CN100558485C - Be used for the oil-based release agent of die casting, method, casting method and the injection unit of setting solvent mixing ratio - Google Patents
Be used for the oil-based release agent of die casting, method, casting method and the injection unit of setting solvent mixing ratio Download PDFInfo
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Abstract
The invention provides a kind of oil-based release agent that is used for die casting, it contains: the solvent of 70 to 98 weight portions, and described solvent has the flash point of regulation; The high viscosity mineral oil of 1 to 10 weight portion and/or artificial oil; 15 weight portions or silicone oil still less; And 1 to 5 additive of weight portion with lubricating function, wherein, the flash point of described releasing agent is in 70 to 170 ℃ scope, and the dynamic viscosity of described releasing agent under 40 ℃ is 2 to 30mm
2/ s or higher, the present invention also are provided at method, casting method and the injection unit of setting solvent mixing ratio under the situation of using this releasing agent.
Description
Technical field
The present invention relates to be used for the oil-based release agent of die casting, the method for setting solvent mixing ratio, the casting method of using this oil-based release agent and injection unit.The present invention also is applicable to drift (plunger chip) as lubricant.
Background technology
Known ground, in press casting procedure, the die cavity portion for lubricated mould by the jet lubrication agent, forms oil film on the mold cavity surface of mould, and this lubricant is known as releasing agent after open form (die opening).This oil film prevents that the so coloured motlten metal of die cavity and for example aluminium, magnesium and zinc on the die cavity from combining, and makes it possible to continuous casting.The releasing agent that is used for die casting broadly is divided into oil-based release agent and water-soluble mold-release agent.In view of productivity ratio, security and working environment, often use water-soluble mold-release agent in recent years.
Yet before 40 years, releasing agent has only (being known as old oil-based release agent hereinafter) of oiliness, and it contains the solid matter of lard, powder and graphite, uses this releasing agent to make machine become sticky after use.The user dilutes this releasing agent with economic kerosene or solvent, and sprays the releasing agent of this dilution.Yet,, worsened working environment and be deposited on the mould so during casting, be dispersed in the powder of the neighboring area of mould because old oil-based release agent contains powder.Therefore, frequent cleaning is indispensable.Old oil-based release agent and kerosene mix, and the flash point of kerosene is lower.This danger close can cause fire, therefore makes die casting be difficult to realize automation.For this reason, old oil-based release agent manually is coated with, and this causes production efficiency low.And, because the refining degree of kerosene is low and contain trace components such as sulphur etc.,, and give out the smell of strong oil so this releasing agent can cause detrimental effects to human body inevitably.That is to say, old oil-based release agent have fire and blast danger, be not suitable for automation, can pollute working environment, and require regular cleaning inevitably with oil and powder.
Because above-mentioned situation, old oil-based release agent has become the little water-soluble mold-release agent of fire hazard, so that automation.Say without exaggeration that now, 99% releasing agent is a water-soluble mold-release agent on the market.On the other hand, the very small amount of oil-based release agent (being called high viscosity oiliness releasing agent below for short) that does not contain solid matter is still continuing use.Such oil-based release agent has superior lubricating property.Yet its viscosity is very high, and (dynamic viscosity under 40 ℃ is 100mm
2And even if such oil-based release agent is injected, the diameter of the mist that is produced is also bigger/s or higher).Therefore, these releasing agents are not suitable for spraying automatically and therefore consumption is big, and the oil ingredient of these releasing agents is entrained in the motlten metal stream and is gasified, thereby remains in the cast article with gas form, thereby causes porosity to increase.Therefore, utilize the superior lubricating property of old oil-based release agent, now, old oil-based release agent only was used to heating operation (warm-up operation) before the coating water-soluble mold-release agent.
On the other hand, there is not the water-soluble mold-release agent of fire hazard that conclusive shortcoming is arranged on its ability.Owing to dilute this releasing agent with about 80 times water in use, 99% of key component is a water, and therefore, this releasing agent causes Leiden Dan Frost (Leidenfrost) phenomenon on mould under about 150 ℃.That is to say that the releasing agent mist is sharply evaporated (explosivelyevaporated) down at about 150 ℃, and die surface is covered by steam blanket.The releasing agent mist of therefore, then coming can not arrive die surface.This causes the adhesive capacity of active principle reduction in the releasing agent on die surface.In order to improve adhesive capacity, by spraying a large amount of water-soluble mold-release agents, mold temperature is remained on below the Dan Frost temperature of Leiden, sacrificed adhesive efficiency simultaneously.In fact, at present, the tonnage of the die locking force of emitted dose and casting machine roughly the same (for example, being about 350cc for 350 tons machines, is about 2500cc for 2500 tons machines).Nature, the neighboring area of machine is dirty, and waste liquid is a lot, thus manpower that need be a lot of and expense clean and dispose waste liquid.And, because that nearly all water-soluble mold-release agent all contains is cured, the cured neighboring area that adheres on the die surface and deposit to machine of therefore solidifying.This needs frequent cleaning.Must consider be not only because of the releasing agent component separate out and adhere to the pollution that causes in the machine neighboring area, to consider also that simultaneously the oxidation of component is degenerated.Patent documentation 1 (the open 8-103913 of Japanese patent application KOKAI) has been described the oil ingredient that suppresses in the water-soluble mold-release agent with antioxidant and has been degenerated.The target of this invention is to prevent that mould is contaminated in rubber vulcanization process.And this invention also discloses the countermeasure that is used for obviously reducing the stain on the mould.
And when injection each time, this mould is heated to about 200 to 350 ℃ by molten aluminium metal, after this is cooled to about 100 to 150 ℃ by water-soluble mold-release agent.In injection each time, from 100 to 200 ℃ of fluctuations of the temperature of die surface.Therefore, in long-time continuous casting back (being several thousand times for large mold, is several ten thousand times for small mould), heat fatigue is accumulated at die surface, and so-called crackle is formed, last, expensive mould breakage.Here it is present case.
And, because water-soluble mold-release agent has strong cooling capacity, be cooled at short notice so inject the molten aluminum of die cavity.The viscosity of motlten metal is enhanced so that has upset molten metal flow.Finally, motlten metal can not arrive each tiny corner of die cavity.As a result, so-called " misrun " and " contraction " phenomenon taking place, and makes and can not make complete cast article.And, because the adhesive efficiency of water-soluble mold-release agent is lower, so the oil film on the metal surface is thinner.At the high-temperature portion place of mould, particularly resembling the so thin portion place of core bar (core pin), sticking type (soldering) may often take place.
The porosity that reduces cast article intensity also is a problem.The cause of porosity is to be entrained to organic matter and water in the turbulent flow of motlten metal and to gasify in cast article.If spray excessive releasing agent, then porosity increases.In the past, in order to reduce porosity, patent documentation 2 (the open 2000-33457 of Japanese patent application KOKAI) discloses a kind of powder-type releasing agent, and it has superior demoulding ability.
In above-described current situation, need to improve the disadvantageous low adhesive efficiency of water-soluble mold-release agent, the injection character of improving high viscosity oiliness releasing agent keeps superior lubricating property simultaneously, and makes it possible to realize " very a spot of injection " " long die life (lie) " and " less waste liquid ".
Summary of the invention
The present invention aims to provide the oil-based release agent that need not water distribution.Described oil-based release agent can be realized long die life, less waste liquid, at high temperature superior demoulding lubricating property and emitted dose seldom.By setting the proper viscosity under 40 ℃, can realize emitted dose seldom, make less steam be dispersed in the air.
And, the present invention aims to provide a kind of establishing method of solvent mixing ratio, under this solvent mixing ratio, can avoid Leidenfrost's phenomenon, this method is that the blending ratio of setting two kinds of solvents or solvent and mineral oil and/or artificial oil when stating the oil-based release agent that is used for die casting in the use and carry out die casting carries out.
And, the present invention aims to provide the oil-based release agent that is used for die casting, casting method, and injection unit, by described oil-based release agent, casting method and injection unit, compare with conventional method, emitted dose can access saving, and, as burr, streamline (flow line), metal wave (metal wave), and the problem of porosity and so on can both be resolved.
1) to achieve these goals, oil-based release agent of the present invention (first invention) contains: (a) solvent of 70 to 98 weight portions, the dynamic viscosity of described solvent under 40 ℃ are 2 to 10mm
2/ s, the flash point of described solvent is in 70 to 170 ℃ scope; (b) high viscosity mineral oil of 1 to 10 weight portion and/or artificial oil, described mineral oil and/or the artificial oil dynamic viscosity under 40 ℃ is 100mm
2/ s or higher; (c) 15 weight portions or silicone oil still less, the dynamic viscosity of described silicone oil under 40 ℃ is 150mm
2/ s or higher; And (d) additive of 1 to 5 weight portion with lubricating ability, wherein, the flash point of described releasing agent is in 70 to 170 ℃ scope, and the dynamic viscosity of described releasing agent under 40 ℃ is 2 to 30mm
2/ s.
According to first invention, described oil-based release agent is not moisture, thereby avoids the inhibition to lubricating property, and, thereby described oil-based release agent is because oil ingredient provides lubricated.On the demoulding lubricating property this point at high temperature, described oil-based release agent is superior especially.And, since not moisture, so mould can not cooled off by releasing agent.Therefore, obtained prolongation die life, the aerial distribution of releasing agent is lowered, and die casting is carried out under the situation of waste liquid not having.Particularly, described releasing agent is suitable for automatic continuous injection, and superior on the coating of a small amount of stoste (neat liquid) and wetability.And according to first invention, described oil-based release agent can be realized the emitted dose littler than traditional releasing agent, and can reduce the die casting problem as burr (galling), streamline, metal wave and porosity etc.
2) the present invention (second invention) provides a kind of method of setting the blending ratio of solvent in the oil-based release agent, to avoid Leidenfrost's phenomenon in die casting.Two or more solvents can be used as to mix uses solvent.Described method is made of the first, second, third and the 4th step.Described first step is the highest serviceability temperature (S) of substitution expection in following equation (1) and (2), so that calculate the required flash point (F) of the releasing agent that will prepare.Described second step is to measure the flash point of three kinds or more kinds of different releasing agents, and described three kinds or more kinds of different releasing agent have the coordinative solvent of variable concentrations.Described third step is to map about the correlation between the flash point of the weight percent values of solvent in each releasing agent and each releasing agent.Described the 4th step be by described figure and by calculate in the described first step the required flash point releasing agent estimating to prepare in the weight percent values of solvent.
S+80＝L (1)
I＝4.4×F+36 (2)
Wherein, S represents the maximum temperature that releasing agent uses; L represents the temperature of Leidenfrost's phenomenon; And F represents the flash point of releasing agent.
According to second invention, when using described oil-based release agent die casting, can avoid Leidenfrost's phenomenon.
3) the present invention (the 3rd invention) provides the method for the blending ratio of a kind of setting solvent and mineral oil and/or artificial oil.This purpose is using oil-based release agent as claimed in claim 1 to carry out avoiding Leidenfrost's phenomenon in the die casting.Said method comprising the steps of: the highest serviceability temperature (S) of substitution expection in superincumbent equation (1) and (2), so that calculate the flash point (F) of releasing agent; Prepare three kinds or more kinds of different releasing agent, described three kinds or how different releasing agent have coordinative solvent, mineral oil and/or the artificial oil of variable concentrations; Study the flash point of the various releasing agents that prepare; Make the figure of correlation of the flash point of the percentage by weight of solvent in the various releasing agents and various releasing agents; And by described figure and by equation (1) and (2) calculate flash point calculate the percentage by weight of solvent in the releasing agent.
The 3rd invention has same effect with second invention.
4) the present invention's (the 4th invention) casting method relates to by using above-mentioned 1) oil-based release agent and utilize the die casting of releasing agent coating machine.According to the 4th invention, provide the casting method that to use first oil-based release agent of inventing to carry out die casting.
5) the present invention's (the 5th invention) injection unit is to be used for to mold ejector and coating as above-mentioned 1) spraying system of described oil-based release agent.Described system comprises: have the releasing agent injection unit of a plurality of nozzles, injection unit is to be coated with oil-based release agent to die surface; And the supercharging feed unit, described supercharging feed unit is coated with a small amount of releasing agent to described injection unit supply releasing agent and to mould under the low pressure condition.According to the 5th invention, can spray the oil-based release agent described in first invention.
6) the present invention (the 6th invention) provides a kind of casting method, described casting method to be used for using as above-mentioned 4) described injection unit and as described in oil-based release agent carry out die casting.
Description of drawings
Figure 1A is the front view of the flexible mould that adopts in the example of the present invention.
Figure 1B is the front view of the fixed mould that adopts in the example of the present invention.
Fig. 2 is the figure that schematically illustrates of spraying system of the present invention.
Fig. 3 be spraying system drawn among Fig. 2 one of them part, be the key diagram of injection unit.
Fig. 4 be spraying system drawn among Fig. 2 one of them part, be the key diagram of supercharging feed unit.
Fig. 5 is the figure that schematically illustrates of adherence test machine, and this adherence test machine is used to measure the adhesive capacity of releasing agent of the present invention.
Fig. 6 A is a key diagram, its be shown as measurement on sample frictional force and make the state of releasing agent from nozzle ejection.
Fig. 6 B is a key diagram, and it shows that ring is placed in state on the testing machine main body by test-bed.
Fig. 6 C is a key diagram, and it shows the measured state of frictional force.
Fig. 7 is a performance plot, and it shows the flash point of various releasing agents and the correlation of Leiden Dan Frost temperature and maximum operation (service) temperature.
Fig. 8 is the key diagram that is used to measure the device of Leiden Dan Frost temperature.
Fig. 9 is the performance plot that shows the correlation between solvent strength and the flash point.
The specific embodiment
To describe the present invention in detail below.
(1) the present invention's (first invention) the oil-based release agent that is used for die casting contains: (a) solvent of 70 to 98 weight portions, the dynamic viscosity of described solvent under 40 ℃ are 2 to 10mm
2/ s, the flash point of described solvent is in 70 to 170 ℃ scope; (b) mineral oil of 1 to 10 weight portion and/or artificial oil, described mineral oil and/or the artificial oil dynamic viscosity under 40 ℃ is 100mm
2/ s or higher; (c) 15 weight portions or silicone oil still less, the dynamic viscosity of described silicone oil under 40 ℃ is 150mm
2/ s or higher; And (d) additive of 1 to 5 weight portion with lubricating function, wherein, the flash point of described releasing agent is in 70 to 170 ℃ scope, and the dynamic viscosity of described releasing agent under 40 ℃ is 2 to 30mm
2/ s.
(2) component (a) in above-mentioned (1) is high volatile volatile and low viscous component, and will be evaporated at die surface.Thus, consider the influence to human body, any solvent with strong polarity should not use as alcohol, ester and ketone, and the oil series solvent and the low viscosity crude oil (base oil) that mainly contain saturated component are preferred.Their example has and after the height refining sulphur component is suppressed to 1ppm or lower saturated solvent and low viscosity artificial oil.In above-mentioned (a), be defined in dynamic viscosity under 40 ℃ and be 2 to 10mm
2/ s.Low excessively when the viscosity of solvent, as being 2mm
2/ s or lower the time, it is low that the viscosity of whole releasing agent also became.On the other hand, sticking excessively when the viscosity of solvent, as being 10mm
2/ s or when higher, it is sticking that the viscosity of whole releasing agent also became.And the ratio of above-mentioned (a) is adjusted to 70 to 97 weight portions, so that optimize the volatility of whole releasing agent.
(3) owing to following reason, the flash point of the component of above-mentioned (1) (a) is adjusted in 70 ℃ to 170 ℃ scope.That is, in order to form thick oil film on die surface, just as the situation of quick-dry type coating, preferably the rapid evaporation solvent drips from die surface with the component of avoiding just having adhered to.Therefore, it is desirable having high evaporation speed.Yet, if evaporation rate is too fast, Leidenfrost's phenomenon may take place, seen during just as the usefulness water-soluble mold-release agent.Therefore, it is not preferred resembling those solvents that have high evaporation speed the gasoline.And if evaporation fast, then the flash point step-down causes the fire risk height.Therefore, flash point is adjusted to and is higher than 43 ℃, and 43 ℃ is the flash point that contains the old oil-based release agent of kerosene.And from practical point of view, preferred flash point is higher than the flash point (70 ℃) of motor vehicle diesel.Therefore, the flash point of composition of the present invention is restricted to 70 ℃ or higher.
On the other hand, under the situation of die material, higher flash point is preferred, so that suppress the evaporation properties of releasing agent.Yet it is higher that the viscosity of releasing agent also becomes.If viscosity height, then the spray regime variation of releasing agent.Viscosity should have the upper limit.The upper limit of viscosity is corresponding to 170 ℃ flash point, and therefore, flash point is confirmed as 170 ℃ or lower.
About (a) component of above-mentioned (1), low viscosity mineral oil and/or artificial oil can be added in the above-mentioned solvent, quantity of solvent is adjusted to 70 to 98 weight portions altogether.In (a) component only is under the situation of solvent, can use two or more solvents.Under the situation of not regulating, can only use a kind of solvent based on Leidenfrost's phenomenon.
(4) component of above-mentioned (1) (b) is that high viscosity mineral oil and/or artificial oil are adhered on the die surface.Make lubricating film thicker thereby adhere to component in about 150 ℃ to 300 ℃ temperature range, and thereby play the effect that keeps lubricated.These components are required to have suitable viscosity under mold temperature, are dripping from die surface corresponding to adhere to oil in several seconds that are ejected into this time that motlten metal is injected into preventing.Yet, the mold temperature difference in each mould machine.Even if it is in uniform machinery, also different in the temperature at a plurality of positions of mould.Therefore, the unitary mould temperature is assumed that 150 ℃ or higher, and high viscosity mineral oil and/or the artificial oil dynamic viscosity under 40 ℃ is adjusted to 100mm
2/ s or higher.
And, if (b) combined amount of component is low, the then lubricating film attenuation on the die surface.If combined amount is too high, then problem may take place.One of them is that it is unstable that spray regime becomes.Another problem is that thick lubricating film may cause cast article appearance change (so-called residual look (remaining color)) partly.In order to address these problems, the addition of component (b) is confirmed as 1 to 10 weight portion.The oil that is exemplified as that is used as component (b) is mineral oil, artificial oil and cylinder oil.
(5) component of above-mentioned (1) (c) is that silicone oil is used to strengthen lubricating property at high temperature.This component is confirmed as 15 weight portions or silicone oil still less, and the dynamic viscosity of described silicone oil under 40 ℃ is 150mm
2/ s or higher.This component also is by adhering on the die surface, in order to remain on the lubricating property under about 250 ℃ to 400 ℃ high temperature.Because it is used for keeping lubricating property in than the higher temperature range of the high viscosity mineral oil of component (b) by expection, so the dynamic viscosity under 40 ℃ preferably is higher than the dynamic viscosity of component (b) under 40 ℃, is 150mm
2/ s or higher.
" silicone oil " about the component (c) of above-mentioned (1) does not have under the coated situation at cast article, and any commercial silicone oil all can be used, and comprises and can use dimethyl siloxane.Yet under situation about applying, becoming sometimes is difficult to form the coating with excellent adhesion.Therefore, dimethyl siloxane is unfavorable in some cases, and acceptability that let it be to the greatest extent depends on the coated weight to die-cast product.In this case, preferably select to have than the longer alkyl-aralkyl of dimethyl functional group (dimethylfunction) or the alkyl-silicone oil of chain alkyl.
The amount of the component of above-mentioned (1) (c) is confirmed as " 15 weight portions or still less ".Its reason is, surpasses 15 weight portions as the amount of fruit component (c), and then silicon itself or silicon catabolite are deposited on the die surface, thereby cause the harmful effect to the cast article shape.Be low to moderate under the situation about being used under the middle temperature (being lower than 250 ℃) at mould, needn't allocating silicone oil into, be added into as component (d) because have the additive of lubricating property.If use silicone oil down at high temperature (250 ℃ or higher), then should allocate the silicone oil that is difficult to be decomposed into.Yet from becoming original consideration, the addition of preferred silicone oil is low.Have lubricating property additive, be that component (d) can comprise for example organic-molybdenum.
(6) have the additive of lubricating property, the i.e. component of above-mentioned (1) (d) reinforcement lubricating property under the temperature in being low to moderate.Described additive for example can comprise: animal and plant fat is as rapeseed oil, soya-bean oil, coconut oil, palm oil, tallow oil and lard; Monohydric alcohol or polyalcohol and the ester such as fatty acid ester, coco-nut oil fatty acid, oleic acid, stearic acid, laurate, palmitic acid and the tallow fatty acids that form than high fatty acid; Organic-molybdenum; Oil soluble soap and gatch.Organic-molybdenum is preferably for example MoDDC and MoDTC, and still, MoDDP and MoDTP are not preferred, because they may cause the reaction of aluminium and phosphorus component.The example of oil soluble soap can comprise sulfonated salts, phosphonate (phinatesalt) and the salicylate of Ca or Mg.Metal salts of organic acids can be used as example, but its dissolubility and unsatisfactory.
(7), have the above-mentioned solvent of described viscosity and flash point and the combination of mineral oil and/or artificial oil and can have four kinds: independent solvent for the present invention; Solvent with the mineral oil combination; Solvent with the artificial oil combination; And with the solvent of mineral oil and artificial oil combination.Described solvent is not limited in a kind of, and two or more solvents can compound mode be used.But, from the viewpoint of workers ' health, preferred oil series solvent.Above-mentioned mineral oil can comprise machinery oil, steam turbine oil, bobbin oil and cylinder oil.Synthetic ester also can be used.
(8) in the present invention, requiring the flash point of releasing agent is 70 to 170 ℃.Here, 70 ℃ lower limit is in order to reduce the risk of fire.This value is higher than the flash point (about 40 ℃) that is used in the kerosene in the old type releasing agent.Therefore, this makes it possible to oil-based release agent is applied to automatic extrusion process.Owing to following reason, the higher limit of flash point is confirmed as 170 ℃.That is, if high viscosity (being high flash point) mineral oil or artificial oil are used, the oil film that then adheres to mould can not parch, and this causes it to drip from die surface.The position of oil owing to drip, the adhesive efficiency variation on the die surface, and surrounding environment variation.Therefore, for fear of this problem, flash point should be 170 ℃ or lower.
(9) dynamic viscosity of releasing agent under 40 ℃ is necessary for 2 to 30mm
2/ s.Its reason is as follows.If dynamic viscosity is lower than 2mm
2/ s, the pump wearing and tearing when then being coated with releasing agent increase.If dynamic viscosity surpasses 30mm
2/ s, thus the pump of releasing agent is inhaled the difficulty that becomes and is caused instability when then being coated with releasing agent.If it is unstable that control becomes, then be coated with 20cc or still less become difficulty.The emitted dose fluctuation of releasing agent when the difficulty if control becomes, then each injection, but thereby can not keep stable castability.For more stable emitted dose and more tiny mist form, dynamic viscosity more preferably 2 to 20mm
2In the scope of/s.
The oil-based release agent of (10) first inventions is compared with traditional water-soluble mold-release agent and is had the following advantages:
1) this oil-based release agent does not cause the reaction of quenching;
2) this oil-based release agent has high hear resistance and anti-stick type (anti-soldering) property;
3) this oil-based release agent prolongs die life and helps not have liquid waste processing;
4) regulate by the flash point of from 70 to 170 ℃ of levels, adhesive efficiency can be maintained at suitable oil film thickness.Therefore, high temperature lubricating character can be guaranteed;
5) by the dynamic viscosity under 40 ℃ is set in 2 to 30mm
2In the proper range of/s, it can be optimized spray characteristic and the aerial distribution of releasing agent is minimized;
6) even if emitted dose is little and oil film thin, it also passes through to form uniform oil film on die surface, thereby has reduced the die casting problem, as burr and sticking type; And
7) because thin oil film, it has also reduced the bubble problem when die-cast product heat-treated technology.
(11) in first invention, based on the stoste meter, during injection each time the releasing agent emitted dose of mould is desirably 20cc or still less, 1cc or still less more preferably, more preferably 0.5cc or still less.Its reason is, because if emitted dose surpasses 20cc, then becoming is difficult to not have the casting that waste liquid produces, and, the degree height of the gas flow of in cast article, carrying secretly, thus porosity highly caused.As described, because emitted dose is 20cc or still less, cast so can realize not having waste liquid.And by the same token, the gas in the cast article is carried secretly and is reduced.And, owing to both do not use powder also not use wax, pile up so can prevent too much adhesion and solid on the die casting machine.
(12) reason of the above-mentioned sticking type of supposition is followed oil film thin excessively between cast article and the die surface and is existed.Particularly, sticking type frequently occurs in the jut just as core bar.Generally speaking, it is said that core bar is positioned at the position that the injection mist is less and the oil film there becomes thinner than other positions.In addition, if use oil-based release agent to begin continuous casting, then mould heating gradually is not because releasing agent is attended by the external refrigeration function.The adhesive capacity of releasing agent on die surface raises along with temperature and reduces, and oil film heat is degenerated, thereby it is thinner that oil film becomes.In order to address this is that, following method is arranged, wherein, the additive that improves wetability is added into to improve adhesive capacity, so that strengthen oil film, perhaps, antioxidant is added into the heat that postpones oil film degenerates.
Therefore, in first invention, except each component (a) of above-mentioned (1) to (d), preferred additive or the antioxidant that improves wetability that add.As the additive that improves wetability, for example, the flash point of 0.1 to 3 weight portion is that 100 ℃ or lower acrylic acid series copolymer or the polysiloxanes of acryloyl group modification can be added into.In above-mentioned scope about interpolation, be to be used for wetability to improve reagent although improve the additive of wetability, it also has adhesiving effect., be added into if improve the additive of wetability, then releasing agent is improved to the wetability of metal surface herein, causes the adhesive capacity on the metal surface to increase.Particularly, if the metal surface is awfully hot, described phenomenon (Leidenfrost's phenomenon) takes place then.For this reason, the light weight component is seethed with excitement suddenly in the releasing agent, and mist of oil drips and is prevented from wetting metal surface.Thereby, suppressed the film on the metal surface and formed.Owing to wetability is enhanced because of the additive that improves wetability, so this phenomenon is suppressed and makes oil film thicker.
(13) also preferably add antioxidant, promptly add one or more antioxidants of 0.2 to 2 weight portion altogether, these antioxidants are selected from the group that is made of amine, phenol, cresols class antioxidant.This component is added into to prevent or oxidation when postponing high-temperature operation is degenerated, and keeps oil film thickness, guarantees lubricating function, and suppresses the generation of sticking type.
The example of above-mentioned amine antioxidants is an alkyl diphenyl base amine, as a nonyl diphenylamine; Dialkyl group diphenyl amine, as 4,4 '-dibutyl phenyl amine, 4,4 '-diamyl diphenylamine, 4,4 '-dihexyl diphenylamine, 4,4 '-diheptyl diphenylamine, 4,4 '-dioctyl diphenylamine and 4,4 '-dinonyl diphenylamine; Poly-alkyl diphenyl base amine is as tetrabutyl diphenylamine, four hexyl diphenylamines, four octyldiphenylamines and four nonyl diphenylamines; Alpha-naphthylamine, PA, fourth PA, penta PA, hexyl PA, heptyl PA and octyl phenyl-alpha-naphthylamine.
The example of above-mentioned phenyl class antioxidant is 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethyl-phenol, 4,4-di-2-ethylhexylphosphine oxide (2, the 6-tert-butyl phenol), 2,2-di-2-ethylhexylphosphine oxide (4-ethyl-6-butylphenol), HMW monocycle phenol, encircle tert-butyl phenol, BHT (butylated hydroxy-methylbenzene), BHA (butylated hydroxyanisol) more.The example of cresols class antioxidant is di-t-butyl-paracresol and 2,6-di-t-butyl-dimethylamino-paracresol.In above-mentioned antioxidant, the mixture of preferred BHT and alkyl diphenyl base amine.
In the present invention, can suitably add antirust agent, surfactant, anticorrisive agent, antifoamer and other additives (as extreme pressure additive, viscosity index (VI) improving agent, detergent dispersant, coloring agent and aromatic).
(14) in the present invention, about containing the above-mentioned oil-based release agent of various components (a) to (d), 1 to 3 kind of optional components in these components is pre-mixed with after obtaining mixture, and remaining then component can be mixed with this mixture to obtain releasing agent.Specifically, composition (b), (c) and (d) be pre-mixed to obtain mixture 1, then, the user can mix component (a) with the formation releasing agent with mixture 1.Also can be, component (a) and (b) mixed to obtain mixture 2, after a while, the user can mix component (c) and mixture (d) 3 to obtain releasing agent with mixture 2.
And, comprising each component (a) and (b), (c) and (d) and in these five kinds of components of the additive of other raising wetability or antioxidant (being defined as component [e]), 1 to 4 kind of optional components is pre-mixed to obtain mixture.Then, remaining ingredient can mix with this mixture in advance to obtain releasing agent.
(15) low viscosity oiliness releasing agent has many advantages.Yet it also has the shortcoming of bringing because of the small injection of anhydrous type releasing agent.Die surface is not by external refrigeration.Mold temperature is a slight fluctuations in the one-period of die casting.Then, this stable state keeps at high temperature.Here, if temperature is about 350 ℃ or lower, then do not have problems fully, but the advantage former state of low viscosity oiliness releasing agent is utilized.Yet, if temperature is higher than said temperature, sticking type taking place sometimes between cast article and mould, and becomes and be difficult to cast continuously.Another bad place is, if oil-based release agent is used to main with in the existing casting machine of operating to the external refrigeration form of a large amount of water-soluble mold-release agent of mold ejector, then need to transform mold system sometimes, to strengthen the inside cooling of oil-based release agent.And for the reason relevant with mould structure or shape of product, inner cooling is impossible sometimes.Therefore, need exploitation to provide high temperature lubricating character and can handle Leiden Dan Frost problem and need not to transform the oil-based release agent of machine.
The establishing method of the present invention's (second invention) solvent mixing ratio is based on that above-mentioned background carries out.Just, second invention is for being used to set the method for above-mentioned solvent mixing ratio, and it is used for avoiding Leidenfrost's phenomenon when using the oil-based release agent die casting of first invention.Two or more solvents are used to above-mentioned solvent.The present invention relates to the first, second, third and the 4th step.First step is the highest serviceability temperature (S) of substitution expection in following equation (1) and (2), so that calculate the flash point (F) of releasing agent.Second step is the flash point of research three kinds or how different releasing agents, and described three kinds or how different releasing agent have all kinds of solvents of variable concentrations.Third step is the figure that makes the correlation of the weight percent values of solvent in the various releasing agents.The 4th step be by described figure and by equation (1) and (2) calculate flash point calculate the weight percent values of solvent in the releasing agent that will prepare.
S+80＝L (1)
L＝4.4×F+36 (2)
Wherein, S represents the maximum temperature that releasing agent uses; L represents the Leidenfrost's phenomenon temperature; And F represents the flash point of releasing agent.
The establishing method of solvent mixing ratio of the 3rd invention is the method that is used to set the blending ratio of above-mentioned solvent and above-mentioned mineral oil and/or artificial oil, it be used for use first invent oil-based release agent die casting the time avoid Leidenfrost's phenomenon.The present invention relates to the first, second, third and the 4th step.First step is a substitution expection maximum operation (service) temperature (S) in above-mentioned equation (1) and (2), so that calculate the flash point (F) of releasing agent.Second step is the flash point of research three kinds or how different releasing agents, and described three kinds or how different releasing agent have all kinds of solvents, mineral oil and/or the artificial oil of variable concentrations.Third step is the figure that makes the correlation of the weight percent values of solvent in the various releasing agents.The 4th step be by described figure and by equation (1) and (2) calculate flash point calculate the weight percent values of solvent in the releasing agent.
(16) then, the Leidenfrost's phenomenon of above-mentioned (15) is described below.
When oil-based release agent contacted with mold heat in season, the hydrocarbon components of light weight was seethed with excitement suddenly in the releasing agent.These hydrocarbon components produce ascending air, and other parts of hydrocarbon components are present in the air as oil droplet.Because ascending air, oil droplet floats from die surface, thereby makes the variation that contacts of oil droplet and die surface.As a result, heat is not passed to oil droplet, thereby makes evaporation rate slow down.Because the active component in the oil droplet is suppressed and sticks on the mould, thus adhesive capacity be lowered, to cause the release property variation.This phenomenon is known as Leidenfrost's phenomenon, and this phenomenon is known under the situation of water-soluble mold-release agent.Under the situation of water-soluble mold-release agent, this phenomenon takes place down at about 150 to 200 ℃, and under the situation of the oil-based release agent of being invented, the just generation under 350 ℃ or higher temperature of this phenomenon.This is based on discovering of carrying out for the present invention.
The inventor has studied the temperature that Leidenfrost's phenomenon takes place on experimental size.In addition, the inventor has studied the maximum operation (service) temperature in the actual die casting machine and the flash point of releasing agent.The result shows in Fig. 7.As shown in Figure 7, when flash point rises, but the Leidenfrost's phenomenon temperature rises and the highest serviceability temperature uprises in actual machine.In this case, the temperature that takes place of Leidenfrost's phenomenon is defined as evaporation rate and becomes the slowest point.But find that when temperature was also lower, evaporation rate was delayed before this point.We can say that just under low about 80 ℃ temperature than Leidenfrost's phenomenon temperature, releasing agent reaches the limit of its actual use.By Fig. 7, can show following correlation:
S+80＝L
L＝4.4×F+36
Wherein, S represent the maximum temperature that oil-based release agent uses (℃); L represent the Leidenfrost's phenomenon temperature (℃); And F represent flash point (℃).
According to being seen by the performance of Fig. 7, if the Leidenfrost's phenomenon of releasing agent point is enhanced, then the highest actual serviceability temperature can be enhanced.There are two kinds of methods to improve the highest actual serviceability temperature herein.Preceding a kind of method is to improve the flash point of releasing agent to confirm practical application by the use actual machine.A kind of method in back is to improve the Leidenfrost's phenomenon temperature by improving flash point.Yet actual applicability needs large-scale experiment and adopts actual machine to confirm.Because it is easier to measure the Leidenfrost's phenomenon method of temperature under laboratory scale, so a kind of method in back is used.Yet if flash point is enhanced and emitted dose is enhanced too much, the smog when spraying thickens, and therefore, need experimentize carefully.
The measuring method of Leidenfrost's phenomenon temperature then, is described with reference to Fig. 8.For this measurement, adopt as Transactions (B volume) of The Japan Society of MechanicalEngineers the device of " Study on Evaporation of Oil-in-Watertype Emulsion Droplets on Heated Face " described Fig. 1 of TakeoTAKASHIMA, Hiroshi SHIOTA among the No 03-1248 of the 70th volume No. 700 (2004-12).
At first, the dish 51 that is made of copper is placed on the heater 52.This dish has columniform saucer-like configuration, and its diameter is 60mm, and the radius of curvature R in the high 30mm, upper surface is 200, and the degree of depth at the center is 4mm.Be coated with insulator 53 on the dish 51, and transformer 54 is connected to heater 52.Thermocouple 55 is embedded in the degree of depth of 2mm under dish 51 centers, and is connected with temperature recorder 56.And video camera 57 is mounted for photographs to fluidized state.Simultaneously, releasing agent is placed in the syringe 58, and syringe 58 is made and be equipped with tubule by polyethylene.The tip of tubule is set at 40mm eminence above the dish center.In this case, the diameter of drop 59 is about 2.7mm.When the temperature of dish 51 reached set point of temperature, a dropping liquid that is in room temperature dripped 59 and drips.And, then, measure evaporation time by stopwatch.And, by the state of video camera 57 observation drops.Carry out above-mentioned observation every 10 ℃, and make the figure of correlation between temperature and the evaporation time.The longest temperature of evaporation time is defined as the Leidenfrost's phenomenon temperature.
(17) above-mentioned releasing agent will be described in more detail.This oil-based release agent is not moisture, powder or emulsifying agent.Should be understood that then mould is cooled still less if do not contain water, and heat fatigue is minimized, therefore, be significantly improved die life.For example, according to little die-cast product, whenever under the situation of water-soluble mold-release agent need carry out the R and M of mould through 20000 injections by using actual die casting machine to obtain.Yet, under the situation of oil-based release agent, even if after 320000 injections, also do not need to repair mould.Thereby proved that the life-span is 16 times so long at least.Under the situation of 350 tons of small-sized machines, economic effect is equivalent to and has reduced millions of yen cost.And, owing to do not have water and can realize a spot of blowing, so do not have waste liquid to be discharged from and the expense of liquid waste processing is also saved significantly.And, because considerably less emitted dose, so cigarette or smog extremely reduce and working environment is significantly improved.
And because oil-based release agent of the present invention does not contain emulsifying agent, and for all water-soluble mold-release agents, emulsifying agent uses all essentially.This oil-based release agent is favourable aspect liquid waste processing.This oil-based release agent also is suitable for avoiding the problem of endocrine disruptor (endocrine disrupting substance).And, because releasing agent of the present invention do not contain powder, thus this releasing agent also help suppressing to device pollution, prevent that releasing agent from taking place because of precipitation that quality changes during storage and maintenance surface smoothness and powder do not cause damage to the cast article surface.
(18) the present invention's (the 4th invention) casting method is used for by using the described die casting that is used for the oil-based release agent and the releasing agent injection unit of die casting of first invention.According to the present invention, can realize die casting by using described oil-based release agent.Figure 1A shows the front view of the flexible mould that uses among the present invention, and Figure 1B shows the front view of the fixed mould part of the mould that uses among the present invention.Above-mentioned mould is made up of flexible mould 1 and fixed mould 2, and flexible mould 1 is provided with top shoe (slide) 3, sliding block 4 and slide core 5.Reference numeral 6 expression pilot pins among the figure; Reference numeral 7 presentation surface pins (surface pin); The stripper pin of Reference numeral 8 expression running channels (runner); And Reference numeral 9 expression fixed core.
(19) the present invention's (the 5th invention) spraying system is the device for mould coating oil-based release agent.This system comprises: injection unit, and it is provided with a plurality of blast tubes so that to the mold ejector releasing agent; With the supercharging feed unit, it is used for releasing agent is delivered in the injection unit that under low pressure uses, so that be coated with a spot of releasing agent to mould.As shown in Figure 2, this spraying system is provided with injection unit 22, and injection unit 22 has a plurality of nozzles 21.Being used for that air is introduced oil-based release agent that wherein air introduces the pipe 23 of usefulness and will be used for die casting introduces wherein releasing agent and introduces the pipe 24 of usefulness and link to each other with injection unit 22.The jar 25 that is used to store oil-based release agent is connected to pipe 24 so that introduce releasing agents by pressure-reducing valve 26 and pump 27, and wherein, pressure-reducing valve 26 is used for the force feed releasing agent, and pump 27 is used for pump and inhales releasing agent.The supercharging feed unit comprises jar 25, is used for the pressure-reducing valve 26 of releasing agent, is used for the pump 27 of pump suction releasing agent and not shown releasing agent force feed flexible pipe herein.Reference numeral 29 among the figure shows the mould with die cavity portion 28.
(20) at the spraying system that is used for water-soluble mold-release agent that above-mentioned oil-based release agent has been existed, promptly have under the situation that the haplotype spraying system of big flow nozzle adopted the problem that existence is mentioned below:
1) because the ratio of viscosities water-soluble mold-release agent height of oil-based release agent, so the emitted dose of each nozzle does not have balance well; And
2) the fine adjusting difficulty of emitted dose.
Therefore, if use under the spraying system that is used for water-soluble mold-release agent and this system situation that process is not transformed that has existed, automatically the coating oil-based release agent then can frequently cause staying as burr, streamline, metal wave and a lot of gas the problem of (porosity) and so in the product to carry out die casting.In order to handle these problems, need equably to mould coating releasing agent.
In injection unit of the present invention, injection unit comprises the injection unit main body, is used for the pipe of air introducing and is used for the pipe that releasing agent is introduced.Each all links to each other with the injection unit main body respectively as one group of pipe in air hose and the releasing agent pipe.Because the pipe of one-to-many group is arranged in or multiple spot place face-to-face at 2, thereby the releasing agent from nozzle can be ejected on the mould equably.
Describe below 2 or more the multiple spot place arrange the reason that pipe respect to one another is right, this reason is as follows.
(21) injection unit that is used for water-soluble mold-release agent has a large amount of nozzles, and these nozzles have releasing agent coating nozzle.Traditionally, have only one group supply opening (being used for the pipe that releasing agent is introduced) and air supply opening (being used for the pipe that air is introduced).Just adopting this injection unit to be coated with under the situation of oil-based release agent without any improving, because the position is near this group oil-based release agent supply opening and air supply opening, so be coated with releasing agent more than needs from nozzle.This is because a small amount of oil-based release agent is used and the viscosity height of the ratio of viscosities water-soluble mold-release agent of oil-based release agent.On the other hand, lack than needs from the emitted dose that is positioned at away from the nozzle at the position of inlet tube, thereby can not be coated with oil-based release agent equably to mould.Therefore, a pair of releasing agent that is used for is introduced and is used for pipe group that air introduces and is arranged in or multiple spot place face-to-face at 2, so that pressure is applied equably by each nozzle, and oil-based release agent and air are fed to nozzle equably.Therefore, can be coated with a spot of oil-based release agent equably for die surface.
In spraying system of the present invention, the supercharging feed unit can comprise: the jar that is used to store oil-based release agent; With the supply flexible pipe that is used to be connected described jar.Between lower position when upper limit position the when apical side height of releasing agent face is set at nozzle and is in standby in jar and releasing agent are injected.
(22) supercharging feed unit 40 has structure shown in Figure 4.Reference numeral 41 among Fig. 4 illustrates die casting machine.Flexible mould 1 shown in Figure 1 and fixed mould 2 are arranged in die casting machine 41 apart from certain distance is arranged each other.The jar 25 that stores oil-based release agent is connected to injection unit 22 by releasing agent force feed flexible pipe 42.Although diagram has not been installed the pump that pressure-reducing valve shown in Figure 3 and pump are inhaled releasing agent in jar 25.Make injection unit 22 move up and down by the supporting pillar 43 that can move up and down (along the direction shown in arrow Y).Supporting pillar 43 is by supporting pillar on the part that is installed in die casting machine 41 44 and transverse bar 45 guiding that are connected to supporting pillar 44.
It below is the reason of setting the apical side height of releasing agent face in the jar in the above described manner.Just, in order to be coated with a spot of oil-based release agent, must the low pressure releasing agent be delivered to injection unit by pump, and the discharge pressure of oil-based release agent being extremely low, is 0.02 to 0.05MPa.Therefore, if the very small amount of air that is blended in the releasing agent is carried by pump with releasing agent, then sizable air layer, be that so-called air section (air spot) is formed on the peak place in the pipe.This air section interrupts releasing agent stream, causes the loss of stability of emitted dose.As a result, in the large-scale production of die-cast product, the repeatable accuracy variation of releasing agent emitted dose control, and the quality of die-cast product affects adversely.
On the other hand, discovery can solve this injection control problem by setting by aforementioned manner.Upper limit position when the apical side height of releasing agent face should be set at nozzle and is in standby in jar (this position than jar high) L
1Lower position L with releasing agent when injected
2Between (with reference to Fig. 4).Just, during when nozzle is in lower position with standby, pressure is enhanced corresponding to the hydraulic pressure that relates to jar position (height of releasing agent), and the flow rate of releasing agent is corresponding to be enhanced, thereby and the air of accumulation also become to flow easily and reduced air section.Yet also lower than above-mentioned position if the tip location of nozzle is configured to, air flows out sooner, but a large amount of releasing agents also is discharged from.This causes being difficult to be coated with a spot of releasing agent.Thereby, need to set the lower position.On the other hand, during the nozzle of top side location was in standby, pressure was low, thereby the mobile of releasing agent is lowered, and the air tip of mass flowing nozzle hardly.And when nozzle was higher than above-mentioned position, the hydraulic pressure of releasing agent was lowered, and final, releasing agent is tending towards returning in the jar, and air is inhaled into from the tip of nozzle sometimes.For this reason, the last height and position of nozzle also is restricted.The position that is used for the jar of releasing agent is set between this lower limit and the upper limit, thereby small injection can be implemented and the air section problem can be resolved simultaneously.And, can supply releasing agent to injection unit with essential minimum supply pressure.Give the credit to this effect, about emitted dose, each nozzle can both be realized being coated with to be low to moderate 0.1 to 0.2cc amount.And, can carry out even and a spot of injection to die surface.
Hereinafter, embodiment of the present invention will be described.Yet the present invention also is not intended to be only limited to illustrated embodiment.
(I) embodiment 1 to 5 and comparative example 1 to 3
(A) result of component and measurement test
Following table 1 shows component, physical property values, the result of adherence test and the result of friction test of embodiment 1,2,3,4 and 5.And, following table 1 shows comparative example 1 to 3, is component, physical property values, the result of adherence test and the result of friction test of the prepared water-soluble mold-release agent of applicant of the present invention that these water-soluble mold-release agents are water colo(u)r releasing agent (trade name: Lubrolene A-704); Water-soluble mold-release agent (trade name: Lubrolene A-201); And water-soluble mold-release agent (trade name: Lubrolene A-1609).
(B) preparation method
With after mixing high viscosity mineral oil, silicone oil, rapeseed oil and organic-molybdenum according to the ratio shown in the percentage by weight in the table 1, this mixture is heated to 40 ℃ and be stirred 10 minutes.This mixture by further with solvent according to the amount of the percentage by weight shown in the table 1, and mixed once more 10 minutes, to make oil-based release agent.
Table 1
*: the surplus of water-soluble mold-release agent and 0.05 weight %, and this surplus is wax, emulsifying agent etc.
In table 1,
Solvent: trade name: Shellsol TM, by-Shell Kagaku K.K. production
High viscosity mineral oil: trade name: Bright stock, produce by Japan Energy Corporation,
Grease (fats): by Meito Yushi Co., the rapeseed oil that Ltd. produces
Silicone oil: trade name: Release Agent TN, by Asahikasei Wacker Silicone Co., Ltd. produces
Organic-molybdenum: trade name: Adeka 165 is produced by Asahi Denka Kogyo
(C) measuring method of flash point
The flash point of each sample is measured according to the Pensky-Martin method of JIS-K-2265.
(D) measuring method of dynamic viscosity
Measure dynamic viscosity under 40 ℃ according to JIS-K-2283.
(E) measuring method of adhesive capacity
(E-1) prepare
Iron plate (SPCC, 100mm * 100mm * 1mm is thick) was cured 30 minutes down in 200 ℃ in baking oven as sample, cool overnight in drier, and this plate weight is measured as the magnitude of 0.1mg.
(E-2) injection of oil-based release agent
The operation of adherence test machine shown in Figure 5 is as follows.
At first, power supply temperature-adjusting device 12 is set at set point of temperature, and, be used to keep stand (stand) 14 of sample to be heated by heater 13., when first thermocouple 17 reaches design temperature, be placed in the metal fixing (metalfitting) 15 that is used to support sample herein as the iron plate 16 of sample, and, make second thermocouple 18 firmly contact with iron plate 16.After this, when the temperature of iron plate 16 reached set point of temperature, the various releasing agents 19 injected devices 20 of ormal weight were ejected on the iron plate 16 automatically.Then, iron plate 16 is removed and vertically stands in regular time in the air, so that oil drips from iron plate 16.
(E-3) measuring method of adhesive capacity
In the baking oven of iron plate 16 that the coating component will be arranged, keep after the stipulated time iron plate being taken out in set point of temperature.Iron plate is cooled off by air, and is further cooled the stipulated time in drier.After this, the weight of bearing the iron plate 16 that is coated with component is measured, and this measurement reaches the magnitude of 0.1mg.And, by calculating adhesive capacity according to empty result of the test iron plate weight change.
(E-4) experimental condition
Testing machine: adhesive capacity testing machine (by Yamaguchi Giken Co., Ltd. makes)
Measuring condition: described in following table 2.
Table 2
| Oiliness | Water-soluble | |
| Release agent solution | Undiluted solution | Dilute 80 times solution |
| Emitted dose (cc) | 0.3 | 10 |
| Air pressure (MPa) | 0.3 | 0.3 |
| Hydraulic pressure (MPa) | 0.003 | 0.2 |
| Test temperature (℃) | 300 | 300 |
| The test back is dry | Drying is 30 minutes under 200 ℃ | Moist |
(F) measuring method of frictional force
(F-1) friction test method
With reference to Fig. 6 A to 6C.At first, frictional force test-bed 2 (the SKD-61 type that will have thermocouple 1,200mm * 200mm * 34mm) be heated to set point of temperature by the heater that is purchased, wherein said thermocouple 1 is connected to MEC International Co., the automatic tension tester of Ltd manufacturing (trade name: Lub Tester U).Then, as shown in Figure 6A, test-bed 2 is vertically erected, and makes nozzle 3 spray releasing agent 4 under the condition shown in the adherence test in the above.After this immediately test-bed 2 levels are placed on the testing machine main body 5, and, with MEC International Co., on the ring 6 of Ltd manufacturing (making internal diameter 75mm, external diameter 100mm, high 50mm by the S45C) centre (with reference to Fig. 6 B).Then, with 90cc dissolve aluminum metal 7 (ADC-12 is at 670 ℃) pour into the ring 6 in, the wherein said aluminum metal 7 that dissolves is to be melted at the smelting furnace place that ceramic process is used.This motlten metal is cooled 40 seconds to be solidified.And the weight 8 of 8.8kg made of iron is placed on this aluminium that solidifies (ADC-12) immediately imperturbably.Then, ring 6 along the direction shown in the arrow X by the geared system of testing machine (gear) tractive, thereby measure frictional force (with reference to Fig. 6 C).
(F-2) friction measurement condition
The friction measurement condition is as shown in following table 3.
Table 3
| Load (total amount of aluminium and weight) | 10Kg |
| Contact surface area (the cross-sectional surface area of ring) | 44.2cm 2 |
| Draw rate | 1cm/sec |
(G) overall result of Ce Lianging (oil-based release agent)
Result of the test about flash point, dynamic viscosity, adhesive capacity (300 ℃) and the frictional force under 300 ℃ and 350 ℃ of the foregoing description and comparative example all is displayed in Table 1.
Testing machine manufacturing merchant confirms that these results and the result who obtains by actual die casting machine have fabulous correlation.The value of 10Kgf is corresponding to the allowed highest level of release property in the actual machine in the testing machine.The value higher than 10Kgf hints in the actual machine as the problem of sticking type and burr and so in the testing machine.
According to the result of function comparative test, the oil-based release agent of embodiment 1 to 5 is found water-soluble mold-release agent than comparative example 1 to 3 and has higher adhesive capacity, lower frictional force and better demoulding ability.And even if take place with water-soluble mold-release agent the time under 350 ℃ the high temperature of sticking type, these oil-based release agents are found also has fully superior demoulding ability.
(II) embodiment 6 to 11 and comparative example 4 to 7
Hereinafter, describe the releasing agent of embodiment 6 to 11 with reference to the releasing agent of comparative example 4 to 7, the releasing agent of embodiment 6 to 11 contains the additive that improves wetability.
(A) component and result of the test
Following table 4 shows component, physical property values, adherence test result and the frictional force result of the test of the oil-based release agent of embodiment 6,7,8,9,10 and 11.Following table 5 shows the oil-based release agent of comparative example 4,5 and 6 and the water-soluble mold-release agent (trade name: LubroleneA-1609 of comparative example 7, by AOKI SCIENCE INSTITUTE CO., Ltd. makes) physical property values, component, adherence test result and friction test result.
Table 4
*1: trade name: the polysiloxanes of EFKA-3236 modification, produce by Wilbur-Ellis Company
*2: trade name: the EFKA-3778 acrylic acid series copolymer, produce by Wilbur-Ellis Company
Other components are with shown in the table 1.
Table 5
*1 He
*2 with shown in the table 4.Other components are with shown in the table 1.
*3: the surplus of water-soluble mold-release agent and 0.05 weight %, and this surplus is wax, emulsifying agent etc.
(B) preparation method
Except mixed the additive that improves wetability before adding solvent, other are with described in the embodiment 1.
(C) measuring method of flash point
To embodiment 9 and comparative example 6, measure by Cleveland Open method, to embodiment 6,7,8,10 and 11 and comparative example 4 and 5 then measure by the Pensky-Martin method.
(D) measuring method of dynamic viscosity
Described in embodiment 1.
(E) measuring method of adhesive capacity
The measurement of preparation and adhesive capacity is all with described in the embodiment 1, and experimental condition is as shown in following table 6.
Table 6
| Oiliness | Water-soluble | |
| Release agent solution | Undiluted solution | Dilute 80 times solution |
| Emitted dose (cc) | 0.3 | 30 |
| Air pressure (MPa) | 0.3 | 0.3 |
| Hydraulic pressure (MPa) | 0.003 | 0.2 |
(F) measuring method of frictional force
The frictional force test method is with embodiment 1, and the friction measurement condition is with described in the table 3.
(G) overall result of Ce Lianging (improving the effect of the additive of wetability)
With embodiment 6 (containing the additive that improves wetability) and comparative example 4 (not containing the additive that improves wetability); Embodiment 7 (containing the additive that improves wetability) and comparative example 5 (not containing the additive that improves wetability); And embodiment 8 (containing the additive that improves wetability) and comparative example 6 (not containing the additive that improves wetability) compare, and finds that the additive of raising wetability has improved adhesive capacity considerably and reduced frictional force.
Releasing agent might not be ejected on the die surface of actual machine equably.Have some hidden die part wetting by a spot of oil droplet, in this case, the releasing agent of embodiment 6 to 11 can show superior release property, and the releasing agent of embodiment 6 to 11 shows high performance aspect adhesive capacity.The additive that improves wetability not only in the releasing agent of embodiment 6,7,8 and 10 effectively, wherein, the viscosity of embodiment 6,7,8 and 10 releasing agent 3 to 5mm
2In the scope of/s.In addition, additive also is that effectively wherein, the viscosity of the releasing agent of embodiment 9 is up to 24mm in the releasing agent of embodiment 9
2/ s.The frictional force of the water-soluble mold-release agent of referential comparative example 7 under 300 ℃ reaches operating limit 10kgf, and oil-based release agent in the frictional force under 300 ℃ in 1 to 3kgf scope, thereby be spendable.
The releasing agent of the present invention that contains the additive that improves wetability is effective for the adhesive capacity that improves on the die surface.Sometimes, the mist of releasing agent scatters hardly, causes at the thin place of mould sticking type taking place.Releasing agent with high-adhesiveness matter is that height can be avoided this problem.We can say that from this viewpoint, oil-based release agent of the present invention is superior.And, because the adhesive efficiency height, so these releasing agents can use slightly and need not make the oil film of adhesion thicker.Even if (a) dilutes these releasing agents with said components, these releasing agents also can be used as low viscosity, the ejection releasing agent of getting over of fine quality.
(embodiment 12)
Then, use description to evenly be coated with the injection unit of oil-based release agent of the present invention.This unit such as top illustrated.In embodiment 12, come the comparison castability by the use actual machine.
Below table 7 show that releasing agent by using embodiment 13 to 16 and comparative example 8,9 and above-mentioned injection unit carry out the character of the product that aluminium die casting obtained.In this case, the releasing agent of embodiment 4 is used to embodiment 13 and 14; The releasing agent of embodiment 6 is used to embodiment 15 and 16; The releasing agent of comparative example 7 is used to comparative example 8; And the releasing agent of comparative example 4 is used to comparative example 9.As shown in Figure 1, the mould that is adopted among the embodiment 12 can be made two products simultaneously, and possesses the cast structure of being made up of the upper and lower slide block in the die cavity portion, and wherein, described die cavity portion is formed by flexible mould and fixed mould.
Injection unit of the present invention is connected on the automatic injection unit, die cavity portion is carried out the injection of oil-based release agent.And special-purpose ejecting unit (shown in Fig. 3) and supercharging feed unit (shown in Fig. 4) are used to oil-based release agent.And releasing agent is inhaled by the pump pump, and is sent to injection unit under 0.02 to 0.05MPa low pressure.Oil-based release agent sprays by the air that uses in the factory, and is applied on the die surface slightly.
By found that shown in the table 7, to compare with 9 releasing agent (latter) with comparative example 8, some goes up better or superior the releasing agent (the former) of embodiment 13-16 below:
1) infers because the superior distribution character of releasing agent just has the performance that excellent removal burr, sticking type, streamline, metal wave and burr take place;
2) porosity in the die-cast product is lower;
3) emitted dose is few, and this helps short injecting time;
4) supply pressure is had superior controllability, this emitted dose that causes each nozzle is stable;
5) because the fluctuation of emitted dose is less, so aspect the control emitted dose, daily work is less;
6) in mould, carry out regular maintenance necessity, dimensional accuracy maintenance and that these several respects of cracking take place is identical or better; And
7) superior aspect the maintenance of mould and precision.
And be not intended to make the present invention to only limit to the embodiment of above explanation.Can under the situation that does not break away from the spirit and scope of the present invention, concrete process conditions and component parts be made improvements and substitute.For example, in the above embodiments, although be used for the pipe that air introduces and be used for the pipe that releasing agent introduces locating to be arranged to face-to-face at 2, yet, these pipes can 3 or more the multiple spot place be installed into aspectant.Thus, need these pipes to be arranged to toward each other as far as possible equably.The layout that relies on this mode, releasing agent can be ejected on the mould by the tip from nozzle more equably.Ripple pattern, gas flow and the coating weight stayed in the product can be improved.
In the foregoing description 12, top side location the when position, top (tip end) of pasta is set at nozzle and is in standby in the jar when stopping to spray and releasing agent are by nozzle between the lower position when injected.Yet, be not limited in described in this example.The jar that is used for releasing agent can not be installed between the above-mentioned position, and by pressurization, the apical position L of the pasta of releasing agent
3Can be set at this position.Rely on such adjustment, under the not injected situation of releasing agent, the stop position of injection unit (the rising limit) is more than the pasta position, and therefore, releasing agent can not drip.On the other hand, releasing agent with applied situation under since injection unit in rest position, be that the lower limit place of injection unit is stopped, so pressure is enough to cause oil-based release agent to drip naturally.Therefore, in hydraulic hose, do not have air section to form, and under the situation that inhomogeneities is inhibited, carry out the injection of oil-based release agent equably by the air pressure in the equipment.
(III) embodiment 17 and comparative example 10 and 11
Hereinafter, will come together to describe embodiment 17 with comparative example 10 and 11.
(A) component and result of the test
Following table 8 shows component, blending ratio and the result of the test of the oil-based release agent of embodiment 17 and comparative example 10,11.
Table 8
*1: trade name: Lasmit BHT, by Daiichi Kogyo Seiyaku Co., Ltd produces
*2: trade name: HiTEC-569, produce by Afton Chemical, and other components are with shown in the table 1.
*3: because the aluminium that solidifies do not slide on test-bed and deposit, so can't measure.
(B) preparation method
Except adopting antioxidant to replace the additive of raising wetability of embodiment 6, other are prepared as described in example 6 above.
(C) measurement of flash point
With measuring the flash point of various releasing agents with mode identical described in the embodiment 1.
(D) measurement of dynamic viscosity
With measuring the dynamic viscosity of various releasing agents with mode identical described in the embodiment 1.
(E) laboratory oxidation test, the ROBT method
According to JIS-K-2514, each releasing agent all is sampled in the enclosed type rotary pump, and oxygen is sealed then.Oxidation is carried out under 150 ℃, and, measure oxygen pressure and reduce the time of being consumed suddenly.
(F) measuring method of frictional force
The test method of frictional force and measuring condition are with described in the embodiment 1.
(G) overall result of Ce Lianging (effect of antioxidant)
In embodiment 17 and comparative example 10,11, flash point (℃), the dynamic viscosity (mm under 40 ℃
2But/s), the laboratory frictional force test under the laboratory oxidation test, 350 ℃ and 400 ℃ and use the measurement of the continuous castability of actual die casting machine to be carried out, thus the result shown in the table 8 obtained.
The result of embodiment 17 (containing antioxidant) and the result of comparative example 11 (not containing antioxidant) are compared, angle from laboratory test, the measured value of comparative example 11 (degeneration time) is 240 minutes, and embodiment 17 is 890 minutes, and the latter demonstrates about 4 times more than durability and degenerates less.Therefore, under the situation of embodiment 17, confirm that antioxidant has suppressed the oxidation degeneration of oil-based release agent.
From the angle of frictional force test, the frictional force of comparative example 11 under 350 ℃ is 5kgf, and this is enough low for reality is used.Yet this releasing agent causes sticking type and deposition under 400 ℃.On the other hand, in embodiment 17, the low 9kgf that reaches of the frictional force under 400 ℃.Compare with the releasing agent of comparative example 11, be found obviously superior at this releasing agent of high temperature lubricating properties.Therefore, under the situation of embodiment 17, confirm that antioxidant demonstrates effect and prevents sticking type.
According to above-mentioned two kinds of experiments, can suppose that antioxidant can at high temperature postpone the oxidation of the component of oil-based release agent and degenerate.Because this delay, antioxidant helps to keep the thickness of oil film.Therefore, because heavy oil film, so that frictional resistance is maintained at is low-level.
On the one hand, when use actual die casting machine evaluate comparative example 11 releasing agent the time, sticking type takes place in the time of the 10th time, cause and can't cast continuously.Under the situation of embodiment 17, manufacturing can continue 220 times or more continuously.Therefore, confirm that antioxidant helps to reduce sticking type and improves the continuous casting number of times.Under the situation of the actual machine that this situation adopted, the moment after product is removed, the temperature of core bar is 410 ℃.Yet under the situation of the combination of actual machine and comparative example 11, the continuous casting under 380 ℃ is the limit.According to these results, we can say that adding antioxidant is improved the durability to high 30 temperature of spending.
And, in order to ensure the lubricating property that is low to moderate the moderate temperature zone, in embodiment 17 and comparative example 11, added organic-molybdenum.On the other hand, in comparative example 10, do not add organic-molybdenum.Compare with comparative example 10, the oxidation stability of comparative example 11 is slightly improved.In the friction test of laboratory, the frictional force under 350 ℃ slightly reduces.The casting number of times slightly improves.Thereby these results show that organic-molybdenum has auxiliaring effect to anti-oxidation.Yet, to compare with phenol or amine antioxidants, effect is not so remarkable.
(embodiment 18)
Hereinafter, with the method for describing according to the setting solvent mixing ratio of second invention.
Can know by Fig. 7 and to see, thereby the flash point that can easily change releasing agent is regulated the Leidenfrost's phenomenon temperature.The inventor exists the flash point F (with reference to equation (1)) of Leidenfrost's phenomenon temperature L and oil-based release agent and the correlation of maximum operation (service) temperature (S) (with reference to equation (2)) for studies show that realization the present invention carries out.Described correlation can by as give a definition:
S+80＝L (1)
L＝4.4×F+36 (2)
Table 9
| | Sample | 1 | |
|
| First solvent | 80.1 | 71.2 | 62.3 | |
| Low viscosity mineral oil | 8.9 | 26.7 | 44.5 | |
| High |
5 | 5 | 5 | |
| |
5 | 5 | 5 | |
| Rapeseed oil | 0.5 | 0.5 | 0.5 | |
| Organic-molybdenum | 0.5 | 0.5 | 0.5 | |
| Flash point (℃) | 95 | 102 | 105 |
1) desired value of substitution maximum operation (service) temperature S in equation (1) is calculated Leidenfrost's phenomenon temperature L.Then, calculate temperature L be updated in the equation (2), to calculate the required flash point F of oil-based release agent.
2) then,, prepare three types releasing agent (sample 1, sample 2, sample 3) by the blending ratio of solvent and mineral oil in the change composition.Table 9 shows the component and the flash point of these three kinds of samples.Recommending the blending ratio of solvent is 80%, 70% and 60%.
3) after this, measure the flash point of these three kinds of releasing agents, and, as shown in Figure 9, to the correlation mapping of solvent (%) and flash point.
4) further, by described figure and use as 1) described in calculate flash point (F) calculate required solvent (volume %).
5) then, by calculate by the ratio that deducts solvent and additive surplus calculate light component (low viscosity mineral oil and/or artificial oil).
In aforesaid way, in embodiment 18, the blending ratio of solvent and mineral oil is suitably set, thereby has avoided Leidenfrost's phenomenon.
In embodiment 18, use solvent and mineral oil condition have been described.Yet the present invention can comprise use solvent and synthetic oil condition; Or use solvent, mineral oil and synthetic oil condition; Or use the situation of two kinds of solvents.
In the above-described embodiments, based on first invention oil-based release agent has been described.Yet the combination of each component, blending ratio and injection conditions can suitably be set so that use following oil-based release agent.Just, this oil-based release agent contains: 50 weight portions or more a kind or various ingredients altogether, these components are selected from by solvent, mineral oil, artificial oil, fat and oil, aliphatic acid, and the group that constitutes of fatty acid ester; 40 weight portions or silicone oil still less; And the additive with lubricating function, the flash point of this oil-based release agent is 50 to 250 ℃, the dynamic viscosity under 40 ℃ is 2 to 50mm
2/ s.Rely on such formation, can as conventional situation, not cause quenching, and this reagent has high-fire resistance, causes gluing type hardly as oil-based release agent, thereby can prolong die life.And, use this oil-based release agent on die surface, to form even and thin film with a small amount of, the foaming on the mould when burr of die-cast product and sticking type and heat treatment can be inhibited.As the situation of above-mentioned oil-based release agent under, the kind of each component and character are for as mentioned above.
Industrial applicability
Oil-based release agent of the present invention is suitable for lubricating die surface by the jet lubrication agent during the die casting and being used for lubricated drift when pouring into motlten metal. Oil-based release agent of the present invention is suitable in making continuously marginally, and Automatic continuous sprays undiluted reagent liquid.
Claims (18)
1. oil-based release agent that is used for die casting, it contains: (a) solvent of 70 to 98 weight %, the dynamic viscosity of described solvent under 40 ℃ are 2 to 10mm
2The flash point of/s and described solvent is in 70 to 170 ℃ scope; (b) high viscosity mineral oil of 1 to 10 weight % and/or artificial oil, described high viscosity mineral oil and/or the artificial oil dynamic viscosity under 40 ℃ is 100mm
2/ s or higher; (c) 15 weight % or silicone oil still less, the dynamic viscosity of described silicone oil under 40 ℃ is 150mm
2/ s or higher; And (d) additive with lubricating function of 1 to 5 weight %, it is characterized in that the flash point of described releasing agent is in 70 to 170 ℃ scope, and the dynamic viscosity of described releasing agent under 40 ℃ is 2 to 30mm
2/ s or higher.
2. oil-based release agent as claimed in claim 1 is characterized in that, by adding low viscosity mineral oil and/or artificial oil, so that the ratio of the component that is comprised (a) adds up to 70 to 98 weight %.
3. oil-based release agent as claimed in claim 1 or 2 is characterized in that, in the injection emitted dose of mould is counted 20ml or still less based on undiluted releasing agent liquid each time.
4. oil-based release agent as claimed in claim 1 further contains the additive that improves wetability.
5. oil-based release agent as claimed in claim 4, the flash point that further contains 0.1 to 3 weight % are 100 ℃ or the lower acrylic acid series copolymer or the polysiloxanes of acryloyl group modification, with as the additive that improves wetability.
6. oil-based release agent as claimed in claim 1 further contains antioxidant.
7. oil-based release agent as claimed in claim 6 it is characterized in that containing one or more antioxidants of 0.2 to 2 weight %, and described one or more antioxidants is selected from the group of being made up of amine, phenol and cresols class antioxidant.
8. oil-based release agent as claimed in claim 1 is characterized in that, described silicone oil is to have chain length than the longer alkyl-aralkyl of dimethyl or the alkyl-silicone oil of alkyl.
9. oil-based release agent as claimed in claim 1, it is characterized in that 1 to the 3 kind of optional arbitrarily component with respective components (a) and (b), (c) and (d) is mixed in advance, to obtain mixture, and then remaining ingredient mixed with described mixture, thereby obtain described releasing agent.
10. as claim 4 or 5 described oil-based release agents, it is characterized in that, be 1 to the 4 kind of optional arbitrarily component mixing in (a) and (b), (c), (d) and the additive that improves wetability in advance with corresponding 5 kinds of components, to obtain mixture, and then remaining ingredient mixed with described mixture, thereby obtain described releasing agent.
11. as claim 6 or 7 described oil-based release agents, it is characterized in that, be that 1 to 4 kind of optional arbitrarily in (a) and (b), (c), (d) and antioxidant component is mixed in advance with corresponding 5 kinds of components, to obtain mixture, and then remaining ingredient mixed with described mixture, thereby obtain described releasing agent.
12. the method for a setting solvent mixing ratio, so that avoid Leidenfrost's phenomenon when any described oil-based release agent carries out die casting in using as claim 1 and claim 3 to 11, it is characterized in that, adopt two or more solvents as solvent, and, described method comprises the steps: the highest serviceability temperature (S) of substitution expection in following equation (1) and (2), so that calculate the flash point (F) of releasing agent; After having prepared the different releasing agents of three kinds or more kinds of coordinative solvents with variable concentrations, study the flash point of the various releasing agents that prepare; Make the figure of correlation of the flash point of the percentage by weight of solvent in the various releasing agents and various releasing agents; And by described figure and by equation (1) and (2) calculate flash point calculate the percentage by weight of solvent in the releasing agent:
S+80＝L (1)
L＝4.4×F+36 (2)
Wherein, S represents the maximum temperature that releasing agent uses; L represents the temperature of Leidenfrost's phenomenon; And F represents the flash point of releasing agent.
13. the method for the blending ratio of a setting solvent and mineral oil and/or artificial oil, when using oil-based release agent as claimed in claim 2 to carry out die casting, to avoid Leidenfrost's phenomenon, described method is characterised in that equation (3) and the highest serviceability temperature (S) of (4) middle substitution expection that comprises the steps: below, to calculate the flash point (F) of releasing agent; After having prepared the different releasing agents of three kinds or more kinds of coordinative solvent, mineral oil and/or artificial oils with variable concentrations, study the flash point of the various releasing agents that prepare; Make the figure of correlation of the flash point of the percentage by weight of solvent in the various releasing agents and various releasing agents; And by described figure and by equation (3) and (4) calculate flash point calculate the percentage by weight of solvent in the releasing agent:
S+80＝L (3)
L＝4.4×F+36 (4)
Wherein, S represents the maximum temperature that releasing agent uses; L represents the temperature of Leidenfrost's phenomenon; And F represents the flash point of releasing agent.
14. a casting method that is used to carry out die casting, described method is carried out as any described oil-based release agent and releasing agent injection unit in the claim 1 to 11 by using.
15. injection unit, it is used for to mold ejector and is coated with as any described oil-based release agent of claim 1 to 11, it is characterized in that comprising: releasing agent injection unit, described releasing agent injection unit contain a plurality of nozzles that are used for to mould coating releasing agent; And the supercharging feed unit, described supercharging feed unit is under low pressure delivered to releasing agent described injection unit and is coated with a small amount of releasing agent to mould.
16. injection unit as claimed in claim 15 is characterized in that, described releasing agent injection unit comprises: the injection unit main body of separately supplying releasing agent and air; Be used for the pipe that releasing agent is introduced, the described pipe that is used for the releasing agent introducing is connected to described injection unit main body; And the pipe that is used for the air introducing, the described pipe that is used for the air introducing is connected to described injection unit main body, wherein, releasing agent introduced and a plurality of groups of being used for that air introduces 2 or more the multiple spot place arrange face-to-face so that be coated with releasing agent equably from described nozzle.
17. injection unit as claimed in claim 15 is characterized in that, described supercharging feed unit comprises: the releasing agent jar that stores oil-based release agent; And the force feed flexible pipe, it connects described releasing agent jar and described releasing agent injection unit, and
When stopping to spray, top side location the when apical position of pasta is set at described nozzle and is in standby in the described releasing agent jar and releasing agent are by described nozzle between the lower position when injected.
18. a casting method, described casting method be used for using as any described injection unit of claim 15 to 17 and as described in oil-based release agent carry out die casting.
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|---|---|---|---|
| JP2004252056 | 2004-08-31 | ||
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| JP5297742B2 (en) | 2008-09-26 | 2013-09-25 | 株式会社青木科学研究所 | Powder-containing oil-based lubricant for molds, electrostatic coating method using the same, and electrostatic coating apparatus |
| CN101628459B (en) * | 2009-04-07 | 2011-06-15 | 上海立汰新模具材料有限公司 | Polyurethane oil-based release agent and application thereof |
| GB201214475D0 (en) * | 2012-08-14 | 2012-09-26 | Dow Corning | Lubricant compositions |
| US9669459B2 (en) * | 2012-10-26 | 2017-06-06 | Ford Motor Company | System and method of making a cast part |
| JP6067608B2 (en) * | 2014-03-12 | 2017-01-25 | 株式会社青木科学研究所 | High-temperature heat-resistant oil-based mold release agent, high-temperature heat-resistant electrostatic coating type oil-based mold release agent and coating method thereof |
| CN106312010B (en) * | 2015-06-17 | 2019-01-25 | 浙江盾安轻合金科技有限公司 | Release agent preheating device and method |
| CN107614150B (en) * | 2015-06-26 | 2019-03-15 | 尤希路化学工业有限公司 | Releasing agent used for casting composition |
| CN107088648B (en) * | 2017-04-18 | 2019-07-02 | 奎克化学（中国）有限公司 | A kind of casting grid of lead-acid accumulator oil-based release agent |
| CN108015892A (en) * | 2017-12-28 | 2018-05-11 | 南方科技大学 | The degasification method and degassing apparatus of ceramic slurry |
| JP6746799B2 (en) * | 2018-06-05 | 2020-09-02 | ユシロ化学工業株式会社 | Release agent composition and die casting method |
| CN108907074B (en) * | 2018-07-16 | 2020-10-16 | 昆山帝邦铸造科技有限公司 | Anti-oxidation release agent and preparation method and use method thereof |
| CN112091184A (en) * | 2020-09-24 | 2020-12-18 | 含山盛荣机械配件厂 | Foundry goods mould demoulding powder spraying equipment with clean function |
| CN112453346A (en) * | 2020-12-01 | 2021-03-09 | 阜阳市世科智能设备有限公司 | Die casting die with automatic cooling and lubricating mechanism |
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Effective date of registration: 20161222 Address after: Tokyo, Japan Patentee after: Aoki Science Inst Co. Ltd Patentee after: Ryobi Ltd Patentee after: Aisan Kogyo K.K. Address before: Tokyo, Japan Patentee before: Aoki Science Inst Co. Ltd Patentee before: Ryobi Ltd Patentee before: KOTOBUKI KINZOKU KOGYO CO LTD Patentee before: Aisan Kogyo K.K. |