CN104093507A - Organic adhesive agent for mold and casting sand composition and mold obtained using same - Google Patents
Organic adhesive agent for mold and casting sand composition and mold obtained using same Download PDFInfo
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- CN104093507A CN104093507A CN201380008283.8A CN201380008283A CN104093507A CN 104093507 A CN104093507 A CN 104093507A CN 201380008283 A CN201380008283 A CN 201380008283A CN 104093507 A CN104093507 A CN 104093507A
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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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Abstract
Provided is an organic adhesive agent for a mold, that greatly reduces the occurrence of odor, stimulus, smoke, etc., during mold making, is capable of improving the handling properties of the obtained mold, and is capable of advantageously increasing the peel-back resistance thereof. Also provided are an RCS obtained using this kind of organic adhesive agent, and a mold having excellent properties and obtained by using said RCS. The organic adhesive agent for the mold is configured by combining: a non-black phenolic resin (A) and a resol-type phenolic resin (B) having a usage ratio, by mass, of A:B = 95:5-5:95; and at least an Arrhenius base and/or a Br nsted base, as a curing accelerator capable of accelerating the curing reaction of these phenolic resins.
Description
Technical field
The present invention relates to mould using for organic binder, use its molding sand composition obtaining and casting mold, be particularly related to and realized the improvement of operating environment in sand casting, and the phenolic resins that can advantageously manufacture the casting mold with excellent specific property is mould using for organic binder, uses its molding sand composition obtaining and use this molding sand composition moulding and the casting mold that forms.
Background technology
All the time, using shell moulded casting as representative sand casting in, conventionally use following shell casting mold,, by fire resistance particle (molding sand) and phenolic resins (adhesive) and the curing agent such as the hexa further using as required carry out mixingly, use the coated sand (following, referred to as " RCS ") obtaining, it is carried out to hot briquetting, form thus the shell casting mold with intended shape.
But, in the time carrying out the manufacture of this RCS, if use hexa as curing agent, when being heating and curing in the time of making molds, except producing formaldehyde because of use phenolic resins, also produce ammonia because of the decomposition of hexa, and these gases become the reason of stench, also become a factor that causes operating environment to worsen, therefore should reduce this addition as the hexa of curing agent, and propose the countermeasure of interpolation of the multiple modification about phenolic resins, various curing accelerators etc.
For example, in patent documentation 1, propose the phenol resin composition and the hexa that in linear phenol-aldehyde resin, contain alkali metal weak or alkali metal hydroxide and form together to carry out mixing with fire resistance bulk material, manufacture thus shell mould casting mold RCS, hence one can see that, can reduce the use amount of hexa, reduced ammonia generation, have simultaneously can making molds curability, and can bring into play also excellent effect of formative nature.But, for the intensity of the casting mold that uses this RCS to obtain is increased to the abundant degree in actual use, need more hexa use amount, therefore, the problem of the stinks such as ammonia and consequent stimulation still exists.
In addition, in patent documentation 2, propose, produce the RCS in crack when pouring into a mould in casting mold in order to be prevented, use linear phenol-aldehyde resin and/or fusible type phenolic resins as phenolic resins, and use polyethylene glycol, and with these phenolic resins and polyethylene glycol coating casting mold fire resistance shot-like particle, use and same a large amount of hexa as curing agent in the past, so ammonia, formaldehyde gas generated many, have the stink causing because of these gas, stimulate, the problem such as be fuming, and using this RCS to overturn in the hollow casting mold of sediment outflow moulding, aspect splitting in the time of upset or the anti-shelling (anti peel-back property) coming off, also have problems, and existence easily produces the insertion defect while casting, the problems such as gas defects.
And then, following methods is disclosed in patent documentation 3: be that binding agent together uses with the reactive curing accelerator being formed by the amine compound that is selected from melamine, urea, dicyandiamide by the phenolic resins being formed by fusible type phenolic resins and linear phenol-aldehyde resin, the surface of coating fire resistance aggregate, obtain the method for RCS, but the casting mold that uses this RCS to obtain, its operability is poor, in the time of the demoulding of casting mold, carrying, easily produce fracture, the problem such as slight crack, and also insufficient aspect anti-shelling.
In addition, following methods is disclosed in patent documentation 4: by further mixing with fusible type phenolic resins emulsion or suspension the fire resistance aggregate that uses linear phenol-aldehyde resin coating surface to form, on the surface of this fire resistance aggregate, further enforcement is resin-coated, manufactures thus the method for the shell mould casting mold casting RCS with low odor, high strength, difficult adhesive.; therefore fusible type phenolic resins can be as the curing agent of linear phenol-aldehyde resin, but while only using this two kinds of phenolic resins coating fire resistance aggregates surperficial, uses the operability of the casting mold that this RCS obtains poor; and anti-shelling is also poor, there is in actual use larger problem.In addition, although also disclose for fusible type phenolic resins emulsion or the suspension of the further coating of fire resistance aggregate and contained the organonitrogen compound such as urea, melamine or hexa, even if but contain this organonitrogen compound, also the raising of anti-shelling while being difficult to fully realize aforesaid operations, hollow making molds, in addition, if increase the use amount of hexa, also can produce the problem such as stink, stimulation.
Patent documentation 1: TOHKEMY 2003-170244 communique
Patent documentation 2: Japanese kokai publication sho 58-119433 communique
Patent documentation 3: No. 4369653 communique of Japan Patent
Patent documentation 4: Japanese kokai publication hei 11-244991 communique
Summary of the invention
Here, the present invention completes taking above-mentioned situation as background, it solves problem and is to provide a kind of generation of stink, stimulation, cigarette etc. while significantly having reduced making molds, can realize the raising of the operability of gained casting mold, and advantageously improve the mould using for organic binder of anti-shelling, and the RCS that uses this organic binder bond to obtain is provided, and use this RCS to carry out the casting mold with excellent specific property that moulding obtains.
In order to solve such problem, the present invention can suitably adopt the following variety of way of enumerating to implement, and, also can adopt any combination of the variety of way of following record.It should be noted that mode of the present invention or technical characterictic are not subject to any restriction of following record content, and are interpreted as the entirety based on description recording to be familiar with.
(1) a kind of mould using for organic binder, it is characterized in that, by linear phenol-aldehyde resin, fusible type phenolic resins and can promote being combined to form of curing accelerator of the curing reaction of these phenolic resins, and this linear phenol-aldehyde resin (A) is counted A:B=95:5～5:95 with the usage rate of this fusible type phenolic resins (B) with quality criteria, simultaneously, as this curing accelerator, at least contain Arrhenius alkali and/or brnsted base.
(2) mould using for organic binder as described in aforesaid way (1), is characterized in that, as described Arrhenius alkali, and at least one of the Arrhenius alkali that the pH that uses the 0.1mol/l aqueous solution is 10～14.
(3) mould using for organic binder as described in aforesaid way (2), is characterized in that, described Arrhenius alkali is selected from NaOH, lithium hydroxide, calcium hydroxide and potassium hydroxide.
(4) mould using for organic binder as described in any one in aforesaid way (1)～(3), it is characterized in that, as described brnsted base, at least one of the alkali metal inorganic salts that the pH that uses the 0.1mol/l aqueous solution is 8～14.
(5) mould using for organic binder as described in aforesaid way (4), is characterized in that, described alkali metal inorganic salts are selected from sodium carbonate, sodium acid carbonate, potash, lithium carbonate, sodium sulfite, sodium aluminate and sodium stannate trihydrate.
(6) mould using for organic binder as described in any one in aforesaid way (1)～(5), it is characterized in that, as described brnsted base, at least one of the alkaline metal organic salt that the pH that uses the 0.1mol/l aqueous solution is 2～7.5.
(7) mould using for organic binder as described in aforesaid way (6), it is characterized in that, described alkaline metal organic salt is selected from sodium alginate, sodium salicylate, Sodium Benzoate, 1-naphthol-5-sulfonic acid sodium, p-phenolsulfonic acid's sodium and paratoluenesulfonic acid sodium salt.
(8) mould using for organic binder as described in any one in aforesaid way (1)～(7), wherein, with respect to total amount 100 mass parts of described linear phenol-aldehyde resin and described fusible type phenolic resins, the total amount of the curing accelerator being formed by described Arrhenius alkali and/or brnsted base is in the scope of 0.2～15 mass parts.
(9) mould using for organic binder as described in any one in aforesaid way (1)～(8), is characterized in that, further contains hexa.
(10) molding sand composition, is characterized in that, uses the mould using for organic binder described in any one in aforesaid way (1)～(9), and by mixing and form to described mould using for organic binder and molding sand.
(11) molding sand composition as described in aforesaid way (10), wherein, with respect to molding sand 100 mass parts, described mould using for organic binder carries out mixing with the ratio of 0.2～10 mass parts.
(12) molding sand composition as described in aforesaid way (10) or (11), wherein, the resin compound of described linear phenol-aldehyde resin and described fusible type phenolic resins is mixing with described molding sand before described curing accelerator.
(13) molding sand composition as described in aforesaid way (10) or (11), wherein, has coordinated the described linear phenol-aldehyde resin of described curing accelerator and described fusible type phenolic resins mixing with described molding sand respectively.
(14) casting mold, is characterized in that, uses the molding sand composition described in any one in aforesaid way (10)～(13) to carry out moulding, and is heating and curing and forms.
invention effect
As mentioned above, because mould using for organic binder of the present invention is by linear phenol-aldehyde resin, fusible type phenolic resins with combine and form as the Arrhenius alkali of curing accelerator and/or brnsted base, and substantially do not use a large amount of hexas as curing agent, therefore can avoid pyrolysis based on this curing agent etc. and produce ammonia, formaldehyde, can reduce as much as possible thus the ammonia from whole binding agents, the generation of formaldehyde, effectively suppress based on stink, stimulate the problem waiting and produce, and can advantageously realize the improvement of operating environment.
And, for this mould using for organic binder of the present invention, due to linear phenol-aldehyde resin, fusible type phenolic resins are combined with Arrhenius alkali and/or brnsted base as curing accelerator, so use the tunicle on the RCS Sand surface of this binding agent formation to be solidified more rapidly and effectively, and can advantageously improve the operability of the casting mold being obtained by this RCS.In addition, by the raising of this operability, can effectively suppress or stop while carrying out the demoulding, carrying after firm making molds etc. fracture, the generation of slight crack etc., and the reduction, the raising of productivity ratio of disqualification rate can advantageously realize casting mold casting time.
Further, for this mould using for organic binder of the present invention, by using its RCS obtaining to carry out in the casting mold of moulding, can effectively improve its anti-shelling, thus, the casting mold of uniform wall thickness can be formed easily, the intensity of casting mold can be maintained simultaneously, thus the insertion defect when advantageously suppressing or avoiding casting, the generation of gas defects.
Detailed description of the invention
In mould using for organic binder of the present invention, form its linear phenol-aldehyde resin and fusible type phenolic resins be under the existence of acidic catalyst or base catalyst, make phenols react with aldehydes and the solid shape that obtains or liquid (for example, varnish shape or emulsion etc.) condensation product (forming line style or fusible type according to the kind of catalyst using), and be under the curing agent of regulation or the existence of curing catalysts or not, to heat and show heat cured phenolic resins.
Can refer to as the phenols of this phenolic resins raw material the derivative of phenol and phenol, for example, except phenol, can also enumerate the known material such as the polyhydric phenols such as the alkyl phenols such as cresols, xylenols, p-t-butyl phenol, nonyl phenol, resorcinol, Bisphenol F, bisphenol-A and their mixture, and can use separately one wherein or be used in combination of two or more.
In addition, as aldehydes, for example, except the formalin as formalin form, can also enumerate paraformaldehyde, trioxane, acetaldehyde, para-acetaldehyde, propionic aldehyde etc., and then can also suitably use except the known aldehyde compound these.And these aldehydes use separately or are used in combination of two or more all without any problem.
In the present invention, operable linear phenol-aldehyde resin is the following phenolic resins forming: use above-mentioned phenols and aldehydes, as everyone knows, pass through acidic catalyst, for example, the organic acids such as the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, xylene monosulfonic acid, and the acidic materials such as zinc oxide, zinc chloride, magnesia, zinc acetate carry out condensation reaction and form.It should be noted that, at this moment, as aldehydes (F) and phenols (P) coordinate mol ratio (F/P), can suitably select according to the kind of the catalysts using etc., preferably in 0.55～0.80 scope, select.
On the other hand, fusible type phenolic resins is to use above-mentioned phenols and aldehydes, and similarly carries out condensation reaction by known base catalyst in the past and form.It should be noted that, as base catalyst, can use the hydroxide of the alkali metal such as NaOH, calcium hydroxide or alkaline-earth metal, the oxide of alkaline-earth metal, in addition, can also use naphthenate (naphthenate), the hydroxide of divalent metal etc. of the amines such as dimethylamine, triethylamine, butylamine, dimethyl benzylamine, naphthylenediamine, ammonia, hexa and divalent metal.In addition, in this condensation reaction, the mol ratio (F/P) that coordinates of aldehydes and phenols can suitably be selected according to the kind of the catalysts using etc., and conventionally in 1.1～4.0 scope, selects.
In mould using for organic binder of the present invention, as its resin-bonded composition, together use the linear phenol-aldehyde resin and the fusible type phenolic resins that obtain as mentioned above, fusible type phenolic resins has played the function as the curing agent of linear phenol-aldehyde resin, simultaneously as the composition that can improve the characteristics such as casting mold bending strength.And, by these linear phenol-aldehyde resins (A) and fusible type phenolic resins (B) used time, their usage rate need to, as A:B=95:5～5:95, it is desirable for the usage rate that advantageously adopts A:B=30:70～70:30 especially taking quality criteria.
It should be noted that, if the usage rate of this is fusible type phenolic resins is with respect to exceeding 95 quality % with the total amount of linear phenol-aldehyde resin, and therefore the usage rate of linear phenol-aldehyde resin is less than 5 quality %, in the time mixing this two kinds of phenolic resins of use, be difficult to them to mix equably, and not many as the residual quantitative change of the fusible type phenolic resins of linear phenol-aldehyde resin curing agent, produce the inadequate problem of raising effect as the curing rate of binding agent entirety.In addition, in contrast, if the usage ratio of fusible type phenolic resins is less than 5 quality %, and the usage rate of linear phenol-aldehyde resin exceedes 95 quality %, cannot make its curing linear phenol-aldehyde resin become many by fusible type phenolic resins, this remaining linear phenol-aldehyde resin is uncured and left behind, and is difficult to realize the completely curing of binding agent, therefore may cause the intensity of casting mold to decline.
In addition think because the curing reaction of this linear phenol-aldehyde resin and fusible type phenolic resins is dehydration condensation substantially, so by providing OH by Arrhenius alkali and/or brnsted base,
-, accept H
+, make the phenyl ring activation of linear phenol-aldehyde resin, promote the dehydration of above-mentioned curing reaction, its reaction speed accelerates.
Herein, can be can generate hydroxyl ion (OH when water-soluble as the Arrhenius alkali of reaction promoter
-) compound, wherein, the Arrhenius alkali that the pH that can preferably use in the present invention the 0.1mol/l aqueous solution is 10～14.Think in the time that the pH of this Arrhenius aqueous alkali is 10～14, demonstrate strong basicity, it is by providing OH
-thereby, make the phenyl ring activation of linear phenol-aldehyde resin, accelerate fusible type phenolic resins and the linear phenol-aldehyde resin dehydration condensation when curing.
In addition, as this Arrhenius alkali, be particularly preferably any in NaOH (pH=13.5), lithium hydroxide (pH=13.0), calcium hydroxide (pH=13.1), potassium hydroxide (pH=13.4), and can use separately wherein a kind of or be used in combination of two or more.It should be noted that, the pH value in each compound unquote is the pH value of the 0.1mol/l aqueous solution of each compound.
And then, in the present invention, as curing accelerator, the brnsted base of above-mentioned Arrhenius alkali and regulation together can be used, or substitute Arrhenius alkali by the brnsted base specifying and use, described brnsted base is in other words for receiving the material of proton, can accepting H
+compound.
And, in the time that this brnsted base is alkali metal inorganic salts, the material that the pH that can preferably use its 0.1mol/l aqueous solution is 8～14.In the time that the pH of the 0.1mol/l aqueous solution of the alkali metal inorganic salts as brnsted base is 8～14, hydrolysis generates OH
-ion, can think thus by the reaction mechanism identical with above-mentioned Arrhenius alkali, the dehydration condensation while having accelerated linear phenol-aldehyde resin and fusible type phenolic resin curing.
In addition, as the alkali metal inorganic salts of this brnsted base, be preferably any in sodium carbonate (pH=11.6), sodium acid carbonate (pH=8.6), potash (pH=11.5), lithium carbonate (pH=11.5), sodium sulfite (pH=9.3), sodium aluminate (pH=11.4), sodium stannate trihydrate (pH=11.8), and can use separately wherein a kind of or be used in combination of two or more.It should be noted that, the pH value in each compound unquote is the pH value of the 0.1mol/l aqueous solution of each compound.
In addition, in the time that brnsted base is alkaline metal organic salt, the material that the pH that can advantageously use its 0.1mol/l aqueous solution is 2～7.5.Think in the time giving this pH value, by accepting the H of phenyl ring of linear phenol-aldehyde resin
+, the dehydration condensation while having accelerated linear phenol-aldehyde resin and fusible type phenolic resin curing.
It should be noted that, as the alkaline metal organic salt of this brnsted base, be preferably any in sodium alginate (pH=7.3), sodium salicylate (pH=6.3), Sodium Benzoate (pH=7.3), 1-naphthol-5-sulfonic acid sodium (pH=3.3), p-phenolsulfonic acid's sodium (pH=5.8), paratoluenesulfonic acid sodium salt (pH=6.5), and can use separately wherein a kind of or be used in combination of two or more.It should be noted that, the pH value in each compound unquote is the pH value of the 0.1mol/l aqueous solution of each compound.
In addition, the use amount of Arrhenius alkali as above, brnsted base, within the scope of the use amount of whole curing accelerators.,, with respect to total amount 100 mass parts of two kinds of phenolic resins as resin-bonded composition, the total amount of Arrhenius alkali and/or brnsted base conventionally in 0.2～15 mass parts, preferably used in the scope of 0.5～8 mass parts.It should be noted that, its reason is, if the use amount of this curing accelerator reduces, is difficult to give full play to its curing facilitation effect, and in addition, if its use amount is too much, the intensity of casting mold can decline.
As mentioned above, for mould using for organic binder of the present invention, use linear phenol-aldehyde resin and fusible type phenolic resins as resin-bonded composition, and the Arrhenius alkali of dehydration condensation when at least these linear phenol-aldehyde resins and fusible type phenolic resin curing have been accelerated in use and/or brnsted base are as curing accelerator, and except these neccessary compositions, can also further add known various gradation compositions.Particularly as curing accelerator or curing agent, further add hexa, aspect the raising of RCS characteristic, be effective, many but if it adds quantitative change, the problems such as stink are again produced, therefore with respect to total amount 100 mass parts of two kinds of phenolic resins as resin-bonded composition, conventionally following with 10 mass parts, preferably 8 mass parts are following, more preferably the ratio below 5 mass parts is used.
And, by so forming the organic binder bond of the present invention forming, by coordinating with known molding sand and its surface of coating, form the RCS for the casting molds such as shell mould casting mold are carried out to moulding.Wherein, as the use amount of the organic binder bond for obtaining RCS, that kind, the desired mould strength etc. of considering the phenolic resins wherein using determined, therefore can not limit entirely, typically, with respect to molding sand 100 mass parts, in the scope of 0.2～10 about mass parts, preferably in 0.5～8 mass parts, more preferably in the scope of 0.5～5 mass parts.
In addition, for the molding sand that carries out coating with this organic binder bond, suitably choice for use known material in the past, its kind is not particularly limited in the present invention.Due to the base material of this molding sand formation casting mold, so as long as thering is the inorganic fire resistance particle that can tolerate the fire resistance of casting and the particle diameter of applicable casting mold formation (moulding), just can use all the time for any known inorganic particulate of shell-molded.In addition, as this fire resistance particle, for example, except common use silica sand (salica sand), can also enumerate the special sand such as olivine sand (olivine sand), zircon sand (zircon sand), chromium sand (chromite sand), aluminum oxide sand (alumina sand); The slag class particles such as ferrochrome class slag (slag), ferronickel class slag, converter slag; The artificial particle of mullite class of Naigai Cerabeads (trade name, ITOCHU Ceratech Co., Ltd.) and so on; Or by the regenerated particle etc. of reclaiming after their castings, they can use separately or be used in combination of two or more.
It should be noted that, in the time using organic binder bond manufacturing objective RCS of the present invention, its manufacture method is not particularly limited, can adopt the hot rubbing method of dry type, half hot rubbing method, cold rubbing method, known any method in the past such as powder solvent method, but in the present invention, special recommendation adopts the hot rubbing method of so-called dry type, , in the mixing rolls such as sand muller or high speed puddle mixer (speed mixer), by after the molding sand of preheating and the resin-bonded composition (linear phenol-aldehyde resin+fusible type phenolic resins) that forms organic binder bond are mixing, add the curing accelerator aqueous solution of regulation, and cooling to make block content disintegration be granular by blowing, add calcium stearate (lubricant).In addition, can suitably select providing two kinds of phenolic resins, curing accelerator and the molding sand of resin-bonded composition that form organic binder bond of the present invention to carry out mixing opportunity, except mixing successively individually, can also suitably combining, it is mixing to carry out.
And then, while using the RCS obtaining as mentioned above to carry out moulding to the casting mold of the regulations such as shell mould casting mold, realize being heating and curing of this RCS, and under heating, carry out the moulding of target casting mold, as this heating formative method, be not particularly limited, can advantageously adopt known any method in the past.For example, can obtain as follows casting mold: by above-mentioned RCS by gravity fall mode or be blown into mode etc. and be filled into and there is the shape space of the expectation of giving target casting mold and be heated in the shaping mould of 150 DEG C～300 DEG C, it is solidified, then by the casting mold demoulding from above-mentioned shaping mould after solidifying.The casting mold obtaining as mentioned above can advantageously be given the feature 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 subject to any restriction of the content of these embodiment records.In addition, it will be appreciated that as in the present invention, except following examples, and then except above-mentioned concrete description, be also included in various changes that in the scope that does not depart from purport of the present invention, the knowledge based on those skilled in the art is made, correction, improvement etc.
It should be noted that, in below recording, " part " and " % ", as long as no being particularly limited, represents respectively " mass parts " and " quality % ".In addition, the various characteristics of the RCS below manufacturing is measured according to following test method.
-Production Example of linear phenol-aldehyde resin-
Drop into 940 parts of phenol, 428 part of 47% formalin and 2.8 parts of oxalic acid to possessing in the reaction vessel of thermometer, agitating device and condenser.It should be noted that, phenol is 0.67 with the mol ratio (F/P) that coordinates of formalin.Then, reaction vessel is slowly heated up, arrive after reflux temperature, carry out back flow reaction 90 minutes, be further heated to reacting liquid temperature and reach 170 DEG C, reduced pressure concentration, obtains linear phenol-aldehyde resin thus.
-Production Example of fusible type phenolic resins-
Drop into after 680 parts of phenol, 535 part of 47% formalin and 101 parts of hexas to possessing in the reaction vessel of thermometer, agitating device and condenser, be warming up to 70 DEG C through about 60 minutes, at this temperature, react 5 hours.It should be noted that, phenol is 1.16 with the mol ratio (F/P) that coordinates of formalin.Then, the reactant liquor of gained is warming up to 90 DEG C, decompression dehydration, obtains fusible type phenolic resins thus.
-embodiment 1-
7000 parts of Flattery silica sands that are heated to 145 DEG C are put in sand muller, linear phenol-aldehyde resin obtained above and fusible type phenolic resins taking cooperation ratio (1:1) the input total amount shown in following table 1 as 175 parts again, mixing 50 seconds.Then, 0.9 part of dissolution of sodium hydroxide as the Arrhenius alkali of curing accelerator, in 105 parts of water, is supplied to the solution forming thus in sand muller, carry out mixing, until sand grains disintegration is then blown cooling, and then add 7 parts of calcium stearates, obtain shell mould RCS.
-embodiment 2～4-
Use respectively 0.9 part of lithium hydroxide as Arrhenius alkali, calcium hydroxide or potassium hydroxide as curing accelerator, replace the NaOH in embodiment 1, in addition, obtain respectively the RCS of embodiment 2～4 according to method similarly to Example 1.
-embodiment 5～11-
In embodiment 1, as curing accelerator, use respectively 0.9 part of sodium carbonate as the alkali metal inorganic salts of brnsted base, sodium acid carbonate, potash, lithium carbonate, sodium sulfite, sodium aluminate or sodium stannate trihydrate, in addition, obtain respectively the RCS of embodiment 5～11 according to method similarly to Example 1.
-embodiment 12～17-
In embodiment 1, as curing accelerator, use respectively 3.5 parts of sodium alginates as the alkaline metal organic salt of brnsted base, sodium salicylate, Sodium Benzoate, 1-naphthol-5-sulfonic acid sodium, p-phenolsulfonic acid's sodium or paratoluenesulfonic acid sodium salt, in addition, obtain respectively the RCS of embodiment 12～17 according to method similarly to Example 1.
-embodiment 18～21-
In embodiment 1, as curing accelerator, use the Arrhenius alkali of the ormal weight shown in following table 3 and the combination of brnsted base or brnsted base combination each other, in addition, obtain respectively similarly to Example 1 the various RCS of embodiment 18～21.
-embodiment 22～25-
The usage ratio of linear phenol-aldehyde resin and fusible type phenolic resins in change embodiment 6 as shown in table 4, adopts the use amount of sodium acid carbonate and sodium salicylate as shown in table 4, in addition, obtains similarly to Example 6 the various RCS of embodiment 22～25.
-embodiment 26～29-
In embodiment 1, as curing accelerator, use the combination of Arrhenius alkali and/or brnsted base and the hexa of the ormal weight shown in following table 4,5, in addition, obtain respectively similarly to Example 1 the various RCS of embodiment 26～29.
-embodiment 30-
7000 parts of Flattery silica sands that are heated to 145 DEG C are put in sand muller, drop into and coordinated in advance 87.5 parts of linear phenol-aldehyde resins and 0.9 part of material that sodium acid carbonate obtains wherein, mixing 50 seconds, and then 87.5 parts of fusible type phenolic resins of interpolation, carry out mixing, until sand grains disintegration is then blown cooling, then add 7 parts of calcium stearates, obtain target RCS.
-comparative example 1-
7000 parts of Flattery silica sands that are heated to 145 DEG C are put in sand muller, the linear phenol-aldehyde resin of manufacturing before dropping into wherein 175 parts, mixing 50 seconds, then add 26.3 parts of hexas are dissolved in to the solution forming in water as curing agent, carry out mixing, until sand grains disintegration.Then, blow cooling, then add 7 parts of calcium stearates, obtain RCS.
-comparative example 2-
Use fusible type phenolic resins to replace the linear phenol-aldehyde resin in comparative example 1, and do not add curing agent, in addition, similarly obtain target RCS with comparative example 1.
-comparative example 3,4-
In embodiment 1, do not use curing accelerator, or use 3.5 parts of melamines to replace the NaOH as curing accelerator, in addition, obtain respectively similarly to Example 1 target RCS.
-evaluation of RCS characteristic-
For the various RCS that obtain in above-described embodiment 1～30 and comparative example 1～4, according to following determination of test method or evaluate its characteristic, the formation of its result and each RCS is together shown in following table 1～table 6.
-mensuration of bending strength-
Use each RCS, according to JIS-K-6910, make JIS formula sample (10mm × 10mm × 60mm, firing condition: 250 DEG C × 60 seconds), for this JIS formula sample obtaining, measure its bending strength (kgf/cm according to JACT test method(s): SM-1
2).This bending strength is higher, represents that casting mold is more high strength.
-mensuration of RCS fusion points-
For the fusion temperature of each RCS, measure according to JACT test method(s): C-1 (fusion points test method(s)).The fusion temperature of this mensuration is higher, and the resistance to blocking of RCS is more excellent.
-mensuration of bending (500gf) amount-
According to the bending test method of JACT test method(s): SM-3, for the each test film (180mm × 40mm × 5mm, firing condition: 250 DEG C × 40 seconds) that uses each RCS to obtain, portion applies the loading of 500gf in the central, use amesdial (dial gauge) to read the deflection (mm) of placing test film central portion after 3 minutes, using this value as bending (500gf) amount.This amount of bow (deflection) is to represent operability after firm making molds and the standard index of casting mold curing rate, and this amount of bow is less, represents that the curing rate of casting mold is faster, and operability is better.
-evaluation of anti-shelling-
According to the shelling test method(s) of JACT test method(s): C-4 (the organic material industry law of the 5-2-1 rising sun), evaluate the anti-shelling of each RCS.Particularly, by tipping bucket (dump box) to being heated to supply with each RCS on the mould of 280 DEG C ± 2 DEG C of temperature, after 40 seconds, take apart a die from tipping bucket, on electric heater, the RCS being attached on this mould is burnt till to filbert, it is solidified, thereby on mould, form test film.Then, for the test film taking off from mould, measure its quality, and by range estimation to the upper RCS in its surface peel off state evaluation, obtain anti-shelling mark.It should be noted that, anti-shelling mark be using test film during without sur-face peeling area as 5 points, when surface is all peeled off, as 1 point, evaluate with 5 stages.Therefore, be 4 points when peeling off when area is 1/4, be 3 points 1/2 time, be 2 points 3/4 time.And this anti-shelling mark is larger, represent by being temporarily attached to the casting mold that forms of RCS on the mould of heating fewer at its splitting or the situation of peeling off.
In addition, for the test film taking out, cut off its central portion from this mould, measure respectively the central authorities of this section and the thickness at two ends, carry out the wall thickness evaluation at 3 positions different in test film.The thicker test film of wall thickness at each position is the good test film of anti-shelling, and the more test films of the quantity at the position of the above thickness of 4mm, represents that anti-shelling is better.
-mensuration of formaldehyde/ammonia generation-
In combustion tube, at the temperature of 300 DEG C, to the each RCS of 1000g heating 5 minutes, on the other hand, take out the atmosphere gas in this combustion tube with the flow of 1L/ minute with pump, then, the formaldehyde gas in the atmosphere gas of this taking-up and ammonia are collected respectively in the pure water of 40ml × 2.Then, this formalin obtaining is carried out quantitatively with acetylacetone,2,4-pentanedione standard measure, on the other hand, for the ammonia spirit obtaining, by titration, ammonia generation is carried out quantitatively.This formaldehyde gas generation, ammonia generation are more, and stink is stronger, cause operating environment more to worsen.
From the result of above-mentioned table 1～table 6, the amount of bow of the each RCS obtaining in embodiment 1～30 is all low, and in addition, in the evaluation of anti-shelling, anti-shelling mark is also high, and confirm test film also have a lot of 4mm with wall thickness compared with thickness portion.Therefore, for the each RCS obtaining in embodiment 1～30, the curing rate of casting mold is fast, and can effectively improve the operability of the casting mold after firm moulding, and the generation of fractureing can advantageously contribute to prevent the demoulding after the firm moulding of casting mold, carrying time, slight crack etc., in addition in the time of making molds, aspect the reduction of disqualification rate and the raising of productivity ratio, be also favourable.And each RCS of these embodiment 1～30 can realize the raising of anti-shelling, can effectively improve thus the uniformity of casting mold wall thickness, and can advantageously contribute to maintain the intensity of casting mold, insertion defect, gas defects while eliminating casting.
In addition, for each RCS of this embodiment 1～30, owing to significantly having reduced formaldehyde gas generation, ammonia generation, therefore think the problem that the operating environment that also can advantageously avoid a large amount of use hexas obtain as curing agent as the RCS of comparative example 1 RCS in the past to cause because of stink worsens.
And then, realize significant improvement aspect at least one in bending strength, fusion points of each RCS of embodiment 1～30, thus, advantageously realize the high strength of casting mold, and also can advantageously realize the raising of resistance to blocking.Even if particularly confirmed only to use a small amount of Arrhenius alkali, brnsted base, the effect of improving of fusion points also becomes more remarkable.
Confirm on the other hand, be equivalent to the RCS obtaining in the comparative example 1 of RCS in the past, formaldehyde gas generation, ammonia generation are many, there is problem frowzy, and the anti-shelling inequality of the RCS of the RCS of comparative example 1 and comparative example 2～4, in addition, also poor than the RCS of embodiment 1～30 aspect fusion points, amount of bow.
Claims (14)
1. a mould using for organic binder, it is characterized in that, by linear phenol-aldehyde resin, fusible type phenolic resins and can promote being combined to form of curing accelerator of the curing reaction of these phenolic resins, and this linear phenol-aldehyde resin (A) is counted A:B=95:5～5:95 with the usage rate of this fusible type phenolic resins (B) with quality criteria, simultaneously, as this curing accelerator, at least contain Arrhenius alkali and/or brnsted base.
2. mould using for organic binder as claimed in claim 1, is characterized in that, as described Arrhenius alkali, and at least one of the Arrhenius alkali that the pH that uses the 0.1mol/l aqueous solution is 10～14.
3. mould using for organic binder as claimed in claim 2, is characterized in that, described Arrhenius alkali is selected from NaOH, lithium hydroxide, calcium hydroxide and potassium hydroxide.
4. the mould using for organic binder as described in any one in claim 1～3, is characterized in that, as described brnsted base, and at least one of the alkali metal inorganic salts that the pH that uses the 0.1mol/l aqueous solution is 8～14.
5. mould using for organic binder as claimed in claim 4, is characterized in that, described alkali metal inorganic salts are selected from sodium carbonate, sodium acid carbonate, potash, lithium carbonate, sodium sulfite, sodium aluminate and sodium stannate trihydrate.
6. the mould using for organic binder as described in any one in claim 1～5, is characterized in that, as described brnsted base, and at least one of the alkaline metal organic salt that the pH that uses the 0.1mol/l aqueous solution is 2～7.5.
7. mould using for organic binder as claimed in claim 6, is characterized in that, described alkaline metal organic salt is selected from sodium alginate, sodium salicylate, Sodium Benzoate, 1-naphthol-5-sulfonic acid sodium, p-phenolsulfonic acid's sodium and paratoluenesulfonic acid sodium salt.
8. the mould using for organic binder as described in any one in claim 1～7, wherein, with respect to total amount 100 mass parts of described linear phenol-aldehyde resin and described fusible type phenolic resins, the total amount of the curing accelerator being formed by described Arrhenius alkali and/or brnsted base is in the scope of 0.2～15 mass parts.
9. the mould using for organic binder as described in any one in claim 1～8, is characterized in that, further contains hexa.
10. a molding sand composition, is characterized in that, right to use requires the mould using for organic binder described in any one in 1～9, and by mixing and form to described mould using for organic binder and molding sand.
11. molding sand compositions as claimed in claim 10, wherein, with respect to molding sand 100 mass parts, described mould using for organic binder carries out mixing with the ratio of 0.2～10 mass parts.
12. molding sand compositions as described in claim 10 or 11, wherein, the resin compound of described linear phenol-aldehyde resin and described fusible type phenolic resins is mixing with described molding sand before described curing accelerator.
13. molding sand compositions as described in claim 10 or 11, wherein, have coordinated the described linear phenol-aldehyde resin of described curing accelerator and described fusible type phenolic resins mixing with described molding sand respectively.
14. 1 kinds of casting molds, is characterized in that, right to use requires the molding sand composition described in any one in 10～13 to carry out moulding, and are heating and curing and form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012023373A JP5876737B2 (en) | 2012-02-06 | 2012-02-06 | Organic binder for mold, method for producing casting sand composition using the same, and method for producing mold |
| JP2012-023373 | 2012-02-06 | ||
| PCT/JP2013/051192 WO2013118573A1 (en) | 2012-02-06 | 2013-01-22 | Organic adhesive agent for mold and casting sand composition and mold obtained using same |
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| CN104093507A true CN104093507A (en) | 2014-10-08 |
| CN104093507B CN104093507B (en) | 2016-11-02 |
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| CN201380008283.8A Active CN104093507B (en) | 2012-02-06 | 2013-01-22 | Mould using for organic binder, use its molding sand composition obtained and casting mold |
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| Country | Link |
|---|---|
| JP (1) | JP5876737B2 (en) |
| CN (1) | CN104093507B (en) |
| WO (1) | WO2013118573A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6024244A (en) * | 1983-07-20 | 1985-02-06 | Sumitomo Deyurezu Kk | Phenolic resin binder for shell mold |
| JPS63101038A (en) * | 1986-10-17 | 1988-05-06 | Aisin Chem Co Ltd | Production of resin coated sand grain for shell mold |
| JP2003170244A (en) * | 2001-12-05 | 2003-06-17 | Hitachi Chem Co Ltd | Phenol resin composition for shell molding and resin coated sand for shell molding mold |
| JP2004154804A (en) * | 2002-11-05 | 2004-06-03 | Lignyte Co Ltd | Resin-coated sand for mold and method for making mold |
| CN102105241A (en) * | 2008-07-29 | 2011-06-22 | 群荣化学工业株式会社 | Binder composition for casting mold formation and process for producing casting mold using the binder composition for casting mold formation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62124046A (en) * | 1985-11-20 | 1987-06-05 | Asahi Organic Chem Ind Co Ltd | Molding material for shell mold |
-
2012
- 2012-02-06 JP JP2012023373A patent/JP5876737B2/en active Active
-
2013
- 2013-01-22 WO PCT/JP2013/051192 patent/WO2013118573A1/en active Application Filing
- 2013-01-22 CN CN201380008283.8A patent/CN104093507B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6024244A (en) * | 1983-07-20 | 1985-02-06 | Sumitomo Deyurezu Kk | Phenolic resin binder for shell mold |
| JPS63101038A (en) * | 1986-10-17 | 1988-05-06 | Aisin Chem Co Ltd | Production of resin coated sand grain for shell mold |
| JP2003170244A (en) * | 2001-12-05 | 2003-06-17 | Hitachi Chem Co Ltd | Phenol resin composition for shell molding and resin coated sand for shell molding mold |
| JP2004154804A (en) * | 2002-11-05 | 2004-06-03 | Lignyte Co Ltd | Resin-coated sand for mold and method for making mold |
| CN102105241A (en) * | 2008-07-29 | 2011-06-22 | 群荣化学工业株式会社 | Binder composition for casting mold formation and process for producing casting mold using the binder composition for casting mold formation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104093507B (en) | 2016-11-02 |
| JP2013158810A (en) | 2013-08-19 |
| WO2013118573A1 (en) | 2013-08-15 |
| JP5876737B2 (en) | 2016-03-02 |
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