CN102448637A - Phenol resin composition for shell molding, resin-coated sand for shell molding, and shell molding die obtained using the same - Google Patents
Phenol resin composition for shell molding, resin-coated sand for shell molding, and shell molding die obtained using the same Download PDFInfo
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- CN102448637A CN102448637A CN2010800229203A CN201080022920A CN102448637A CN 102448637 A CN102448637 A CN 102448637A CN 2010800229203 A CN2010800229203 A CN 2010800229203A CN 201080022920 A CN201080022920 A CN 201080022920A CN 102448637 A CN102448637 A CN 102448637A
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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
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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
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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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Mold Materials And Core Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Provided are a phenol resin composition for shell molding, from which a molding die having a low thermal expansion coefficient and high deflectability can be advantageously formed, a resin-coated sand obtained using the same, and a shell molding die obtained using such a resin-coated sand. A naphthol is used together with a phenol. These phenol components are caused to react with an aldehyde to obtain a phenol resin. The phenol resin is combined with a fatty acid amide to constitute a phenol resin composition for shell molding, which is capable of exhibiting useful die characteristics.
Description
Technical field
The present invention relates to shell mould with phenol resin composition and shell mould with coated sand and use the shell mould of its formation to use casting mold, relate in particular to the shell mould that can solve thermal expansivity and contractility problem simultaneously with phenol resin composition with use its coated sand that obtains and manufacturing approach and use its moulding and the shell mould that forms is used casting mold.
Background technology
All the time; In shell mould (shell mold) casting, use following shell casting mold usually; That is, use coated sand (hereinafter to be referred as making " RCS "), it is carried out hot briquetting; Form the shell casting mold with intended shape thus, said coated sand is to carry out mixing obtaining through the curing agent such as hexa with fire resistance particle (molding sand) and phenolic resins (adhesive) and use as required.
But, in such casting mold, particularly under the situation of making IC engine cylinder head and so on casting mold cast article, complex-shaped, in the casting operation that uses this casting mold, have the problem that is prone to cause be full of cracks or slight crack (below, be called " slight crack " of casting mold).
Therefore; For the coefficient of thermal expansion that prevents that casting mold from producing slight crack, it is generally acknowledged to reduce casting mold, increase contractility simultaneously, disclose in the patent documentation 1 through using 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 though said method can to a certain degree be eliminated the problem that casting mold produces slight crack, contractility is also insufficient.
In addition, following method is disclosed, promptly in the patent documentation 2; Make that to have number-average molecular weight among the RCS be 1500～40000 polyethylene glycol; Prevent the slight crack (crackle) of casting mold thus, the raising of thermal expansion character and contractility and insufficient remains and is improving the space when still adopting this method.
On the other hand; In patent documentation 3, disclose through after the shakeout operation after using RCS more effectively to reclaim casting as the block of shell; Said RCS utilizes and uses aphthols to form as the surface that the difficult destructive phenolic resins of phenols manufacturing coats molding sand at least, the raising of the regeneration rate of the shell sand after therefore can realizing using and also can make the steady quality of reclaimed sand.Linear phenol-aldehyde resin or fusible type phenolic resins in embodiment, have been enumerated; Said linear phenol-aldehyde resin or fusible type phenolic resins are to use catalyst such as hydrochloric acid or ammoniacal liquor; The reaction of alpha-Naphthol or betanaphthol or said naphthols and phenol and formalin is obtained; But, use in the resin of hydrochloric acid as catalyst the safety issue that the vigorous reaction when having resin manufacture produces, the mould etching problem when reaching casting and molding especially herein.In addition, in this patent documentation 3, do not have the open phenolic resins that obtains as catalyst with oxalic acid fully and use its RCS that obtains, become when openly not making casting mold more fully problem, phenomenon such as casting mold slight crack.
Patent documentation 1: japanese kokai publication sho 59-178150 communique
Patent documentation 2: japanese kokai publication sho 58-119433 communique
Patent documentation 3: japanese kokai publication sho 63-30144 communique
Summary of the invention
Here; The present invention is that background is accomplished with above-mentioned situation; Solution problem of the present invention is to provide a kind of shell mould with phenol resin composition, and RCS and the manufacturing approach thereof of using this phenol resin composition to obtain, further provides to use said RCS to carry out the shell mould that moulding obtains to use casting mold.
In order to solve above-mentioned problem; The inventor etc. further investigate with phenol resin composition shell mould; The result finds to use the phenol composition that will use phenols and aphthols simultaneously and form and aldehydes reaction and the phenolic resins that obtains, this phenolic resins and fatty acid amide is made up the phenol resin composition that can obtain having useful characteristic; Particularly; The casting mold that obtains for utilizing the RCS that uses this phenol resin composition to obtain to carry out moulding helps realizing keeping low-thermal-expansion rate and the big characteristic of contractility, thereby has accomplished the present invention.
That is, in order to solve above-mentioned problem, main points of the present invention are that shell mould uses phenol resin composition, it is characterized in that comprise phenolic resins and fatty acid amide as neccessary composition, said phenolic resins is that phenols, aphthols and aldehydes reaction are obtained.
Need to prove that shell mould according to the present invention is with a preferred version of phenolic resins, to count 95～50 in mass ratio: 5～50 ratio is used above-mentioned phenols and above-mentioned aphthols.
In addition, according to another preferred version of the present invention, above-mentioned aphthols is 1-naphthols and/or beta naphthal.
And according to another preferred version of the present invention, above-mentioned phenolic resins is to be that the reaction of 0.40～0.80 ratio forms through making above-mentioned phenols (P), above-mentioned aphthols (N) and above-mentioned aldehydes (F) the cooperation mol ratio with them: F/ (P+N).
And then, according to a preferred version more of the present invention, being that the ratio of 1～15 mass parts is used above-mentioned fatty acid amide with respect to the above-mentioned phenolic resins of 100 mass parts.
In addition, according to preferred version of the present invention, above-mentioned fatty acid amide is monoamides class, substituted amide class or bisamide class.
In addition, the further preferred scheme according to the present invention, above-mentioned fatty acid amide is the aliphatic acid bisamide, more preferably the saturated fatty acid bisamide.
In addition, other preferred versions according to the present invention further cooperate silane coupler.
Main points of the present invention are that also shell mould with RCS (coated sand), is characterized in that, said shell mould is to use aforesaid shell mould to coat the fire resistance particle with phenol resin composition with RCS and obtains.
In addition, shell mould according to the present invention is used above-mentioned phenol resin composition with the preferred version of RCS with the ratio that is 0.2～10 mass parts with respect to the above-mentioned fire resistance particle of 100 mass parts.
In addition, main points of the present invention are that also shell mould uses casting mold, are to use as stated shell mould to carry out moulding with RCS, and it are heating and curing obtain.
In addition, main points of the present invention also are the manufacturing approach of shell mould with RCS, it is characterized in that, comprise following operation:
(a) phenols, aphthols and aldehydes are reacted in the presence of the catalyst of regulation and obtain the operation of phenolic resins;
(b) said phenolic resins and fatty acid amide melting mixing are used or make respectively the operation that is used for coating the fire resistance particle.
In addition, according to preferred version of the present invention, above-mentioned catalyst is divalent slaine and/or oxalic acid.
For according to the shell mould of the invention described above with phenol resin composition owing to phenols and aphthols are reacted the phenolic resins that obtains with aldehydes, this phenolic resins and fatty acid amide are combined for using; So, form the clad that forms by this phenol resin composition through fire resistance particle surface in regulation, constitute shell mould and use RCS; Then; Use this RCS, casting mold is carried out moulding, can help keeping the low-thermal-expansion rate of the casting mold that obtains thus; Simultaneously improve the contractility of casting mold effectively, thereby can solve the casting flaw problem of crackle that the slight crack of casting mold causes and so on simultaneously.And; Because not hydrochloric and so on corrosivity composition in can the phenolic resins of use; So also have following characteristic: when moulding, do not cause problems such as mould corrosion, can advantageously enjoy can be easily and the serviceability on the industries such as advantage such as manufacturing objective casting mold safely.
Description of drawings
The key diagram of the mensuration scheme among [Fig. 1] expression embodiment in the determination method that adopt, contractility.
The specific embodiment
As stated, constitute shell mould of the present invention and be to use phenols and aphthols and aldehydes, utilize the catalyst of regulation that their reactions are obtained with the phenolic resins of phenol resin composition.
,, known all the time material can be enumerated here, for example, except that phenol, alkyl phenols such as cresols, xylenols, p-t-butyl phenol, nonyl phenol can also be enumerated as the phenols of one of reacted constituent of said phenolic resins; Polyhydric phenols such as resorcinol, Bisphenol F, bisphenol-A and their mixture etc. can use a kind in them separately or make up more than 2 kinds and use.
One of characteristic of the present invention is together also to use aphthols as the phenol composition with aforesaid phenols, thus, can help to improve effectively the characteristic of the phenolic resins that obtains.Need to prove,, consider from being easy to viewpoints such as acquisition, cost as said aphthols; Preferably can use 1-naphthols or beta naphthal separately or use with the form of mixture; Wherein, from considering, preferably use the 1-naphthols with the aspects such as reactive excellence of aldehydes.In addition, by quality ratio, making the ratio of said phenols and aphthols (1-naphthols or beta naphthal) is phenols: aphthols=95～50: 5～50 use, and in other words, making aphthols is to use below the 50 quality % of whole phenol compositions.When its reason was that the usage ratio of said aphthols surpasses 50 quality %, the generation possibility of tar increased during casting, in addition, when use amount is less than 5 quality %, can not give full play to the effect of contractility.Need to prove, consider that from the viewpoint of mould strength phenols: the ratio of aphthols is preferably 90～60: in 10～40 the scope, more preferably 90～70: use in 10～30 the scope.
In addition, in order to obtain phenolic resins of the present invention, as can with the aldehydes of above-mentioned phenols and aphthols reaction, can enumerate formalin, paraformaldehyde, trioxane, acetaldehyde, para-acetaldehyde, propionic aldehyde etc.Certainly,, be not limited to the above-mentioned material of enumerating, also can suitably use the known raw material except that above-mentioned, and then above-mentioned aldehydes can use separately, also can make up the raw material that uses more than 2 kinds, have no qualification as said aldehydes.
In addition; Among the present invention; In order to make above-mentioned phenols (P) and aphthols (N) and above-mentioned aldehydes (F) reaction obtain good phenolic resins as target, recommend the cooperation mol ratio of above-mentioned substance: F/ (P+N) in 0.40～0.80 proportion, make the reaction of said phenols and aphthols and aldehydes.Wherein, be below 0.75, particularly in particular for below 0.70 through making said cooperation mol ratio: F/ (P+N), can further improve contractility.Need to prove; Through the value that makes said F/ (P+N) is more than 0.40; Can obtain target phenolic resins with sufficient yield, on the other hand, be below 0.80 through the value that makes said F/ (P+N); The shell mould that the phenolic resins that uses gained is formed can help improving the intensity of said shell mould being carried out the casting mold of moulding gained with RCS with among the RCS.
Need to prove, in the present invention, when above-mentioned phenols and aphthols and aldehydes reaction; Can suitably select to use the existing known various catalyst of acid catalyst and so on; Particularly, as above-mentioned catalyst, recommend to use arbitrary at least side in divalent slaine and the oxalic acid.Through using above-mentioned specific catalyst, can keep the low-thermal-expansion rate, realize the further raising of contractility simultaneously, simultaneously, can help solving problems such as mould corrosion.Therefore; As the divalent slaine; For example; The slaine that lead naphthenate, zinc naphthenate, lead acetate, zinc acetate, Firebrake ZB, lead oxide, zinc oxide etc. have the divalent metallic element can be enumerated, in addition, the acidic catalyst that can form above-mentioned slaine and combination of base catalyst etc. can also be enumerated.In the above-mentioned specific catalyst, preferably use oxalic acid.Generally with respect to the phenols and the aphthols that amount to 100 mass parts, above-mentioned to contain at least a kind the catalyst that is selected from divalent metal salt and the oxalic acid be the ratio of 0.01～5 mass parts, when being preferably the ratio of 0.05～3 mass parts, help using.
In addition, when using the catalyst of stipulating to make phenols and aphthols and aldehydes reaction, likewise carry out with the manufacturing approach of existing phenolic resins.The phenolic resins that obtains as stated demonstrates the form of solid, shaped or liquid (for example varnish shape or emulsion etc.), for example, in the presence of curing agent such as hexa or the curing catalysts or not, through it is heated, demonstrates thermosetting.Need to prove, among the present invention, the preferred phenolic resins of number-average molecular weight in 400～1300 scopes that obtains through gel permeation chromatography (GPC) analysis that uses.When the number-average molecular weight of said phenolic resins is too small; Contain shell mould that the resin combination of this resin forms with RCS for coating, the fillibility when impairing moulding, the possibly full intensity that can't guarantee the gained casting mold; On the other hand; When the number-average molecular weight of phenolic resins was excessive, resin flow property was destroyed during heating, the full intensity of the casting mold that possibly can't guarantee obtains.
And the present invention is in the phenolic resins that obtains as stated, and the combination fatty acid amide constitutes shell mould and uses phenol resin composition as neccessary composition.Through making up this phenolic resins and fatty acid amide, can help keeping the low-thermal-expansion rate of the shell mould casting mold that obtains, improve contractility simultaneously.Need to prove that the usage ratio of said phenolic resins and fatty acid amide can suitably be confirmed according to the characteristic that requires of casting mold, but usually with respect to the phenolic resins of 100 mass parts, use the fatty acid amide of the ratio of 1～15 mass parts.This is because the use amount of this fatty acid amide when very few, become and can not give full play to effect and the effect of using fatty acid amide and bringing, in addition, and also because its use amount when too much, is difficult to expect the raising with corresponding effect of its use amount and effect.
In addition, as the fatty acid amide that uses with this phenolic resin composition, can enumerate monoamides classes such as saturated fatty acid monoamides and unrighted acid monoamides; The substituted amide class; Bisamide classes such as saturated fatty acid bisamide, unrighted acid bisamide, fragrant same clan bisamide wherein, are preferably used the aliphatic acid bisamide, especially preferably use the saturated fatty acid bisamide.
In addition; In above-mentioned fatty acid amide,, can enumerate lauramide, myristamide, palmitamide, stearmide 、 Shan Yu acid amides etc. as the object lesson of saturated fatty acid monoamides; In addition; As the object lesson of unrighted acid monoamides, can enumerate oleamide, mustard acid amides etc., in addition; As the object lesson of substituted amide, can enumerate N-stearyl stearmide, N-oleyl (oleyl) stearmide, N-stearyl mustard acid amides, methylol stearmide, methylol Shan Yu acid amides etc.In addition; As the object lesson of saturated fatty acid bisamide, can enumerate di-2-ethylhexylphosphine oxide stearmide, ethylenebisstearamide, di-2-ethylhexylphosphine oxide lauramide, di-2-ethylhexylphosphine oxide Shan Yu acid amides, hexa-methylene bis-stearamides, the two hydroxyl stearmides of hexa-methylene, N, N '-distearyl adipamide etc.; In addition; As the object lesson of unrighted acid bisamide, can enumerate ethylenebisoleoamide, ethylenebis mustard acid amides, the two oleamide of hexa-methylene, N, N '-two oleyl adipamide etc.; In addition; As the object lesson of aromatic series bisamide, can enumerate the two hydroxyl stearmides of xylylene bis-stearamides, xylylene, N, benzenedicarboxamide etc. between N '-distearyl.
Need to prove that among the present invention, for the combination of above-mentioned phenolic resins and fatty acid amide and be used for shell mould, from the purposes such as rerum natura of improving casting mold, but proper fit is used normally used all the time various additives as required.For example, can be used silane couplers such as γ-An Jibingjisanyiyangjiguiwan or γ-glycidoxypropyltrime,hoxysilane etc.; Usually, with respect to phenolic resins 100 mass parts, above-mentioned silane coupler with 0.01～5 mass parts about, the ratio about preferred 0.05～2.5 mass parts cooperates.
When making shell mould of the present invention and using RCS, mixing aforesaid shell mould is used phenol resin composition in the fire resistance particle of regulation.At this moment; Because the shell mould among the RCS of the present invention is that the resin kind considering to use and desired mould strength etc. are definite with the use level of phenol resin composition; Therefore can not limit entirely; Usually with respect to 100 mass parts fire resistance particles, in the scope about 0.2～10 mass parts, preferably in 0.5～8 mass parts, more preferably in the scope of 0.5～5 mass parts.
In addition, for can with above-mentioned shell mould with the mixing fire resistance particle of phenol resin composition, its kind is not special in the present invention to be limited.Because above-mentioned fire resistance particle is as the base material of casting mold; So get final product so long as have the fire resistance that can tolerate casting and be suitable for the inorganic particulate that casting mold forms the particle diameter of (moulding), can use to be used for any known inorganic particulate of shell-molded all the time.As above-mentioned fire resistance particle, except that the silica sand of general frequent use, can also enumerate for example special sand such as olivine sand, zircon sand, chromium sand and aluminum oxide sand; Slag class particles such as ferrochrome class slag, ferronickel class slag and converter slag; Naigai Cerabeads (trade name, ITOCHU Ceratech Co., Ltd.) and so on mullite class porous plasmid; Or the regenerated particle that its casting back reclaiming is obtained etc., they can use separately, or make up more than 2 kinds and use.
When making above-mentioned shell mould and using RCS; Its manufacturing approach is not special to be limited, and also can adopt the hot rubbing method of dry type (dry-hot-coating), half hot rubbing method (semi-hot-coating), cold method with plastic film, and known any method at present such as powder solvent method, but the hot rubbing method of preferred especially so-called dry type among the present invention; Promptly; In mixing rolls such as sand muller or high speed puddle mixer, will after the fire resistance particle of preheating and shell mould are mixing with resin combination, add hexa (curing agent) aqueous solution; It is granular making block content disintegration through the air-supply cooling simultaneously, adds calcium stearate (lubricant) then.Need to prove,, except melting mixing is used for coating the fire resistance particle, can also independently use, coat the fire resistance particle for constituting the phenolic resins and the fatty acid amide of shell mould of the present invention with the regulation of resin combination.
And then, use aforesaid shell mould with RCS during to the making molds of regulation, as its heating formative method, not special the qualification can advantageously be adopted existing known any method.For example; Can obtain casting as follows and use casting mold: with above-mentioned RCS through the gravity fall mode or be blown into mode etc. and be filled into and make its curing in the shaping mould; Then; With the casting mold demoulding from above-mentioned shaping mould after solidifying, said shaping mould has the shape space of giving the expectation of target casting mold and is heated to 150 ℃～300 ℃.The casting mold that obtains as stated can help bringing into play the effect of above-mentioned excellence.
Embodiment
Below, provide some embodiments of the present invention, the present invention more specifically is described, self-evident the present invention does not receive any restriction of the content of these embodiment records.In addition, should be appreciated that in the present invention except that following embodiment, and then except that 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, correction, improvement etc.
Need to prove that below " part " reaches " % " short of special instruction in the record, expression " mass parts " reaches " quality % " respectively.In addition, the shell mould of manufacturing is measured according to following test method with the various characteristics of RCS.
The contractility evaluation of-casting mold-
At first, at firing condition: under 250 ℃ * 40 seconds, (120mm * 40mm * 5mm) casting mold is used in evaluation as contractility, and normal temperature is placed and be cooled to this casting mold to make the casting mold sheet that has used each RCS.
Next, as shown in Figure 1, the above-mentioned casting mold sheet that obtains is installed on the support platform; Then; Since 200 ℃ of slowly heating, make it be warming up to 800 ℃, at this moment with heater (Erema Elema); Laser displacement gauge is installed in position apart from the leading section 10mm of this casting mold sheet, directly to personal computer input data.As the situation of displacement, at first, through with the heating of this casting mold sheet, based on expansion behavior and this casting mold bending tablet begins deflection afterwards soon, at last this casting mold sheet roughly at central portion, be the heating part fracture of heater.So-called " contractility " representes that with the maximum deflection that obtains until fracture this value is big more here, and the expression casting mold is yielding more, is rich in flexibility.Need to prove, in this mensuration, also consider the mensuration cycle of next casting mold sheet mensuration beginning when the temperature of heater is 200 ℃ of left and right sides, carry out this mensuration.
The evaluation of-coefficient of thermal expansion-
Anxious coefficient of thermal expansion determination test method according to putting down in writing in the JACT test method(s) M-2 coefficient of thermal expansion determination test method is carried out.Will be at firing temperature: 280 ℃, firing time: the sample of making under 120 seconds the condition (28.3mm φ * 51mmL, the about quarter turn of cutting) be arranged in the high temperature modification sand test device of adjustment to 1000 in the stove ℃, taking-up 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 (%)=[(before the anxious heat back-urgency heat) specimen length] * 100/ (specimen length before the anxious heat)
-resin manufacture example 1-
In the reaction vessel that thermometer, agitating device and condenser are installed, drop into 8000 parts of phenol, 2000 parts of 1-naphthols, 4106 part of 47% formalin and 30 parts of oxalic acid.Then, reaction vessel is slowly heated up, behind the arrival reflux temperature, carried out back flow reaction 90 minutes, further under normal pressure, dewater, under reduced pressure be heated to 180 ℃ afterwards, remove unreacted phenol, obtain phenol-formaldehyde A thus.
-resin manufacture example 2-
Except that dropping into 8000 parts of phenol, 2000 parts of 1-naphthols, 4865 part of 47% formalin and 30 parts of oxalic acid, according to obtaining bakelite B with resin manufacture example 1 same flow process.
-resin manufacture example 3-
Except that dropping into 8000 parts of phenol, 2000 parts of 1-naphthols, 3159 part of 47% formalin and 30 parts of oxalic acid, according to obtaining bakelite C with resin manufacture example 1 same flow process.
-resin manufacture example 4-
Except that dropping into 9000 parts of phenol, 1000 parts of 1-naphthols, 4260 part of 47% formalin and 30 parts of oxalic acid, according to obtaining phenolic resins D with resin manufacture example 1 same flow process.
-resin manufacture example 5-
Except that dropping into 6000 parts of phenol, 4000 parts of 1-naphthols, 3799 part of 47% formalin and 15 parts of oxalic acid, according to obtaining phenolic resins E with resin manufacture example 1 same flow process.
-resin manufacture example 6-
Except that dropping into 8000 parts of phenol, 2000 parts of beta naphthals, 4106 part of 47% formalin and 30 parts of oxalic acid, according to obtaining phenolic resins F with resin manufacture example 1 same flow process.
-resin manufacture example 7-
Except that dropping into 2000 parts of phenol, 8000 parts of bisphenol-As (BPA), 2339 part of 47% formalin and 30 parts of oxalic acid, according to obtaining phenolic resins G with resin manufacture example 1 same flow process.
-embodiment 1-
In 1000 parts of phenol-formaldehyde As, heating and melting mixes 50 parts of ethylenebisstearamides and 10 parts of silane couplers (3-aminopropyltriethoxywerene werene), obtains resin combination 1.
-embodiment 2-
Except the addition that makes ethylenebisstearamide is 120 parts, according to obtaining resin combination 2 with embodiment 1 same flow process.
-embodiment 3-
Except the addition that makes ethylenebisstearamide is 15 parts, according to obtaining resin combination 3 with embodiment 1 same flow process.
-embodiment 4-
Except ethylenebisstearamide being replaced with the di-2-ethylhexylphosphine oxide stearmide, according to obtaining resin combination 4 with embodiment 1 same flow process.
-embodiment 5-
Except ethylenebisstearamide being replaced with ethylidene Shuan Shan Yu acid amides, according to obtaining resin combination 5 with embodiment 1 same flow process.
-embodiment 6-
Except ethylenebisstearamide being replaced with ethylenebis mustard acid amides, according to obtaining resin combination 6 with embodiment 1 same flow process.
-embodiment 7-
Except ethylenebisstearamide is replaced with the stearmide, according to obtaining resin combination 7 with embodiment 1 same flow process.
-embodiment 8-
Except phenol-formaldehyde A is replaced with the bakelite B, according to obtaining resin combination 8 with embodiment 1 same flow process.
-embodiment 9-
Except phenol-formaldehyde A is replaced with the bakelite C, according to obtaining resin combination 9 with embodiment 1 same flow process.
-embodiment 10-
Except phenol-formaldehyde A being replaced with the phenolic resins D, according to obtaining resin combination 10 with embodiment 1 same flow process.
-embodiment 11-
Except phenol-formaldehyde A being replaced with the phenolic resins E, according to obtaining resin combination 11 with embodiment 1 same flow process.
-embodiment 12-
Except phenol-formaldehyde A being replaced with the phenolic resins F, according to obtaining resin combination 12 with embodiment 1 same flow process.
-comparative example 1-
Except phenol-formaldehyde A being replaced with the phenolic resins G, according to obtaining resin combination 13 with embodiment 1 same flow process.
-comparative example 2-
Except in phenol-formaldehyde A, not adding the fatty acid acyl amine, according to obtaining resin combination 14 with embodiment 1 same flow process.
-comparative example 3-
Except in phenolic resins D, not adding the fatty acid acyl amine, according to obtaining resin combination 15 with embodiment 1 same flow process.
-comparative example 4-
Except in phenolic resins E, not adding the fatty acid acyl amine, according to obtaining resin combination 16 with embodiment 1 same flow process.
-comparative example 5-
Except in phenolic resins F, not adding the fatty acid acyl amine, according to obtaining resin combination 17 with embodiment 1 same flow process.
-RCS prepares routine 1-
With 7000 parts be heated to 130～140 ℃ fire resistance particle (regeneration silica sand), and 105 parts of the foregoing descriptions 1～12 and comparative example 1～5 in the resin combination 1～17 that obtains drop into experiment with in the sand muller, mixing 60 seconds.Next, add making 23 parts of hexas be dissolved in the solution that forms in 105 parts of water, the cooling of blowing afterwards, is added 7 parts of calcium stearates, obtains shell mould respectively with RCS (sample 1～17).
-RCS prepares routine 2-
With 7000 parts be heated to 130～140 ℃ fire resistance particle (regeneration silica sand) and be used for obtaining resin combination 18,105 parts of above-mentioned phenol-formaldehyde As and ethylenebisstearamide put into experiment respectively for 5.25 parts and use sand muller, mixing 60 seconds.Next, add making 23 parts of hexas be dissolved in the solution that forms in 105 parts of water, the cooling of blowing afterwards, is added 7 parts of calcium stearates, obtains shell mould with RCS (sample 18).
-estimate-
According to above-mentioned test method, above-mentioned each RCS that obtains (sample 1～18) is carried out the mensuration of the contractility and the coefficient of thermal expansion of casting mold respectively.Creating conditions of result who obtains and phenolic resins is shown in below table 1 and table 2 in the lump.
[table 1]
[table 2]
Result by above-mentioned table 1 and table 2 can know; For as material (sample 1～12) RCS of the present invention, that use resin combination 1～12 to obtain; All be to keep low-thermal-expansion rate, the big material of contractility simultaneously, said resin combination is that the fatty acid amide with the phenol-formaldehyde A～F of resins example 1～6 and regulation makes up and obtains.On the other hand, use phenol and bisphenol-A to obtain the phenolic resins G of resins example 7 as the phenol composition, for the RCS (sample 13) that the said phenolic resins G of use obtains, contractility is little.In addition, although for utilizing the RCS (sample 14～17) that has used phenol-formaldehyde A, D, E, F not to cooperate the resin combination 14～17 of fatty acid amide and obtained, contractility is poor.In addition; To be used for obtaining resin combination, phenol-formaldehyde A and fatty acid amide be engaged in the fire resistance particle respectively and prepare RCS (sample 18); For the material that uses said RCS (sample 18) to obtain, low thermal expansion characteristics and contractility are all good.
Claims (14)
1. a shell mould is used phenol resin composition, it is characterized in that, comprises phenolic resins and fatty acid amide as neccessary composition, and said phenolic resins is that phenols, aphthols and aldehydes reaction are obtained.
2. shell mould as claimed in claim 1 is used phenol resin composition, and wherein, to count 95～50 in mass ratio: 5～50 ratio is used said phenols and said aphthols.
3. according to claim 1 or claim 2 shell mould is used phenol resin composition, and wherein, said aphthols is 1-naphthols and/or beta naphthal.
4. use phenol resin composition like each described shell mould in the claim 1～3; Wherein, said phenolic resins is to be that the reaction of 0.40～0.80 ratio forms through making said phenols (P), said aphthols (N) and said aldehydes (F) the cooperation mol ratio with them: F/ (P+N).
5. use phenol resin composition like each described shell mould in the claim 1～4, wherein, being that the ratio of 1～15 mass parts is used said fatty acid amide with respect to the said phenolic resins of 100 mass parts.
6. use phenol resin composition like each described shell mould in the claim 1～5, wherein, said fatty acid amide is monoamides class, substituted amide class or bisamide class.
7. use phenol resin composition like each described shell mould in the claim 1～6, wherein, said fatty acid amide is the aliphatic acid bisamide.
8. shell mould as claimed in claim 7 is used phenol resin composition, and wherein, said aliphatic acid bisamide is the saturated fatty acid bisamide.
9. use phenol resin composition like each described shell mould in the claim 1～8, wherein, further cooperate silane coupler.
10. a shell mould is used coated sand, it is characterized in that, is to use in the claim 1～9 each described shell mould to coat the fire resistance particle with phenol resin composition and obtains.
11. shell mould as claimed in claim 10 is used coated sand, wherein, uses said phenol resin composition with the ratio that is 0.2～10 mass parts with respect to the said fire resistance particle of 100 mass parts.
12. a shell mould is used casting mold, it is characterized in that, be to use claim 10 or 11 described shell moulds to carry out moulding with coated sand, and it is heating and curing obtain.
13. a shell mould is characterized in that with the manufacturing approach of coated sand, comprises following operation:
Make the reaction in the presence of the catalyst of regulation of phenols, aphthols and aldehydes obtain the operation of phenolic resins;
Said phenolic resins and fatty acid amide melting mixing are used or make respectively the operation that is used for coating the fire resistance particle.
14. shell mould as claimed in claim 13 is with the manufacturing approach of coated sand, wherein, said catalyst is divalent slaine and/or oxalic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009172135 | 2009-07-23 | ||
| JP2009-172135 | 2009-07-23 | ||
| PCT/JP2010/061591 WO2011010559A1 (en) | 2009-07-23 | 2010-07-08 | Phenol resin composition for shell molding, resin-coated sand for shell molding, and shell molding die obtained using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102448637A true CN102448637A (en) | 2012-05-09 |
Family
ID=43499029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800229203A Pending CN102448637A (en) | 2009-07-23 | 2010-07-08 | Phenol resin composition for shell molding, resin-coated sand for shell molding, and shell molding die obtained using the same |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20120029113A1 (en) |
| JP (1) | JP5764490B2 (en) |
| KR (1) | KR20120046271A (en) |
| CN (1) | CN102448637A (en) |
| AU (1) | AU2010274450B2 (en) |
| MY (1) | MY155464A (en) |
| WO (1) | WO2011010559A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688979A (en) * | 2012-06-26 | 2012-09-26 | 长沙南托造型材料有限公司 | Coated sand with long shelf life, and production method of coated sand |
| CN109128009A (en) * | 2018-06-29 | 2019-01-04 | 宁夏共享化工有限公司 | A kind of casting chaplet box resin curing agent |
| CN114130946A (en) * | 2021-11-29 | 2022-03-04 | 江苏丽莎环保科技有限公司 | Copolymer for casting and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6054774B2 (en) * | 2013-02-26 | 2016-12-27 | 旭有機材株式会社 | Resin-coated sand for high-temperature easily disintegratable shell mold, and mold and casting produced using the same |
| JP5933800B1 (en) * | 2015-10-20 | 2016-06-15 | 山川産業株式会社 | Mold-containing binder-containing sand and its production method |
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| JPH0578437A (en) * | 1991-09-18 | 1993-03-30 | Meiwa Kasei Kk | Phenolic novolak resin and curing agent for sealing semiconductor |
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| JPH07106420B2 (en) * | 1988-04-20 | 1995-11-15 | 旭有機材工業株式会社 | Mold material |
| JP3235813B2 (en) * | 1994-08-04 | 2001-12-04 | 住友ベークライト株式会社 | Phenolic resin composition |
| DE10112620A1 (en) * | 2001-03-14 | 2002-09-19 | Bakelite Ag | Binder mixtures and their use |
-
2010
- 2010-07-08 CN CN2010800229203A patent/CN102448637A/en active Pending
- 2010-07-08 AU AU2010274450A patent/AU2010274450B2/en not_active Ceased
- 2010-07-08 MY MYPI2012000124A patent/MY155464A/en unknown
- 2010-07-08 KR KR1020127004501A patent/KR20120046271A/en not_active Application Discontinuation
- 2010-07-08 JP JP2011523605A patent/JP5764490B2/en active Active
- 2010-07-08 WO PCT/JP2010/061591 patent/WO2011010559A1/en active Application Filing
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2011
- 2011-10-11 US US13/270,524 patent/US20120029113A1/en not_active Abandoned
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| JPH04331223A (en) * | 1991-05-07 | 1992-11-19 | Hitachi Chem Co Ltd | Production of naphthol-modified phenolic resin |
| US5206333A (en) * | 1991-05-07 | 1993-04-27 | Hitachi Chemical Company, Ltd. | Method of producing a naphthol-modified phenolic resin of highly increased molecular weight |
| JPH0578437A (en) * | 1991-09-18 | 1993-03-30 | Meiwa Kasei Kk | Phenolic novolak resin and curing agent for sealing semiconductor |
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| CN102688979A (en) * | 2012-06-26 | 2012-09-26 | 长沙南托造型材料有限公司 | Coated sand with long shelf life, and production method of coated sand |
| CN109128009A (en) * | 2018-06-29 | 2019-01-04 | 宁夏共享化工有限公司 | A kind of casting chaplet box resin curing agent |
| CN114130946A (en) * | 2021-11-29 | 2022-03-04 | 江苏丽莎环保科技有限公司 | Copolymer for casting and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140187667A1 (en) | 2014-07-03 |
| AU2010274450B2 (en) | 2013-06-06 |
| JPWO2011010559A1 (en) | 2012-12-27 |
| AU2010274450A1 (en) | 2011-11-03 |
| JP5764490B2 (en) | 2015-08-19 |
| US20120029113A1 (en) | 2012-02-02 |
| MY155464A (en) | 2015-10-15 |
| KR20120046271A (en) | 2012-05-09 |
| WO2011010559A1 (en) | 2011-01-27 |
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Application publication date: 20120509 |