WO2022220133A1 - Composition de résine pour moules - Google Patents

Composition de résine pour moules Download PDF

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Publication number
WO2022220133A1
WO2022220133A1 PCT/JP2022/016177 JP2022016177W WO2022220133A1 WO 2022220133 A1 WO2022220133 A1 WO 2022220133A1 JP 2022016177 W JP2022016177 W JP 2022016177W WO 2022220133 A1 WO2022220133 A1 WO 2022220133A1
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Prior art keywords
mold
resin
phenolic
resin composition
phenolic resin
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PCT/JP2022/016177
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English (en)
Japanese (ja)
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鉄山
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旭有機材株式会社
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Priority to JP2022554340A priority Critical patent/JP7247427B2/ja
Publication of WO2022220133A1 publication Critical patent/WO2022220133A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/30—Condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only

Definitions

  • the present invention relates to a resin composition for casting molds, and more particularly to a resin composition that is advantageously used in the production of casting molds such as shell molds capable of effectively suppressing or preventing the occurrence of casting defects. be.
  • the casting surface deteriorates due to the insertion and seizure of molten metal.
  • the surface of the mold is coated with a coating agent containing graphite, zircon, aluminum oxide, etc.
  • the coating work is a complicated work.
  • there are inherent problems such as deterioration of the disintegration of the mold after casting.
  • Patent Document 1 Patent No. 4656474.
  • a mold is prepared by coating the surface of a refractory aggregate with a thermosetting resin and a carbonaceous material, and casting is performed by pouring molten metal.
  • the carbonaceous material has a fixed carbon content of 50 to 98% by mass, and a mold molded using this resin-coated sand is heated at 1000 ° C. to 240 ° C. It has been proposed that the amount of gas generated when heated for a second is 20 mL or more per 1 cm 3 of the mold.
  • a mold molded using such a resin-coated sand can protect the shell mold (mold) from the high temperature of the molten metal without using a mold wash agent, and improve the casting surface of the casting. It is said that it is possible to
  • the present invention has been made against the background of such circumstances, and the problem to be solved is to effectively suppress or prevent the occurrence of casting defects such as seizure and insertion. It is an object of the present invention to provide a composition for a casting mold, which can advantageously produce a casting mold that can be used. In addition, the present invention provides a casting composition that can advantageously produce a casting mold such as a shell mold that can effectively improve the casting operation without applying a washing agent. This is a problem to be solved.
  • the present invention can be suitably implemented in various aspects as listed below. Adoptable. It should be noted that the aspects and technical features of the present invention are not limited to those described below, and can be recognized based on the inventive idea grasped from the description of the entire specification and the drawings. should be understood.
  • the ratio of the amount of gas generated within 20 seconds from the start of measurement to the total amount of gas generated must be 50% or more.
  • a casting mold resin composition characterized by: (2) The mold resin composition according to aspect (1), wherein the phenolic resin is one or more selected from the group consisting of novolac-type phenolic resins, modified novolac-type phenolic resins and resol-type phenolic resins. thing. (3) The casting mold resin composition according to the aspect (1) or the aspect (2), wherein the carbonization accelerator is an organic phosphoric acid ester and/or an organic halide. (4) The mold resin composition according to any one of the above aspects (1) to (3), which is used for making a mold for casting molten iron. (5) A resin-coated sand comprising the casting mold resin composition according to any one of the aspects (1) to (4) and a refractory aggregate. (6) Molding using the resin-coated sand according to the aspect (5), A mold made by heating and hardening.
  • the cured product containing a specific phenolic resin and a carbonization accelerator and completely cured at 150°C generates gas in a reducing atmosphere at 850°C. It is prepared and configured so that the ratio of the amount of gas generated in 20 seconds from the start of measurement to the total amount of gas generated is 50% or more when the amount is measured.
  • a resin-coated sand (mold-making material) is produced using the resin composition for a mold according to such a configuration, and the resin-coated sand is molded and cured by heating.
  • FIG. 2 is a vertical cross-sectional explanatory view of a sand mold for casting tests for producing castings used for evaluation of mold characteristics in Examples.
  • FIG. 3 is a longitudinal cross-sectional explanatory view of a cast iron casting obtained using the sand mold for casting test shown in FIG. 2 ;
  • the ratio of the total value of the peak area of the phenolic monomer and the peak area of the phenolic dimer to the total area of the peaks in the gel filtration chromatographic measurement as the phenolic resin serving as the caking component. is 13.0% or more as the first essential component. If a phenolic resin with such a ratio is less than 13.0% is used, it becomes difficult to solve the problems of the present invention, that is, problems such as seizure prevention and insertion prevention, and it is difficult to eliminate casting defects. Become.
  • the ratio of the total value can be calculated according to a known area percentage method as an analysis method for gel filtration chromatography measurement.
  • the phenol resin is a solid or liquid (varnish) obtained by reacting phenols and aldehydes in the presence of an acidic catalyst or a basic catalyst. or in the form of an emulsion), which are called novolak-type or resol-type condensation products depending on the type of catalyst used therein, in the presence or absence of a given curing agent or curing catalyst. It expresses thermosetting property by heating in the presence.
  • the phenolic resin produced by the above reaction generally contains unreacted phenolic monomers and phenolic dimers, and those sold as phenolic resins contain such phenolic monomers.
  • the ratio of the total value of the peak area of the phenolic monomer and the peak area of the phenolic dimer to the total area of the peaks in gel filtration chromatograph measurement is 13.0% or more, Either resol type phenolic resin or novolac type phenolic resin can be used.
  • phenols used as raw materials for phenolic resins include phenol and phenol derivatives.
  • aldehydes include formalin, which is an aqueous solution of formaldehyde, paraformaldehyde, trioxane, acetaldehyde, and paraaldehyde. , propionaldehyde, etc., and other known aldehyde compounds can be used as appropriate. Any of the phenols and aldehydes may be used alone, or two or more of them may be used in combination.
  • the novolak-type phenolic resin used in the present invention is prepared by using the above-described phenols and aldehydes, and as is well known, an acid catalyst such as inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and oxalic acid. , p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, etc., and further acidic substances such as zinc oxide, zinc chloride, magnesium oxide, zinc acetate, etc., through a condensation reaction.
  • the blending molar ratio (F/P) of the aldehydes (F) and the phenols (P) can be appropriately selected depending on the type of reaction catalyst used, etc., but is preferably , 0.55 to 0.80.
  • the phenols to be reacted with the aldehydes not only phenol is used, but at least part of the phenol is used as a raw material for modification. It is also possible to use a modified novolac-type phenolic resin obtained by reacting aldehydes with an acidic catalyst by using a material (phenol + modifying raw material) substituted for .
  • phenol derivatives can be used as modifying raw materials to replace phenol, but resorcinol, bisphenol F, Polyhydric phenols such as bisphenol A and purification residues of these bisphenols; polycyclic phenols such as 1-naphthol, 2-naphthol, 1-hydroxyanthracene, and 2-hydroxyanthracene; At least one of alkylphenols is employed.
  • the modification ratio of the modified novolac-type phenolic resin in other words, the substitution ratio of phenol by the raw material for modification is generally 20 to 100% by mass, preferably 25 to 95% by mass, more preferably 30 to 90% by mass.
  • the modification rate of such a modified novolac-type phenolic resin is too low, the decomposition of the resin cannot be sufficiently accelerated, and there is the problem that it becomes difficult to effectively increase the volatilization rate.
  • the modification rate is high, the heat resistance of the resin is lowered, and there is a risk that the generation of gas, etc., will end before the molten metal such as molten cast iron to be cast is solidified. .
  • the resol-type phenolic resin is formed by using the above-mentioned phenols and aldehydes and conducting a condensation reaction with a known basic catalyst in the same manner as in the past.
  • a known basic catalyst hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide, and oxides of alkaline earth metals can be used.
  • the blending molar ratio (F/P) of aldehydes and phenols in such a condensation reaction is appropriately selected according to the type of reaction catalyst used therein, but is generally 1.1. It will be selected within the range of ⁇ 4.0.
  • novolak-type phenolic resins It is possible to produce novolak-type phenolic resins, modified novolak-type phenolic resins, and resol-type phenolic resins according to the above-described reactions.
  • the ratio of the total value of the peak area of the group monomer and the peak area of the phenolic dimer is at least 13.0%. It is possible to manufacture by
  • the phenolic resins used in combination are all peaks of phenolic monomers with respect to the total area of peaks in gel filtration chromatograph measurement It is preferable that the ratio of the total value of the peak area of the area and the phenolic dimer (hereinafter simply referred to as "the ratio of the total value”) is 13.0% or more.
  • the ratio of the total value of the entire phenolic resin constituting the mold resin composition is, more specifically, when two or more phenolic resins are used, the two or more phenolic resins As long as the ratio of the total value of the mixture of is 13.0% or more, it is also possible to use a phenolic resin having a ratio of the total value of less than 13.0%. When two or more phenolic resins are used together, it is particularly preferable to use a modified novolac phenolic resin and a resol phenolic resin together.
  • a cured product of a resin composition containing a modified novolak-type phenolic resin and a resol-type phenolic resin tends to have a relatively low cross-linking density and generate a large amount of gas when heated, and thus more advantageously enjoy the effects of the present invention. It becomes possible to
  • the blending ratio is based on the mass of the modified novolak-type phenol resin: resol-type phenol.
  • a use ratio of resin 10:90 to 95:5, preferably 20:80 to 90:10 will be advantageously employed.
  • the ratio of modified novolac-type phenolic resin used increases (the ratio of resol-type phenolic resin used decreases), the curing speed tends to become slower, and the ratio of modified novolac-type phenolic resin used decreases, so resol-type If the amount of phenol resin increases, problems such as a decrease in mold strength will occur.
  • a carbonization accelerator for promoting carbonization of the heated phenolic resin is used as a second essential component together with the specific phenolic resin described above.
  • a carbonization accelerator for promoting carbonization of the heated phenolic resin is used as a second essential component together with the specific phenolic resin described above.
  • the carbonization of the phenolic resin is effectively promoted, and in particular, after the middle stage of casting (a stage relatively long after the start of pouring), the carbonization of the phenolic resin is formed.
  • a carbonized film is advantageously formed between the mold and the molten metal, thereby effectively protecting the mold from the high-temperature molten metal and effectively suppressing or preventing the occurrence of seizure. Problems such as insertion of molten metal can be prevented, and the casting surface of the obtained casting can be effectively improved.
  • the carbonization accelerator in the present invention is not particularly limited as long as it can promote the carbonization of the phenolic resin when heated together with the phenolic resin.
  • organic phosphates used as carbonization accelerators include halogen-containing phosphates such as tris(tribromopentyl)phosphate and tris( ⁇ -chloropropyl)phosphate (TCPP), and halogen-free Non-halogen phosphates and halogen-free non-halogen condensed phosphates can be exemplified.
  • non-halogenated phosphates include aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, methyldiethyl phosphate, methyldibutyl phosphate, and ethyl dibutyl phosphate; Phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) Aromatic phosphoric acid esters such as phosphate, isopropylphenyldiphenylphosphate, bis-(isopropylphenyl)diphenylphosphate, tris-(isopropylphen
  • non-halogenated phosphate esters When such non-halogenated phosphate esters are used as the carbonization accelerator of the present invention, those having a phosphorus content of 8% or more calculated by the following formula (1) are advantageously used.
  • [Phosphorus content] (%) [(atomic weight of phosphorus element in compound
  • organic halides used as carbonization accelerators include chlorinated paraffin, chlorinated diphenyl, chlorinated ethane, chlorinated polyethylene, chlorinated polyphenyl, chlorinated diphenyl, vinyl chloride, perchlorocyclopenta Organic chlorine compounds such as decanone, tetrachlorobisphenol A, trischloroethyl phosphate, trisdichloropropyl phosphate, tris- ⁇ -chloropropyl phosphate; brominated paraffin, polybrominated biphenyl (PBB), tetrabromoethane, tetrabromobenzene , decabromodiphenyl oxide, octabromodiphenyl oxide, hexabromocyclododecane, bis(tribromophenoxy)ethane, ethylenebistetrabromophthalimide, hexabromobenzene, polyd
  • the cured product completely cured at 150 ° C. is measured for the amount of gas generated in a reducing atmosphere at 850 ° C., and the measurement of the total amount of gas generated is started.
  • the molding resin composition according to the present invention can be obtained by adjusting the ratio of the amount of gas generated in 20 seconds to 50% or more. In this way, among the amount of gas generated when the cured product is heated in a reducing atmosphere, the amount of gas generated particularly at the initial stage of heating is increased, so that the carbonization accelerator is blended. Therefore, it is possible to enjoy the effects of the present invention.
  • the amount of the carbonization accelerator used is usually about 2 to 50 parts by mass, preferably in the range of 3 to 50 parts by mass, with respect to 100 parts by mass of the phenolic resin. It will happen.
  • the timing of blending the carbonization accelerator in the preparation of the casting resin composition can be appropriately selected based on the knowledge of those skilled in the art.
  • a carbonization accelerator to the phenol resin. It may be blended (mixed) at the time of resin synthesis, or may be mixed with a molten novolak-type phenolic resin immediately after synthesis. It is also possible to add a carbonization accelerator during or after kneading with the resin and mix.
  • the resin composition for molds of the present invention may optionally contain various kinds of compounds that have been generally used in the past for the purpose of improving the physical properties of the mold making material itself and improving the physical properties of the mold to be molded.
  • Additives can also be blended as appropriate.
  • lubricants that contribute to the improvement of fluidity of casting mold materials include waxes such as paraffin wax, synthetic polyethylene wax, and montanic acid wax; stearic acid, stearyl alcohol, stearic acid monoglyceride; stearyl stearate; metal stearates such as calcium stearate, zinc stearate, magnesium stearate and lead stearate; hardened oils and the like can be added.
  • a coupling agent that strengthens the bond between the refractory aggregate and additive components such as binder resin.
  • additive components such as binder resin.
  • silane coupling agents, zircon coupling agents, titanium coupling agents, etc. are used. can do
  • release agents such as paraffin, wax, light oil, machine oil, spindle oil, insulating oil, waste oil, vegetable oil, fatty acid ester, organic acid, mica, vermiculite, fluorine release agent, silicone release agent, etc. is also available.
  • Each of these additives is used in a proportion of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, per 100 parts by weight of the phenolic resin.
  • RCS casting mold material
  • silica sand and artificial silica sand including silica sand and artificial silica sand, special sand such as alumina sand, olivine sand, zircon sand, chromite sand, and slag particles such as ferrochrome slag, ferronickel slag, and converter slag; artificial particles such as alumina-based particles and mullite-based particles, and regenerated particles thereof; alumina balls, magnesia clinker, and the like.
  • These refractory aggregates may be new sand, or recycled or recovered sand that has been used once or more than once for molding molds as foundry sand.
  • refractory aggregates are generally used with a particle size of about 40 to 200, preferably about 60 to 150, in terms of AFS index.
  • a binder resin predetermined Phenolic resin
  • a carbonization accelerator and other additives selected as necessary are added, and after kneading, a predetermined curing agent such as hexamethylenetetramine and a curing accelerator are added, and air cooling Therefore, a so-called dry hot coating method, in which the lump content is broken into granules and then calcium stearate (lubricant) is added, is advantageously employed.
  • the timing of kneading the molding resin composition of the present invention and the refractory aggregate can be appropriately selected based on the knowledge of those skilled in the art.
  • each component constituting the resin composition for casting molds is added to the refractory aggregates.
  • the carbonization accelerator can be mixed with the phenolic resin, or all components can be mixed at the same time.
  • a large amount of additives such as a carbonization accelerator it is possible to adopt a divided addition method such as adding both the phenol resin and the refractory aggregate and phenol resin after kneading. be.
  • the mold-making material obtained as described above is heated to harden by heating.
  • the desired mold is molded, but such a heat molding method is not particularly limited, and any conventionally known method can be advantageously used.
  • the mold-making material as described above is filled into a mold heated to about 150 to 300° C., which has a desired molding space that provides the desired mold, by a gravity drop method, a blow method, or the like, and cured. After that, the desired casting mold can be obtained by removing the hardened mold from the mold.
  • such a casting mold is advantageously molded at a filling rate of 50% or more, and by realizing such a filling rate, the internal structure of the mold takes a stone wall structure. This makes it possible to prevent the intrusion of molten metal and advantageously increase the gas pressure from the mold.
  • a mold filling rate can be measured by a known method, and for example, a method as disclosed in paragraph [0060] of JP-A-2019-177402 can be employed.
  • the mold thus obtained is advantageously endowed with the above-mentioned excellent features such as seizure resistance. It can be advantageously used for casting of iron-based molten metal, and its characteristics can be exhibited more effectively.
  • the ratio (%) of the total value is simply referred to as "area ratio (%)".
  • the area ratios of the phenol resins A to D are shown in Tables 1 to 3 below, respectively.
  • Example 16 Comparative Example 4 and Comparative Example 5 using any two of the phenolic resins A to D, phenol mixed at the ratio shown in Table 2 or Table 3 below Using the resin mixture as a sample, GPC measurement was performed, and the area ratio (%) calculated from the measurement results is shown in Tables 2 and 3 below.
  • the resin compositions for molds according to the following examples and comparative examples were pulverized and mixed as necessary depending on the components, then the resin compositions were placed in an aluminum cup, and the aluminum cup was heated to about 150°C. It is placed on a metal plate, and after the resin composition in the cup is thermally melted, it is cured for 5 minutes while stirring the inside of the cup with a spatula. After that, the aluminum cup is transferred from the metal plate to a thermo-hygrostat heated to 150° C. and placed in the thermo-hygrostat for 30 minutes to completely cure the resin composition in the aluminum cup.
  • a cured product of the obtained resin composition is pulverized, and the pulverized product is put into a copper tube and sealed with glass wool to obtain a sample.
  • the sample is placed in a furnace having a reducing atmosphere at 850° C. in a gas generation amount measuring machine, and the amount of gas generated from the pulverized material is measured immediately after the placement. The measurement is continued until the generation of gas is finished, and from the measurement results, the amount of gas generated in 20 seconds from immediately after placing the sample in the furnace and the total amount of gas generated are calculated. From the calculation result, the ratio (%) of the amount of gas (a) generated within 20 seconds to the total amount of gas generated (A) is calculated.
  • FIG. 1 the measurement results of the amount of gas generated for each mold resin composition according to Example 1 and Comparative Example 1 are shown in FIG. 1 as a graph.
  • a half hollow main mold 6 (cavity diameter: 6 cm, height: 6 cm), a circular airless element having a skirting part 8, which was molded by blowing and filling each mold molding material into a mold heated to 250 ° C. and heating for 120 seconds.
  • 10 (diameter: 5 cm, height: 5 cm) is adhesively fixed by the baseboard fixing part 4, and then the half-split hollow main mold 6 is adhesively fixed to each other to prepare a sand mold 12 for casting test.
  • the bonded main mold is clamped with a vise or the like, or tightly fixed by wrapping it with a wire.
  • molten cast iron FC200 (temperature: 1380° C. ⁇ 40° C.) is poured from the molten metal injection port 2 of the sand mold 12 for casting test and allowed to solidify. 3, a cylindrical casting 16 is removed. Then, the resulting casting 16 is cut in half, and the conditions of seizure and casting surface (casting surface) are visually and tactilely confirmed. evaluate.
  • Phenolic Resin A A reaction vessel equipped with a thermometer, stirrer and condenser was charged with 350 parts phenol, 118 parts 47% formalin, 30 parts 92% paraformaldehyde and 3 parts oxalic acid. Next, the temperature of the reaction vessel was gradually raised while stirring the inside of the vessel until it reached the reflux temperature, and then the reflux reaction was carried out for 90 minutes while maintaining the reflux temperature. 430 parts of phenolic resin A, which is a novolac-type phenolic resin, was obtained by concentrating under reduced pressure while heating until the content reached . The area ratio of the phenolic resin A (in GPC measurement, the ratio of the sum of the peak area of the phenolic monomer and the peak area of the phenolic dimer to the total peak area) was 13.9%.
  • Phenolic Resin B- A reaction vessel equipped with a thermometer, stirrer and condenser was charged with 115 parts phenol, 110 parts 47% formalin, 450 parts bisphenol A, 100 parts water and 2 parts oxalic acid. Next, the temperature of the reaction vessel was gradually raised while stirring the inside of the vessel until it reached the reflux temperature, and then the reflux reaction was carried out for 90 minutes while maintaining the reflux temperature. 600 parts of phenolic resin B, which is a modified novolac-type phenolic resin, was obtained by concentrating under reduced pressure while heating until the content reached 600 parts. The area ratio of the phenolic resin B (in GPC measurement, the ratio of the sum of the peak area of the phenolic monomer and the peak area of the phenolic dimer to the total peak area) was 26.0%.
  • Phenolic Resin D- A reaction vessel equipped with a thermometer, stirrer and condenser was charged with 400 parts phenol, 217 parts 47% formalin, and 3 parts oxalic acid. Next, the temperature of the reaction vessel was gradually raised while stirring the inside of the vessel until it reached the reflux temperature, and then the reflux reaction was carried out for 90 minutes while maintaining the reflux temperature. 570 parts of phenolic resin A, which is a novolac-type phenolic resin, was obtained by concentrating under reduced pressure while heating until the content reached . The area ratio of the phenolic resin D (in GPC measurement, the ratio of the sum of the peak area of the phenolic monomer and the peak area of the phenolic dimer to the total peak area) was 10.6%.
  • Example 1- 100 parts of a phenolic resin A and 10 parts of an aliphatic condensed phosphate: PNX (trade name: Fyrol PNX-LE, manufactured by ICL JAPAN Co., Ltd.) as a carbonization accelerator as components of a resin composition for a mold. and 15 parts of hexamethylenetetramine as a curing agent dissolved in water.
  • PNX trade name: Fyrol PNX-LE, manufactured by ICL JAPAN Co., Ltd.
  • PNX aliphatic condensed phosphate
  • the phenolic resin A of the mold resin composition and the carbonization accelerator (PNX) were sequentially put into a whirl mixer and mixed for 60 seconds. Kneaded. Further, a hardening agent (hexamethylenetetramine) dissolved in water was added, air cooled, and then 5 parts of calcium stearate was added to obtain a mold material for shell mold (molding material).
  • PNX carbonization accelerator
  • Example 2- For shell molds, following the same procedure as in Example 1, except that an aromatic condensed phosphate ester (trade name: CR-733S, Daihachi Chemical Industry Co., Ltd.) was used instead of PNX as the carbonization accelerator. A mold material was obtained.
  • an aromatic condensed phosphate ester trade name: CR-733S, Daihachi Chemical Industry Co., Ltd.
  • Example 3- A mold material for a shell mold was obtained in the same manner as in Example 1, except that 2,4,6-tribromophenol (TBP), which is an organic halide, was used as the carbonization accelerator instead of PNX. rice field.
  • TBP 2,4,6-tribromophenol
  • Example 4- A mold material for a shell mold was obtained in the same manner as in Example 1, except that tetrabromobisphenol A (TBBA), which is an organic halide, was used as the carbonization accelerator instead of PNX.
  • TBBA tetrabromobisphenol A
  • Example 5- A mold material for a shell mold was obtained in the same manner as in Example 1, except that the amount of carbonization accelerator (PNX) used was 3 parts.
  • Example 6- A mold material for shell mold was obtained in the same manner as in Example 1, except that phenol resin B was used instead of phenol resin A.
  • Example 7- A mold material for shell mold was obtained in the same manner as in Example 2, except that phenol resin B was used instead of phenol resin A.
  • Example 8- A mold material for a shell mold was obtained in the same manner as in Example 7, except that the amount of carbonization accelerator (CR-733S) used was 3 parts.
  • Example 9- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin A and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts. A mold material for a shell mold was obtained in the same manner as in Example 1.
  • Example 10- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin A and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts.
  • a shell mold material was obtained in the same manner as in Example 2.
  • Example 11- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin A and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts. A shell mold material was obtained in the same manner as in Example 3.
  • Example 12- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin A and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts. A shell mold material was obtained in the same manner as in Example 4.
  • Example 13- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin B and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts.
  • a mold material for a shell mold was obtained in the same manner as in Example 1.
  • Example 14- Instead of 100 parts of phenolic resin A, 75 parts of phenolic resin B and 25 parts of phenolic resin C were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts.
  • a shell mold material was obtained in the same manner as in Example 2.
  • Example 15- A mold material for shell mold was obtained in the same manner as in Example 1, except that phenolic resin C was used instead of phenolic resin A and the curing agent (hexamethylenetetramine) was not used.
  • Example 16- Instead of 100 parts of phenolic resin A, 25 parts of phenolic resin C and 75 parts of phenolic resin D were used, and the amount of curing agent (hexamethylenetetramine) used was 4 parts.
  • a mold material for a shell mold was obtained in the same manner as in Example 1.
  • Example 1 A mold material for shell mold was obtained in the same manner as in Example 1, except that phenolic resin D was used instead of phenolic resin A.
  • Example 2- A mold material for a shell mold was obtained in the same manner as in Example 1, except that no carbonization accelerator (PNX) was used.
  • PNX carbonization accelerator
  • Example 4 A mold material for a shell mold was obtained in the same manner as in Example 9, except that no carbonization accelerator (TBP) was used.
  • TBP carbonization accelerator
  • Example 5 A mold material for a shell mold was obtained in the same manner as in Example 13, except that no carbonization accelerator (PNX) was used.
  • PNX carbonization accelerator
  • Example 7- A mold material for a shell mold was obtained in the same manner as in Example 1, except that phenolic resin D was used instead of phenolic resin A and no carbonization accelerator (PNX) was used.
  • Example 8 A mold material for a shell mold was obtained in the same manner as in Example 1, except that the amount of carbonization accelerator (PNX) used was 1 part.
  • PNX carbonization accelerator

Abstract

La présente invention concerne une composition pour moules, la composition étant apte à produire avantageusement un moule apte à supprimer ou à empêcher efficacement l'apparition de défauts de coulée dus au soudage, à la pénétration de métal ou similaire.　Une composition de résine pour moules selon la présente invention contient (a) une résine phénolique, le rapport de la somme de la surface de pic d'un monomère phénolique et de la zone de pic d'un dimère phénolique à la zone de pic totale telle que déterminée par chromatographie de filtration sur gel étant de 13,0 % ou plus, et (b) un accélérateur de carbonisation qui accélère la carbonisation de la résine phénolique ; et la présente composition de résine pour moules est préparée de telle sorte que, par rapport à la mesure de la quantité de génération de gaz dans une atmosphère réductrice à 850 °C de (c) un produit durci, qui est obtenu par durcissement complet de ladite composition de résine pour des moules à 150 °C, le rapport de la quantité de gaz généré pendant 20 secondes à partir du début de la mesure à la quantité totale de gaz généré est de 50% ou plus.
PCT/JP2022/016177 2021-04-15 2022-03-30 Composition de résine pour moules WO2022220133A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5756137A (en) * 1980-09-20 1982-04-03 Toyoda Autom Loom Works Ltd Molding material for shell molding
JPS5978747A (ja) * 1982-10-28 1984-05-07 Aisin Chem Co Ltd シエルモ−ルド用樹脂被覆砂粒
JPH06179040A (ja) * 1992-12-14 1994-06-28 Kao Corp シェルモールド用レジンコーテッドサンド
JP2005095933A (ja) * 2003-09-25 2005-04-14 Sumitomo Bakelite Co Ltd シェルモールド用ノボラック型フェノール樹脂
WO2007010848A1 (fr) * 2005-07-15 2007-01-25 Komatsu Ltd. Sable enduit de resine pour une utilisation pour de l'acier coule, moule fabrique a partir de ce sable, et moulage d'acier moule en utilisant ce moule
JP2014161883A (ja) * 2013-02-26 2014-09-08 Asahi Organic Chemicals Industry Co Ltd 高温易崩壊性シェルモールド用レジンコーテッドサンド及びそれを用いて得られた鋳型並びに鋳物の製造方法
WO2018047893A1 (fr) * 2016-09-08 2018-03-15 旭有機材株式会社 Composition de résine pour moulage en coquille et sable enrobé de résine obtenu à l'aide de celle-ci
JP2019177402A (ja) * 2018-03-30 2019-10-17 旭有機材株式会社 鋳型用骨材及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5881539A (ja) * 1981-11-10 1983-05-16 Sumitomo Deyurezu Kk レジンコ−テツドサンドとその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5756137A (en) * 1980-09-20 1982-04-03 Toyoda Autom Loom Works Ltd Molding material for shell molding
JPS5978747A (ja) * 1982-10-28 1984-05-07 Aisin Chem Co Ltd シエルモ−ルド用樹脂被覆砂粒
JPH06179040A (ja) * 1992-12-14 1994-06-28 Kao Corp シェルモールド用レジンコーテッドサンド
JP2005095933A (ja) * 2003-09-25 2005-04-14 Sumitomo Bakelite Co Ltd シェルモールド用ノボラック型フェノール樹脂
WO2007010848A1 (fr) * 2005-07-15 2007-01-25 Komatsu Ltd. Sable enduit de resine pour une utilisation pour de l'acier coule, moule fabrique a partir de ce sable, et moulage d'acier moule en utilisant ce moule
JP2014161883A (ja) * 2013-02-26 2014-09-08 Asahi Organic Chemicals Industry Co Ltd 高温易崩壊性シェルモールド用レジンコーテッドサンド及びそれを用いて得られた鋳型並びに鋳物の製造方法
WO2018047893A1 (fr) * 2016-09-08 2018-03-15 旭有機材株式会社 Composition de résine pour moulage en coquille et sable enrobé de résine obtenu à l'aide de celle-ci
JP2019177402A (ja) * 2018-03-30 2019-10-17 旭有機材株式会社 鋳型用骨材及びその製造方法

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