CN101977709B - Phenol resin composition for shell mold, resin-coated sand for shell mold, and mold obtained by using the same - Google Patents
Phenol resin composition for shell mold, resin-coated sand for shell mold, and mold obtained by using the same Download PDFInfo
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- CN101977709B CN101977709B CN200980109619.3A CN200980109619A CN101977709B CN 101977709 B CN101977709 B CN 101977709B CN 200980109619 A CN200980109619 A CN 200980109619A CN 101977709 B CN101977709 B CN 101977709B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Disclosed is a phenol resin composition for shell molds which advantageously provides a mold having low thermal expansion and high collapsibility, which produces little tar during casting. Also disclosed are resin-coated sand obtained by using the phenol resin composition for shell molds, and a mold obtained by using the resin-coated sand. The phenol resin composition for shell molds contains propylene glycol and/or a polymerized product thereof as an indispensable component in addition to a phenol resin.
Description
Technical field
The present invention relates to shell mould with phenol resin composition, shell mould with coated sand and the casting mold that uses its formation, particularly relate to the growing amount of the thermal decomposition product (hereinafter to be referred as making " tar ") that produces in the time of can suppressing to cast and solve simultaneously thermal expansivity and the shell mould of contractility problem with phenol resin composition, use its coated sand that obtains and use it to carry out the casting mold of moulding formation.
Background technology
All the time, in shell mould (shell mold) casting, usually use following shell casting mold, namely, use coated sand (hereinafter to be referred as making " RCS "), it is carried out hot briquetting, form thus the shell casting mold with desired shape, described coated sand is to carry out mixing obtaining by the curing agent such as hexa with fire resistance particle (molding sand), phenolic resins (adhesive) and as required use.
But, in such casting mold, particularly in the situation for casting IC engine cylinder head and so on casting mold cast article, complex-shaped, in the casting operation that uses this casting mold, there is the problem easily cause be full of cracks or slight crack (below, be called " slight crack " of casting mold).In addition, in the process that makes complex-shapedization of casting mold, the tendency that exists steam vent to reduce, therefore, the generation of the tar (Tar) of Autoadhesive also becomes a serious problem when casting.
In order to prevent that casting mold from producing slight crack, it is generally acknowledged the coefficient of thermal expansion that can reduce casting mold, increase simultaneously contractility, disclose in the patent documentation 1 by using the bisphenols such as bisphenol-A or bis-phenol E as adhesive ingredients, anxious coefficient of thermal expansion can be reduced, therefore low heat expansion can be realized.But, although said method can be eliminated the problem that casting mold produces slight crack fully, but produced new problem, namely the generation quantitative change of tar is many when casting.
In addition, following method is disclosed, namely in the patent documentation 2, make that to have number-average molecular weight among the RCS be 1500～40000 polyethylene glycol, prevent thus the slight crack (crackle) of casting mold, the raising of thermal expansion character and contractility and insufficient remains and is improving the space when still adopting the method.
Patent documentation 1: Japanese kokai publication sho 59-178150 communique
Patent documentation 2: Japanese kokai publication sho 58-119433 communique
Summary of the invention
Herein, the present invention finishes take above-mentioned situation as background, solution problem of the present invention be to provide a kind of shell mould with phenol resin composition, use the RCS that said composition obtains and use above-mentioned RCS to carry out the casting mold that moulding obtains, described shell mould is conducive to obtain tar growing amount casting mold few, that coefficient of thermal expansion is low and contractility is large when the casting with phenol resin composition.
In order to solve above-mentioned problem, the inventor conducts in-depth research with phenol resin composition shell mould, found that, by in phenolic resins, cooperating propane diols and/or its polymer, obtain RCS, carry out moulding with the RCS of gained and obtain casting mold, in this casting mold process, be conducive to suppress the tar growing amount, in addition, be conducive to the characteristic that realizes that coefficient of thermal expansion is low and contractility is large, thereby finished the present invention.
That is, in order to solve above-mentioned problem, main points of the present invention are a kind of shell mould phenol resin composition, it is characterized in that, contain phenolic resins and propane diols and/or its polymer as necessary constituent.
Need to prove, use one of preferred version of phenol resin composition according to shell mould according to the present invention, with respect to 100 mass parts phenolic resins, above-mentioned propane diols and/or its polymer use with the ratio of 1～30 mass parts, in addition, according to another preferred version, the number-average molecular weight of above-mentioned glycol polymers is 300～3000.
And then main points of the present invention also are a kind of shell mould RCS, it is characterized in that, are formed with coating at the fire resistance particle surface of stipulating, described coating is formed with phenol resin composition by aforesaid shell mould.
In addition, the invention still further relates to a kind of casting mold, described casting mold is to use shell mould as described above to carry out moulding with RCS, and it is heating and curing obtain.
Therefore, shell mould phenol resin composition according to the invention described above, owing to contain phenolic resins and propane diols and/or its polymer as necessary constituent, so form the coating that is formed by said composition by the fire resistance particle surface in regulation, consist of shell mould RCS, use this RCS that casting mold is carried out moulding, can be conducive to reduce the tar growing amount that is produced by above-mentioned casting mold, in addition, meanwhile the coefficient of thermal expansion of gained casting mold is low, and improve fully the contractility of casting mold, thereby produce the gas defects problem that tar causes in the time of can solving simultaneously because of casting, reach crackle and so on casting flaw problem.
Description of drawings
The schematic diagram of the mensuration form of the contractility that [Fig. 1] measures among the embodiment for expression.
The specific embodiment
As mentioned above, shell mould phenol resin composition of the present invention combination phenolic resins and propane diols and/or its polymer are as must constituent and form.
The phenolic resins that herein can use is following phenolic resins: obtain the condensation product of solid shape or liquid (such as varnish shape or emulsion etc.) by make the reaction of phenols and aldehydes in the presence of acidic catalyst and/or base catalyst, in the presence of the curing agent of regulation or the curing catalysts or not it is being heated and presenting thermosetting, particularly, can enumerate linear phenol-aldehyde resin, fusible type phenolic resins, nitrogenous fusible type phenolic resins, benzyl ether type phenolic resins etc., they can use separately or make up more than 2 kinds and use.
In addition, when preparing above-mentioned shell mould and using phenol resin composition, as the phenols as the phenolic resins raw material, such as enumerating phenol or the alkyl substituted phenols such as phenol, cresols, xylenols, reach the polyhydric phenols such as bisphenol-A, Bisphenol F, reaching their mixture etc., and then, as aldehydes, can enumerate formalin, paraformaldehyde, trioxane, acetaldehyde, para-acetaldehyde, propionic aldehyde etc.Certainly be not limited to the above-mentioned material of enumerating as above-mentioned phenols and aldehydes, can suitably use the resin raw material of any known in addition.In addition, above-mentioned phenols and aldehydes all can use separately, also can use simultaneously the raw material more than 2 kinds, without any restriction.
In addition, preparation method as the phenolic resins that uses among the present invention, be not particularly limited, can adopt present known the whole bag of tricks, for example preferably adopt following method, namely, use the acidic materials such as oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, or the alkaline matters such as ammonia, NaOH, calcium hydroxide, or the catalyst such as metal salts of organic acids, divalent metal salt, make the reaction of phenols and aldehydes.
In addition, preparation is during phenolic resins, and the mol ratio (F/P) that cooperates of aldehydes (F) and phenols (P) can suitably be selected according to the kind of the catalysts that uses etc., but preferred settings is in 0.55～0.80 scope.Need to prove, be more than 0.55 by making above-mentioned cooperation mol ratio, can obtain target phenolic resins with sufficient yield, on the other hand, by being below 0.80, use the phenolic resins of gained to form shell mould RCS, when it is carried out moulding and obtains casting mold, can advantageously improve the intensity of gained casting mold.
The phenolic resins that obtains as mentioned above can present the form of solid shape or liquid (such as varnish shape or emulsion etc.), such as in the presence of the curing agent such as hexa or the curing catalysts or not, by it is heated, present thermosetting.Need to prove, among the present invention, the preferred phenolic resins of number-average molecular weight in 400～900 scopes that obtains by gel permeation chromatography (GPC) analysis that uses.When several mean molecule quantities of above-mentioned phenolic resins are too small, the shell mould RCS that will contain the resin combination coating formation of above-mentioned resin, fillibility when moulding is destroyed, possibly can't guarantee that the gained casting mold has sufficient intensity, on the other hand, when the number-average molecular weight of phenolic resins was excessive, resin was mobile destroyed during heating, possibly can't guarantee that the gained casting mold has sufficient intensity.
Need to prove, among the present invention, for physical property of improving casting mold etc., can in above-mentioned phenolic resins, suitably cooperate various additives commonly used at present to phenolic resins in advance, particularly preferably cooperate the silane couplers such as γ aminopropyltriethoxy silane and γ-glycidoxypropyltrime,hoxysilane; The lubricants such as ethylenebisstearamide and methylene distearyl acid amides etc.
Shell mould of the present invention has made up above-mentioned phenolic resins and propane diols (hereinafter to be referred as making " PG ") and/or its polymer as necessary constituent simultaneously with phenol resin composition.Wherein, among the present invention, the boiling point of the polymer of PG is high and not volatile, so particularly preferably use.
More specifically, among the present invention, in the polymer of PG, particularly preferably using the number-average molecular weight that is obtained by the gel permeation chromatography analysis is 300～3000 polypropylene glycol (hereinafter to be referred as making " PPG ").The number-average molecular weight of above-mentioned PPG is 300 when above, because the temperature of its boiling point when casting mold is carried out moulding, and not volatile, so more be conducive to bring into play the effect of aforesaid PPG.In addition, the number-average molecular weight of PPG is 3000 when following, can be conducive to suppress the strength decreased of gained shell casting mold.PPG with above-mentioned number-average molecular weight has various commercially available products, and the present invention can suitably select from these commercially available products.
In addition, the PG among the present invention and/or its polymer are not particularly limited the mixing ratio of phenolic resins, with respect to 100 mass parts phenolic resins, usually use more satisfactory with the ratio of 1～30 mass parts.The mixing ratio of PC and/or its polymer is that 1 mass parts is when above, can further bring into play fully the effect that prevents that gained shell casting mold from cracking, in addition, the mixing ratio of PC and/or its polymer is 30 mass parts when following, can be conducive to suppress the strength decreased of shell casting mold.
Above-mentioned PG and/or its polymer make up by cooperating with phenolic resins etc., thus, realized shell mould of the present invention one of scheme of phenol resin composition, wherein, as the method that PG and/or its polymer and phenolic resins are made up, be not particularly limited among the present invention, in the time of can beginning by the reaction at preparation during phenolic resins, phenols and aldehydes, in the reaction or reaction finish after any time, with PG and/or its polymer suitably cooperation realize.In addition, can also suitably adopt following method, that is, behind preparation phenolic resins, phenolic resins be pulverized the method for mixing with the polymer of PG; And utilize the mixers such as extruder mix phenolic resins with PG and/or its polymer melting method etc.And then, can also in the manufacturing process of RCS, cooperate PG and/or its polymer.When in the manufacturing process of RCS, cooperating, can before the interpolation of phenolic resins or after adding, cooperate, perhaps can also when adding phenolic resins, cooperate.In addition, PG and/or its polymer can directly cooperate, and perhaps it can also be dispersed or dissolved in any medium to cooperate, without any restriction.
When making shell mould of the present invention and using RCS, can also fire resistance particle and above-mentioned shell mould is mixing with phenol resin composition.Herein, shell mould among the RCS of the present invention use level of phenol resin composition, determine according to the resin kind of using and desired mould strength etc., therefore can not limit entirely, but generally with respect to 100 mass parts shell mould phenol resin compositions, in the scope of fire resistance particle about 0.2～10 mass parts, preferably in the scope of 0.5～8 mass parts, more preferably in the scope of 0.5～5 mass parts.
In addition, for fire resistance particle that can be mixing with above-mentioned shell mould usefulness phenol resin composition, its kind is not particularly limited in the present invention.Because above-mentioned fire resistance particle forms the base material of casting mold, so be suitable for the inorganic particulate that casting mold forms the particle diameter of (moulding) and get final product so long as have the fire resistance of ability casting and have, can use all the time for any known inorganic particulate of shell-molded.As above-mentioned fire resistance particle, except normally used silica sand, can also enumerate special sand such as olivine sand, zircon sand, chromium sand and aluminum oxide sand; The slag class particles such as ferrochrome class slag, ferronickel class slag and converter slag; NaigaiCerabeads (trade name, ITOCHU Ceratec Co., Ltd.) and so on mullite class Porous particle; The regenerated particle that reclaiming obtains after maybe will casting etc., they can use separately, perhaps make up more than 2 kinds and use.
When making above-mentioned shell mould and using RCS, its manufacture method is not particularly limited, also can adopt the hot rubbing method of dry type (dry hot coat method), half hot rubbing method (semi hot coat method), cold method with plastic film and powder solvent method etc. be known any method at present, but among the present invention, the hot rubbing method of so-called dry type particularly preferably, namely, in the mixing rolls such as sand muller or high speed puddle mixer, will be after the fire resistance particle of preheating and shell mould be mixing with resin combination, add hexa (curing agent) aqueous solution, it is granular making block content disintegration by the air-supply cooling simultaneously, then adds calcium stearate (lubricant).
And then, when using above-mentioned shell mould with RCS casting mold to be carried out moulding, as its heating formative method, be not particularly limited, can adopt all the time known any favourable method.For example, can followingly obtain casting mold: with above-mentioned RCS by the gravity fall mode or be blown into mode etc. and be filled in the shaping mould, make its curing, then, with the casting mold demoulding from above-mentioned shaping mould after solidifying, described shaping mould has to be given the desired shape space of target casting mold and is heated to 150 ℃～300 ℃.The casting mold that obtains as mentioned above can be conducive to bring into play the effect of above-mentioned excellence.
Embodiment
Below, provide several embodiments of the present invention, be described more specifically the present invention, self-evident the present invention is not subjected to any restriction of the content of these embodiment records.In addition, it will be appreciated that for, among the present invention, except following embodiment and then except above-mentioned concrete description, also be included in the various changes made based on those skilled in the art's knowledge in the scope that does not break away from purport of the present invention, modification, improvement etc.
Need to prove that below in the record, " part " reaches " % " as long as no being particularly limited, expression " mass parts " reaches " quality % " respectively.In addition, making the shell mould that obtains measures according to following test method with the various characteristics of RCS.
The mensuration of-mould strength-
Use and make the shell mould RCS that obtains, making is (wide: 10mm * thick: 10mm * length: 60mm) based on the JIS formula sample of JIS-K-6910 (firing condition of sample: lower 60 seconds at 250 ℃), for gained JIS formula sample (following sample or the TP of also simply being called), according to JACT test method(s) SM-1, measure this mould strength (N/cm
2)
The mensuration of-tar growing amount-
With 4 mould strengths measure with sample (size: 10mm * 10mm * 60mm) pack into glass developmental tube (internal diameter 27mm * long 200mm) interior after, the measured glass silk flosssilk wadding of scale (2.5g) inserts near the opening part of developmental tube in advance, makes tar growing amount determinator.Then, pack into temperature in the stove of said determination device is remained in 700 ℃ the tubulose heating furnace, carry out anxious heat treatment after 6 minutes, take out, cooling is placed to normal temperature.Afterwards, the glass silk flosssilk wadding is taken out from this determinator, measure its quality.Need to prove that the growing amount of tar (mg) is the glass fiber cotton amount (mg) after the anxious heat to be deducted the glass fiber cotton amount (mg) before the anxious heat and the value that obtains.
The contractility evaluation of-casting mold-
At first, at firing condition: under 250 ℃ * 40 seconds, make the casting mold sheet (120mm * 40mm * 5mm) as contractility evaluation casting mold, this casting mold is placed to normal temperature, and cooling that use each RCS.
Next, as shown in Figure 1, after being installed in casting mold sheet obtained above on the brace table, with heater (globar) it is slowly heated since 200 ℃, be warming up to 800 ℃, at this moment, in the position apart from the leading section 10mm of this casting mold sheet laser displacement gauge is installed, directly to personal computer input data.As the displacement situation, at first, by to the heating of this casting mold sheet, because of this casting mold bending tablet of action that expands, begin soon afterwards deflection, at last this casting mold sheet roughly at central portion, be the heating part fracture of heater.Herein so-called " contractility " with until the maximum deflection that fracture obtains represents that this value is larger, represents that casting mold is more yielding, is rich in flexibility.Need to prove, also consider the determination period of next casting mold sheet mensuration beginning when the heater temperature is 200 ℃ of left and right sides, carry out this mensuration.
The evaluation of-coefficient of thermal expansion-
Carry out according to the anxious coefficient of thermal expansion determination test method of putting down in writing in the JACT test method(s) M-2 coefficient of thermal expansion determination test method.Will be at firing temperature: 280 ℃, firing time: the sample of making under 120 seconds the condition (
Cut about quarter turn) be arranged in the high temperature modification sand test device of adjustment to 1000 in the stove ℃, take out after 1 minute.Then, according to following calculating formula, by before the anxious heat with anxious heat after specimen length calculate coefficient of thermal expansion.
Coefficient of thermal expansion (%)={ (after the anxious heat-anxious heat before) specimen length }/(specimen length before the anxious heat) * 100
The manufacturing of-phenol-formaldehyde A-
In the reaction vessel that thermometer, agitating device and capacitor are installed, add 940 parts of phenol, 428 parts of 47% formalin, 2.8 parts of oxalic acid.Next, reaction vessel is slowly heated up, reach reflux temperature after, carried out back flow reaction 90 minutes, and then, heat and reduced pressure concentration until reacting liquid temperature reaches 170 ℃, obtain thus phenol-formaldehyde A.
The manufacturing of-bakelite B-
In the reaction vessel that thermometer, agitating device and capacitor are installed, add 650 parts of phenol, 350 parts of bisphenol-As, 270 parts of 47% formalin, 3 parts of oxalic acid.Next, reaction vessel is slowly heated up, reach reflux temperature after, carried out back flow reaction 70 minutes, and then, heat and reduced pressure concentration until reacting liquid temperature reaches 170 ℃, obtain thus bakelite B.
-embodiment 1-
After making 100 parts of phenol-formaldehyde A heating and meltings, be that 2000 PPG (trade name: Hiflex D-2000, Di-ichi Kogyo Seiyaku Co., Ltd.'s system) mixes with 3 umber average molecular weights, cooling, solidify, obtain thus phenol resin composition.Next, pack 105 parts of gained phenol resin compositions and 7000 parts of fire resistance particles (regeneration silica sand) that are heated to 130～140 ℃ into experiment with in the balance wheel type mixing roll, mixing 60 seconds.Add that again 23 parts of hexas are dissolved in formed solution in 105 parts of water, the cooling of blowing afterwards, is added 7 parts of calcium stearates, obtains RCS.
-embodiment 2～6-
Embodiment 2, using respectively 5 parts, 10 umber average molecular weights in 3 is 2000 PPG, use 5 parts of PG among the embodiment 4, use 5 umber average molecular weights are 400 PPG among the embodiment 5, the use number-average molecular weight is 4000 PPG among the embodiment 6, replace among the embodiment 1 the 3 umber average molecular weights that the use PPG as 2000 take this, in addition, adopt method similarly to Example 1 to obtain RCS.
-comparative example 1-
Be 2000 the PPG except not adding 3 umber average molecular weights, adopt method similarly to Example 1 to obtain RCS.
-comparative example 2-
Except use 5 umber average molecular weights be 2000 polyethylene glycol (PEG) to replace 3 umber average molecular weights be 2000 the PPG, adopt method similarly to Example 1 to obtain RCS.
-comparative example 3-
Replace phenol-formaldehyde A with bakelite B, and do not add PPG, in addition, carry out the step same with above-described embodiment 1, obtain RCS.
-estimate-
According to above-mentioned test method, to the RCS of gained carry out respectively that mould strength is measured, the tar growing amount is measured, casting mold contractility and coefficient of thermal expansion measure.It the results are shown in following table 1.
By the result of above-mentioned table 1 as can be known, among the embodiment 1～6 of RCS of the present invention, the growing amount of tar is few, and coefficient of thermal expansion is low and contractility is large simultaneously.On the other hand, do not add in the phenolic resins comparative example 1 of propane diols and/or its polymer RCS, and add the RCS that polyethylene glycol replaces the comparative example 2 of propane diols and/or its polymer, coefficient of thermal expansion is high, and contractility is little.And then, using among the RCS of the comparative example 3 that has low heat expansion phenolic resins now, tar is many, although thermal expansion is suppressed in addition, contractility is little.
Claims (11)
1. shell mould phenol resin composition, it is characterized in that, described composition contains linear phenol-aldehyde resin and propane diols and/or polypropylene glycol simultaneously as necessary constituent, with respect to 100 mass parts phenolic resins, uses propane diols and/or polypropylene glycol in the ratio of 1～30 mass parts.
2. shell mould phenol resin composition as claimed in claim 1 is characterized in that, the number-average molecular weight of described polypropylene glycol is 300～3000.
3. shell mould phenol resin composition as claimed in claim 1, wherein, described phenolic resins is to use the catalyst of regulation to make aldehydes (F) and phenols (P) react and obtain as 0.55～0.80 take cooperation mol ratio (F/P).
4. shell mould phenol resin composition as claimed in claim 2, wherein, described phenolic resins is to use the catalyst of regulation to make aldehydes (F) and phenols (P) react and obtain as 0.55～0.80 take cooperation mol ratio (F/P).
5. shell mould phenol resin composition as claimed in claim 1, wherein, the number-average molecular weight of described phenolic resins is in 400～900 scope.
6. shell mould phenol resin composition as claimed in claim 2, wherein, the number-average molecular weight of described phenolic resins is in 400～900 scope.
7. shell mould phenol resin composition as claimed in claim 3, wherein, the number-average molecular weight of described phenolic resins is in 400～900 scope.
8. shell mould phenol resin composition as claimed in claim 4, wherein, the number-average molecular weight of described phenolic resins is in 400～900 scope.
9. a shell mould coated sand is characterized in that, is formed with coating on the surface of fire resistance particle, and described coating is formed with phenol resin composition by each described shell mould in the claim 1 to 8.
10. shell mould coated sand as claimed in claim 9 wherein, with respect to the described fire resistance particle of 100 mass parts, uses the described shell mould phenol resin composition of 0.2～10 mass parts.
Require 9 or 10 described shell moulds to carry out moulding with coated sand 11. a casting mold, described casting mold are rights to use, and it is heating and curing obtain.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-072179 | 2008-03-19 | ||
| JP2008072179 | 2008-03-19 | ||
| PCT/JP2009/001216 WO2009116287A1 (en) | 2008-03-19 | 2009-03-18 | Phenol resin composition for shell mold, resin-coated sand for shell mold, and mold obtained by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101977709A CN101977709A (en) | 2011-02-16 |
| CN101977709B true CN101977709B (en) | 2013-03-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980109619.3A Expired - Fee Related CN101977709B (en) | 2008-03-19 | 2009-03-18 | Phenol resin composition for shell mold, resin-coated sand for shell mold, and mold obtained by using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5491382B2 (en) |
| CN (1) | CN101977709B (en) |
| WO (1) | WO2009116287A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149007A (en) * | 1995-10-18 | 1997-05-07 | 博登公司 | Urethane foundry binders resistant to water-based coatings |
| CN1150070A (en) * | 1995-11-08 | 1997-05-21 | 花王株式会社 | Binder composition for casting mould, mould composition and mould manufacturing method |
| CN1289655A (en) * | 1993-12-28 | 2001-04-04 | 日本铸造技术咨询公司 | Method for making formed refractory casting mould with core installed |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58119433A (en) * | 1982-01-07 | 1983-07-15 | Sumitomo Deyurezu Kk | Resin coated sand for shell mold |
| US6391942B1 (en) * | 2000-04-27 | 2002-05-21 | Ashland Inc. | Furan no-bake foundry binders and their use |
| JP2001347339A (en) * | 2000-06-08 | 2001-12-18 | Gun Ei Chem Ind Co Ltd | Binder composition for mold and material for mold |
| JP3831668B2 (en) * | 2002-01-25 | 2006-10-11 | 旭有機材工業株式会社 | Resin binder composition for mold |
| JP4428997B2 (en) * | 2003-12-09 | 2010-03-10 | 旭有機材工業株式会社 | Resin coated sand for laminated molds |
-
2009
- 2009-03-18 JP JP2010503781A patent/JP5491382B2/en active Active
- 2009-03-18 CN CN200980109619.3A patent/CN101977709B/en not_active Expired - Fee Related
- 2009-03-18 WO PCT/JP2009/001216 patent/WO2009116287A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289655A (en) * | 1993-12-28 | 2001-04-04 | 日本铸造技术咨询公司 | Method for making formed refractory casting mould with core installed |
| CN1149007A (en) * | 1995-10-18 | 1997-05-07 | 博登公司 | Urethane foundry binders resistant to water-based coatings |
| CN1150070A (en) * | 1995-11-08 | 1997-05-21 | 花王株式会社 | Binder composition for casting mould, mould composition and mould manufacturing method |
Non-Patent Citations (1)
| Title |
|---|
| 黄仁和等.铸造用聚氨酯粘合剂组份Ⅰ酚醛树脂合成研究.《中国铸造装备与技术》.2007,(第06期),第9-12页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5491382B2 (en) | 2014-05-14 |
| WO2009116287A1 (en) | 2009-09-24 |
| JPWO2009116287A1 (en) | 2011-07-21 |
| CN101977709A (en) | 2011-02-16 |
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