures of steel-making flux, initiates exothermic reaction in a material based on aluminum ash at the start of granulation molding, to cause ignition and combustion leading to fires, and therefore, the exothermic reaction, along with crushing strength, were measured to obtain data, and as a result, it was confirmed that although the temperature of the starting composition A was 60° C. during molding, the temperature was decreased with time. Further, the starting composition A exhibited significant crushing strength, to confirm the effectiveness of the present resin as a binder.  
     [0109] The binder in the starting composition B was confirmed to be unsafe because the temperature of granulated moldings, which was 60° C. during molding, was increased to 90° C., to show a reaction initiating heat evolution to cause ignition depending on storage conditions. Granulated moldings of the starting composition C were free of exothermic reaction, but were poor in crushing strength and collapsed with time due to swelling, and could thus not be evaluated as articles.  
               TABLE 5                          Weight and proportion of starting composition                                             Styrene acrylic   Generally used                   resin   dimer-timer           Aluminum ash   Lightly burned   (milled to 10   acid-based           (Metal Al 50%)   magnesia   microns)   binder                                             Starting   70W% (5,600 Kg)   25W% (2,000 Kg)   5W% (400 Kg)   —       composition A       Starting   70W% (5,600 Kg)   22W% (1,760 Kg)   —   5W% (400 Kg)       composition B               Slaked lime 3W%       Starting   75W% (6,000 Kg)   25W% (2,000 Kg)   —   —       composition C                  
 
     [0110]               TABLE 6                          Results of change with time in temperature and crushing strength                 (Kgf)                         Sample                                 Starting composition A   Starting composition B   Starting composition C                                             Temperature   Crushing   Temperature   Crushing   Temperature   Crushing       Time elapsed   (° C.)   strength   (° C.)   strength   (° C.)   strength                                                 At time of molding   60.8   98.6   61.5   50.8   62.4   34.5        1 hour   60.5   98.8   68.4   50.1   61.8   34.1        6 hours   51.7   98.5   80.6   55.4   52.4   34.2        12 hours   47.2   98.4   91.4   60.2   46.9   33.8        24 hours   31.4   98.6   90.2   60.5   32.2   5.4        48 hours   26.6   98.4   80.3   61.1   25.9   Collapsed        72 hours   26.7   98.3   60.5   55.4   26.1   —        96 hours   26.3   97.5   40.1   56.7   26.4   —       120 hours   26.5   95.4   28.6   54.1   26.2   —       144 hours   26.1   93.9   28.7   48.2   26.1   —       168 hours   26.4   93.7   28.3   45.9   26.2   —                     Measurement of   1 ton of granulated moldings were introduced into a 1.1 m 3  flexible       temperature   container, and after insertion of thermocouple of 50 cm in length into           central upper part, temperature was measured with recorder.       Crushing strength   Average measured strength of 10 samples left in atmosphere is shown.                    
     [0111] When the granulated moldings (steel-making flux) of the starting composition A were used in a steel manufacturer, the reaction for modification of steel-making slug was good, and there was no black smoke generated from the binder component at the time of introduction into melt steel, and further the molding strength was so high that powdering did not occur at a step of transfer on a belt conveyer in a steel-making factory, thus giving a high rating in evaluation for the environment, reducing a loss in dust collection and raising the yield of flux added. Further, the granulated moldings were excellent in water resistance and did not show a moisture absorption action as exhibited by starch.  
     Example 5  
     [0112] Confirmation of the Binder Effect of Waste Toners  
     [0113] The present inventors attracted their attention to the fact that components of waste toners (with a maximum particle diameter of 12 μm or less) are composite resins of styrene-acrylic copolymer, polyester resin, polyol resin, organic acid salts and the like, and conducted the same test in the same manner as in the fourth example except that waste toners were compounded and granulated and molded as the binder such that its resin components were identical with those of the binder resin in the fourth example. As a result, the same results as those by the starting composition A in the fourth example was confirmed.  
     [0114] As described above, the binder of the present invention can be used in granulation molding of powder particles to give safe moldings having high crushing strength and superior in change with time.  
     [0115] The binder of the present invention does not require addition of water and is excellent in water resistance, and is thus suitable for granulation molding of aluminum residues and the like.  
     [0116] It is required at present to positively address creation of a recycling society, and the present invention can utilize waste toners regarded as industrial waste, thus contributing to creation of a recycling society.  
     [0117] The waste toners are conventionally disposed of, but the costs for disposal are high, and the place for disposal of the waste toners is hardly found. Accordingly, the present invention is very useful in that utilization of the waste toners can eliminate the costs and labor for disposal, and the costs of the starting material of the binder can be reduced to nearly 0, thus significantly reducing the costs of the product.  
     [0118] Although the invention has been described with respect to a specific embodiment for a complete and clear disclosure, the appended claims are not to be thus limited but are to be construed as embodying all modifications and alternative constructions that may occur to one skilled in the art which fairly fall within the basic teaching herein set forth.