CN104125868B

CN104125868B - Mold release compositions

Info

Publication number: CN104125868B
Application number: CN201380006153.0A
Authority: CN
Inventors: 铃木干典; 押本康成; 松木有; 酒向茂; 石黑正昭; 森正至; 上坂直人; 安田一正; 师冈将义
Original assignee: Denso Corp
Current assignee: Denso Corp
Priority date: 2012-01-23
Filing date: 2013-01-21
Publication date: 2016-01-13
Anticipated expiration: 2033-01-21
Also published as: DE112013000661T5; CN104125868A; US20150057401A1; JP2013173183A; WO2013111708A1

Abstract

The invention provides mold release compositions, described mold release compositions by be applied to for the squeeze casting, low pressure casting etc. of metal mould or use for the mould of die forging.Described mold release compositions comprises mineral oil or artificial oil, kollag, thermosetting resin, and polymer compound.Described mold release compositions uses by being applied to the inner surface of the mould for casting or forging.

Description

Mold release compositions

Technical field

The present invention relates to mold release compositions (dierelaseagentcomposition).More particularly, the present invention relates to mold release compositions, described mold release compositions by be applied to for the squeeze casting, low pressure casting etc. of aluminium alloy etc. mould or use for the mould of the die forging (dieforging) of aluminium alloy, aluminum steel etc.

Background technology

As the metal forming process using mould, there are casting method and die forging method.The example of casting method comprises low-pressure casting method, compression casting method etc.In such casting method, filling before mould with motlten metal, use releasing agent for suppressing the reaction between mould and motlten metal (welding) and contributing to the object of the demoulding of shaped article.In low-pressure casting method, as a kind of squeeze casting method etc. in compression casting method, due to by the low velocity of motlten metal as aluminium alloy filler die cavity, so keep mold temperature and molten metal temperature to be retained as higher than typical high speed compression casting method, to ensure the mobility of motlten metal during filling.As the releasing agent being applicable to such high-temperature molding, in most of the cases use the releasing agent containing powder to provide effect of heat insulation.In low pressure casting, the mould washing agent (diewash) comprising inorganic powder and waterglass can be used.

Usually, releasing agent comprises water base type and oil base type.Such as, in casting method, before cast, releasing agent is applied to casting mould to form coating to use casting mould by spraying.As the releasing agent of water type, use such composition, wherein water be used as decentralized medium and the inorganic powder of talcum etc., adhesive component as water-soluble polymer, for dispersant that this inorganic powder is dispersed in water and be intended to provide lubricate and the organic compound preventing from biting (seizing) as wax or organosilicon (silicone, silicone) mixed etc.As oil base releasing agent, use such composition, the wherein dilution such as silicone oil solvent.

But in each in low-pressure casting method and squeeze casting method, filling speed is low and mold temperature and molten metal temperature are retained as height, so that occurs a large amount of problems relevant to releasing agent.Such as, when water type releasing agent, step on Dan Frost phenomenon (Leidenfrostphenomenon) due to Lay and be difficult to form coating.In order to obtain enough film thicknesses, need increase spray time and cause mold temperature to decline.On the other hand, oil type releasing agent has the coating formable being better than water type releasing agent, but needs spray control techniques to limit the excessive injection of releasing agent.In addition, excessive coating formation due to releasing agent decomposition of components caused by and cause the pollution of mould, thus affect accuracy to size.When mold temperature is high especially, release agent components generating gasification and be comprised in product (as cast article), thus cause the problem such as occurring internal flaw.Therefore, in order to suppress the generation of such problem, the method reducing emitted dose can be used.

More specifically, as using water as the releasing agent of decentralized medium containing powder, known such aqueous release agent, it contains (such as, see, patent document 1) of inorganic lubricant, spherical resin particle and organic metal carboxylate.Equally, as respective containing powder and with an organic solvent as the releasing agent of decentralized medium, known such lubricant releasing agent, its contain pulverulent solids lubricant, adhere to improver (adhesionimprover) and volatile solvent (see, such as, patent document 2), and known such metal casting releasing agent, it contains the inorganic powder (see patent document 3) of the solvent of the dynamic viscosity with regulation, the inorganic powder with the tone of regulation and graphite, carbon black etc.

Prior art document

Patent document

Patent document 1

JP-A-2001-259788

Patent document 2

JP-A-2000-33457

Patent document 3

JP-A-2008-93722

Summary of the invention

The problem that invention will solve

But water type releasing agent to be deposited on owing to using continuously on mould thus adversely to affect accuracy to size and the outward appearance of product.This makes need regular clean operation and cause production efficiency to reduce.On the other hand, a kind of method being intended to reduce deposition causes releasing agent adhesiveness (coating formable) to decline.Therefore, be not easy suppress to deposit simultaneously and coating formable is provided.In addition, reduce emitted dose and in most cases cause spray nozzle clogging, especially when releasing agent contains powder to suppress excessively being formed in of coating.Therefore, need such releasing agent, even if its have allow also to allow under more than the high mold temperature of 300 DEG C to obtain enough hot retentivities and enough can the coating formable of release property (can release property, releasability) and its to be unlikely deposited on mould and plug nozzle.

In low-pressure casting method, mould washing agent can be used, but cause the problem of the high surface roughness of such as uneven coating layer thickness and the cast article caused by rough coatings surface.In addition, because coating becomes thinner in time, the problem that the accuracy to size that also there is product declines.

Achieve the present invention in view of above-mentioned conventional cases, and its objective is and provide a kind of releasing agent, described releasing agent is by being applied to for the mould of the squeeze casting, low pressure casting etc. of aluminium alloy etc. or using for the mould of the die forging of aluminium alloy, aluminum steel etc.

The means of dealing with problems

When the thermosetting resin with excellent heat resistance is used as the adhesive component in releasing agent, form solid cladding and can being also enhanced by the behavior of the thermal decomposition of thermosetting resin by release property of this coating.That is, by the thermosetting resin of mix predetermined quantities in the technique forming coating, form solid cladding and, after contacting with high-temperature molten metal, this coating becomes fragile and easily removes.Use kollag as the oil type releasing agent of mold release compositions containing mineral oil as decentralized medium by providing equally, the decomposition of releasing agent is suppressed and formation has the coating of adequate thickness, thus ensures hot retentivity and allow to keep predetermined mold temperature.

In addition, depend on mold temperature, by mixed polymerization compounds as wax, the releasing agent with more excellent properties can be obtained.That is, when kollag and thermosetting resin are dispersed in mineral wet goods and add wax etc. to it, coating can be formed under the short spraying phase, even if on the mould of the special high-temperature more than 400 DEG C, and the production efficiency improved.On the other hand, when releasing agent be no more than be tending towards exceedingly adhering to mould at the temperature of 400 DEG C and the rippability of coating is tending towards deterioration time, use other wax, be different from the another kind of polymer compound of wax, such as, polybutene etc. provide similar high coating formable, do not damage the rippability of coating simultaneously.

As mentioned above, by selecting according to mold temperature and optionally utilizing the combined amount of the polymer compound species that will use and this polymer compound of adjustment further, can provide simultaneously the first performance as can release property or hot retentivity and the second performance as rippability.In addition, by carrying out process as high-speed stirred in the process preparing releasing agent, kollag can be disperseed fully.This can prevent spray nozzle clogging.

Thermosetting resin has and depends on its mean molecule quantity and different viscosity (when heat fusing), curing rate etc., and can provide adhesion strength according to its molecular weight.Therefore, by using the thermosetting resin with predetermined mean molecule quantity as mold temperature according to forming method and condition of molding, solid cladding can be formed between shaping period, and allow to utilize the thermal decomposition of thermosetting resin subsequently and the easily demoulding.The easy equally residue from die surface removing releasing agent.In addition, by using the thermosetting resin with predetermined mean molecule quantity, can also provide such mold release compositions, described mold release compositions has the trend being unlikely deposited on mould and causing spray nozzle clogging.

Achieve the present invention based on such discovery.

The present invention is as follows.

1. a mold release compositions, described mold release compositions comprises mineral oil or artificial oil, kollag, thermosetting resin and polymer compound, and is used by the inner surface being applied to the mould for casting or forging.

2., according to the mold release compositions of above-mentioned 1st, wherein said kollag is at least one in talcum, boron nitride, graphite, mica, molybdenum bisuphide and fullerene (fullerene).

3. according to the mold release compositions of above-mentioned 1st or the 2nd, the average grain diameter of wherein said kollag is 0.5 to 30 μm, and when the total content of described mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the content of described kollag is 1 to 10 quality %.

4. the mold release compositions any one of above-mentioned 1 to 3, wherein said thermosetting resin is phenol resin (phenolic resins, phenolresin) at least one, in epoxy resin, urea resin (Lauxite, urearesin), melmac (melamineresin), alkyd resins (alkydresin) and unsaturated polyester resin.

5. the mold release compositions any one of the claims the 1 to 4, wherein after described mold release compositions is applied to mould, described thermosetting resin serves as adhesive and temperature between shaping period issues solution estranged.

6. the mold release compositions any one of the claims the 1 to 5, wherein, when the number-average molecular weight of described thermosetting resin be 5,000 to 500,000 and forming temperature is 300 to 550 DEG C time, adhesion strength is 0.1 to 5.0MPa.

7. the mold release compositions any one of above-mentioned 1 to 6, wherein said polymer compound is at least one in synthetic wax and native paraffin.

8. the mold release compositions any one of above-mentioned 1 to 6, wherein said polymer compound is at least one in synthetic wax and polybutene.

9. according to the mold release compositions of above-mentioned 8th, wherein, during being applied to mould at described mold release compositions, the temperature of described mould be not less than 250 DEG C and lower than 400 DEG C time, use described polybutene, and when during described mold release compositions is applied to mould, when the temperature of described mould is not less than 400 DEG C and is no more than 550 DEG C, use described synthetic wax.

Note, the mean molecule quantity in the present invention is the polystyrene equivalent number-average molecular weight of being infiltrated chromatography measurement by gel.

Invention effect

Mold release compositions according to the present invention contains mineral oil or artificial oil, kollag, thermosetting resin and polymer compound.Therefore, even if on the mould being in high temperature, also promptly can form coating by the component of releasing agent, and suppress the temperature of mould to decline.In addition, between shaping period, coating is easily by occurring decompose thus become fragile from the heat of mould and motlten metal, and this significantly reduces the deposition of release agent components.As a result, the product with excellent di mension accuracy and excellent appearance can be provided.In addition, because releasing agent has high-fire resistance, the sand holes of the induced gas that the internal flaw with minimizing can also be provided to produce as the decomposition due to release agent components.

When kollag is at least one in talcum, boron nitride, graphite, mica, molybdenum bisuphide and fullerene wherein, the decomposition of release agent components is adequately suppressed.This allows formation have the coating of predetermined thickness and ensure hot retentivity.As a result, predetermined mold temperature can be kept.

Wherein the average grain diameter of kollag be 0.5 to 30 μm and when the total content of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the content of described kollag is 1 to 10 quality % when, powder particle is not assembled.As a result, the suppressed and inhomogeneities of coating surface caused by coarse particles of the blocking of nozzle is also reduced.

When thermosetting resin is at least one in phenol resin, epoxy resin, urea resin, melmac, alkyd resins and unsaturated polyester resin, form sufficient solid cladding and the rippability of coating is improved further by the thermal decomposition behavior of thermosetting resin wherein.

Wherein when thermosetting resin after mold release compositions is applied to mould serve as adhesive and temperature between shaping period issues solution estranged, solid cladding can be formed and be thermal decomposited afterwards between shaping period.This allows the easy demoulding and easily removes releasing agent residue from die surface.

Wherein when the number-average molecular weight of thermosetting resin is 5,000 to 500,000 and forming temperature when being 300 to 550 DEG C, when adhesion strength is 0.1 to 5.0MPa, by using the thermosetting resin with predetermined mean molecule quantity according to forming method, condition of molding etc., the mold release compositions with enough adhesion strengths can be provided.

When polymer compound is at least one in synthetic wax and native paraffin wherein, even if on the mould of the extra high temperature more than 400 DEG C, under the short spraying phase, also can forms coating, and enhance productivity.

When polymer compound is at least one in synthetic wax and polybutene, by optionally using these polymer compounds according to mold temperature, coating can be formed in wider mold temperature range wherein.

Wherein during being applied to mould at mold release compositions, the temperature of described mould be not less than 250 DEG C and lower than 400 DEG C time, use polybutene, and when during mold release compositions is applied to mould, the temperature of mould is not less than 400 DEG C and is no more than 550 DEG C, easily can form coating with shorter spray time, and have nothing to do with the temperature of mould.

Accompanying drawing explanation

[Fig. 1] Fig. 1 is explanatory, and its display is for spraying mold release compositions to form coating and the sketch map of the device of the air blast of coating that formed of removing.

[Fig. 2 (a) and 2 (b)] Fig. 2 (a) is explanatory, it is shown wherein releasing agent and is applied with the state forming coating to steel plate by spraying, and Fig. 2 (b) is explanatory, the metallic cylinder that mould is wherein simulated in its display is placed in coating and molten aluminum is applied to the state in this cylinder.

[Fig. 3 (a) is to 3 (d)] Fig. 3 (a) is explanatory, it is shown wherein mold release compositions and is applied with the state forming coating to steel plate by spraying, Fig. 3 (b) is explanatory, the metallic cylinder that mould is wherein simulated in its display is placed in coating and molten aluminum is provided to the state in cylinder, Fig. 3 (c) is explanatory, it shows the state that wherein metallic cylinder and discoid formed body have removed above coating, and Fig. 3 (d) is explanatory, its display is wherein by the state of air blast removing coating.

[Fig. 4 (a) is to 4 (c)] Fig. 4 (a) is the explanatory for measuring the sample destroying shear stress to 4 (c), wherein Fig. 4 (a) is the cross section of iron plate before joint and the schematic diagram on surface, Fig. 4 (b) is the cross section of iron plate after engaging and the schematic diagram on surface, and Fig. 4 (c) shows the schematic diagram in direction that wherein two iron plates engaged are pulled.

[Fig. 5] Fig. 5 is curve map, the number-average molecular weight of its display phenol resin and depend on correlation between the destruction shear strength different in conjunction with temperature.

[Fig. 6] Fig. 6 is curve map, and it relates to the correlation between the number-average molecular weight of phenol resin and adhered area ratio.

Detailed description of the invention

Below in detail the present invention will be described.

Mold release compositions of the present invention contains mineral oil or artificial oil, kollag, thermosetting resin and polymer compound.Described mold release compositions uses by being applied to the inner surface of the mould for casting or forging.

Be not particularly limited as the mineral oil of decentralized medium or artificial oil.As mineral oil, the oil of various mineral matter can be used.The example of mineral oil is included in the turbine oil described in JISK2213, the gear oil described in JISK2219, the machine oil etc. that describes in JISK2238.As artificial oil, the various oil of polyalphaolefin class, polyesters, polyethylene glycols etc. can be used.Especially, for coating formable and suppress kollag precipitation, use have according to JISK2283 40 DEG C measure, be preferably 10 to 400mm ²/ s, be more preferably 10 to 250mm ²/ s or most preferably be 10 to 100mm ²the mineral oil of the dynamic viscosity of/s or artificial oil.When the total amount of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the combined amount of mineral oil or synthetic resin is preferably 75 to 90 quality % or is more preferably 80 to 85 quality %.

Kollag is also not particularly limited.The example of kollag comprises talcum, boron nitride, graphite, mica, molybdenum bisuphide and fullerene.Preventing in nozzle during spraying blocking, the mean molecule quantity of kollag preferably no more than 30 μm, or is more preferably 0.5 to 30 μm.When the total amount of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the combined amount of kollag is preferably 1 to 10 quality %, or is more preferably 3 to 7 quality %.The aggregate particles of kollag may cause nozzle during spraying to block.When aggregate particles applies with former state, therefore coarse particles to be present in coating thus to cause and such as in the product surface formed, occur irregular problem.In order to prevent this problem, during preparing mold release compositions, preferably by the abundant dispersing solid lubricant of mechanical treatment using high speed agitator, colloid mill etc.

Thermosetting resin is also not particularly limited.The example of thermosetting resin comprises phenol resin, epoxy resin, urea resin, melmac, alkyd resins, unsaturated polyester resin etc.Thermosetting resin allows to form solid cladding by being comprised in mold release compositions.Thermosetting resin has and improves the rippability of coating as the high-performance of adhesive and by being thermal decomposited after shaping.The mean molecule quantity of thermosetting resin is preferably 6,000 to 1, and 000,000.When obtaining king-sized adhesion strength, its mean molecule quantity is preferably 6,000 to 100, and 000.In order to allow easily to peel off when the demoulding, its mean molecule quantity preferably more than 100,000 and be no more than 1,000,000.Therefore, the mean molecule quantity of thermosetting resin preferably considers that adhesion strength and rippability are determined.And, in raising rippability, when the total amount of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the combined amount of thermosetting resin is preferably 1 to 15 quality %, be more preferably 2 to 12 quality %, or most preferably be 3 to 7 quality %.

The example of polymer compound comprises synthetic wax as paraffin, Tissuemat E, polypropylene wax, polyethylene glycol oxide wax and PPOX wax, and native paraffin is as beeswax, Brazil wax and montan wax, polybutene, poly-(alkylidene) glycol etc.Note, produce gas, so the excessive mixing of polymer compound may affect the quality of coating and shaped article because polymer compound occurs to decompose by heat.Therefore, when the total amount of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 quality %, the combined amount of polymer compound is preferably 2 to 15 quality %, is more preferably 2 to 10 quality %, or most preferably is 4 to 8 quality %.

As polymer compound, synthetic wax, polybutene etc. are preferred.As synthetic wax, paraffin, polyethylene glycol oxide wax or PPOX wax are preferred, and especially, paraffin or Tissuemat E are preferred.Preferably, optionally polymer compound is used according to mold temperature.Especially preferredly be, as polymer compound, use synthetic wax as paraffin or polybutene, and when during releasing agent is applied to mould, the temperature of mould be not less than 250 DEG C and lower than 400 DEG C time, use polybutene, and when during releasing agent is applied to mould, when the temperature of mould is not less than 400 DEG C and is no more than 550 DEG C, use synthetic wax as paraffin.By this way, the coating with predetermined thickness can easily be formed under short spray time.

Mold release compositions can also be made to contain and to be different from the another kind of lubricant of above-mentioned kollag as lubricant composition.Another kind of lubricant is not particularly limited.The example of another kind of lubricant includes organic silicon compound, wax, is different from the above-mentioned another kind of artificial oil, inorganic powder etc. that are used as the artificial oil of decentralized medium.As organo-silicon compound, except silicone oil or silicone wax, can use organopolysiloxane etc., it is by the partially or completely modification such as alkyl, aralkyl, carboxyalkyl or carboxyalkyl, hydroxyl-alkyl, aminoalkyl.

As another kind of lubricant, except above-mentioned various lubricant, grease can be used as animal/vegetable fat, Polyester synthetic lubricant fluid, ZnDTP, MoDTP, ZnDTC, MoDTC, phosphorus system or sulphur system EP agent, sulfoacid calcium etc.Except these lubricants, any lubricant of the releasing agent being generally used for compression casting can be used and be not particularly limited.When the total amount of mineral oil or artificial oil, kollag, thermosetting resin and polymer compound is 100 mass parts, the combined amount of another kind of lubricant is preferably 1 to 10 mass parts.

The thickness of the coating using mold release compositions to be formed can be controlled as 2 to 20 μm.The thickness of coating is preferably 3 to 15, or is preferably 5 to 10 μm.When the thickness of coating is less than 2 μm, lubricity, hot retentivity or can release property may have problems so that releasing agent enough performances are not provided.On the other hand, when the thickness of coating is more than 20 μm, can release property be deteriorated and the residue of release agent components may be deposited on die surface, this may cause less desirable release agent components, its catabolite etc. to be blended in the product of formation.In order to be remained on by the thickness of coating in above shown scope, depend on the shape etc. of mould, relative to being 0.004m ²the area of inner surface of mould, mold release compositions is usually with 0.07 to 0.17cm ³(or in particular, about 0.10 to 0.14cm ³) amount apply.

Be not particularly limited for forming the method for coating, the preparation of formed body and the method for removing coating after shaping on molding die surface.Such as, use device as in figure 1, formation, the preparation of formed body and the removal of coating of coating can be carried out by the method as schematically shown in Fig. 2 and 3.

The nozzle used during coating formation is not particularly limited.External mix two-fluid mixing nozzle can be used, as the two-fluid mixing nozzle 1 with needle-valve in Fig. 1.In FIG, pipeline b is connected to compressor and forced air from this compressor is sent in three pipelines by connector 6.Pipeline 63 is provided with the head tank 4 that pressure-control valve 34 and Qi Nei accommodate mold release compositions.On the other hand, pipeline 61 is provided with pressure-control valve 32 and port magnetic valve (SOL) (magnetic valve) 22.Equally, pipeline 62 is provided with pressure-control valve 33 and port magnetic valve 23.

In the device of above-mentioned Fig. 1, under the pressure being adjusted to predetermined value, releasing agent in head tank 4 is fed to from pipeline 63 to be had in the two-fluid mixing nozzle 1 of needle-valve, simultaneously under a predetermined and supply from pipeline 61 with the air of predetermined flow velocity (wanting injected air).In addition, carry out operation port magnetic valve 23 by only handling solenoid control timer 5 in interval when preset, and air (control air) is supplied from pipeline 62.By air (control air), operation needle-valve and, during only operationally stating needle-valve, the releasing agent supplied from pipeline 63 and the air supplied from pipeline 61 injected and mix at the point of nozzle.Meanwhile, mixed release agent components and air adhere to mould and form coating.Then, in mould, molten metal feed is as molten aluminium alloy, cooling, then discharges from mould thus produces shaped article.

Equally in FIG, pipeline a is connected to compressor and the forced air from compressor to be regulated and through velocity of flow adjust in port magnetic valve 21 through excess pressure in pressure-control valve 31.Forced air through excess pressure adjustment and velocity of flow adjust blows out to remove the release agent components and catabolite thereof that retain on the mold surface from the air-blast nozzle 40 [seeing Fig. 3 (d)] being connected to pipeline c in coating.Afterwards, these steps are repeated.

Embodiment

Hereinafter, by use embodiment and utilize Fig. 2 and 3 to describe the present invention particularly.

In the embodiment of following display, steel plate 7 and cylindrical mold 20 is used to simulate mould.For for spraying mold release compositions to form coating and to remove the air blast of coating after shaping, use the device shown in above-mentioned Fig. 1.

Embodiment 1 to 10

[1] preparation of mold release compositions

Mineral oil (has the 20mm measured at 40 DEG C according to JISK2283 ²the dynamic viscosity of/s) in, use typical agitator (revolution; 300rpm) as device, by paraffin (embodiment 1 to 4,6,7,9 and 10 and table 1 and 2 in each in be called as " wax ") or polybutene (embodiment 5 and 8) with each mass ratio shown in table 1 and 2 be mixed into mineral oil (have according to JISK2283 40 DEG C measure 20mm ²the dynamic viscosity of/s) in be dissolved in wherein.Note, when wax will be comprised, by heating wax is dissolved in mineral oil and then carries out said process.Then, high speed agitator (revolution is used with the quality shown in tables 1 and 2 than the kollag of separately display in mixture table 1 and 2 and thermosetting resin; 7000rpm) stir with mixing.Thus, obtained mold release compositions.

Table 1

Table 2

[2] performance evaluation

For the performance of the various mold release compositions of preparation in each project appraisal following above-mentioned [1].

(1) adhesion property

Often kind of mold release compositions of display in table 1 and 2 is loaded in the head tank 4 of Fig. 1 and uses forced air that the internal pressure of this groove is adjusted to 0.1MPa.Then, steel plate 7 (to be made up of SKD61 steel and the length measured and width are 100x100mm, and thickness being 10mm) is placed on the heaters.The temperature of steel plate 7 uses in it thermocouple 8 of the position of below the middle part surface that is inserted into and is located at in-plane upper steel plate 7 2mm to measure, and is adjusted to the set temperature of 300 DEG C, 350 DEG C and 400 DEG C.Then, at each set temperature, steel plate 7 place that apply, the two-fluid mixing nozzle 1 certainly with needle-valve sprays 0.3cm ³mold release compositions (distance between nozzle and steel plate is 75mm, and injecting time is 1.8 seconds, and is 0.3MPa for the pressure of the air sprayed) [see Fig. 2 (a) and 3 (a)].Afterwards, steel plate 7 naturally cools to 30 DEG C.Formed by mold release compositions and adhere to the thickness use electromagnetic spectrum measurer for thickness measurement of the coating of steel plate 7 and evaluate its adhesiveness.The result display of measuring in table 3.

Note, each film thickness in table 3 is the mean value when often kind of mold release compositions being applied under each set temperature three times.

Table 3

Numeric representation film thickness (unit; μm)

As can be seen from Table 3, depend on type and the combined amount thereof of kollag, thermosetting resin and polymer compound, the varied in thickness of coating is very large.Therefore, by considering that the type of motlten metal, condition of molding are as the rippability of temperature, shaping rear coating etc. and regulate the thickness of coating to predetermined value, can carry out shaping.

(2) hot retention

With with above-mentioned (1) in evaluates adhesion property time same way, when steel plate 7 reaches the set temperature of 300 DEG C, by spraying, often kind of mold release compositions is applied on steel plate 7 to form coating.Then, as motlten metal, supply the 25g molten aluminium alloy (" ADC12 " that describe in JISK2219) [seeing Fig. 2 (b) and 3 (b)] at 680 DEG C.Then, continue to measure the temperature of steel plate 7 and check the maximum temperature of steel plate.In this case, can say, because the maximum temperature of steel plate 7 is lower, so heat is unlikely transferred to steel plate 7 from motlten metal, that is, the hot retentivity of the coating formed by often kind of mold release compositions is higher, or in other words, hot retention is more excellent.The result display of measuring in table 4.

Table 4

Mold release compositions	The maximum temperature (DEG C) of steel plate
		Embodiment 1	430
Embodiment 2	440
		Embodiment 3	435
Embodiment 4	475
		Embodiment 5	440
Embodiment 6	465
		Embodiment 7	460
Embodiment 8	455
		Embodiment 9	435
Embodiment 10	430

As can be seen from Table 4, scope is steel plate maximum temperature difference 45 DEG C between minimum and maximum temperature of 430 DEG C (in embodiments 1 and 10) to 475 DEG C (in embodiments 4), and depend on the composition of mold release compositions, hot retention alters a great deal.Therefore, by considering that hot retentivity and other performances are as adhesiveness, rippability etc., can arrange the composition of mold release compositions.

(3) stripping performance of coating

With with above-mentioned (1) in evaluates adhesion property time same way, when steel plate 7 reaches the set temperature of 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C and 500 DEG C, by spraying, often kind of mold release compositions is applied on steel plate 7.Then, former state keep steel plate 7 reach 30 seconds, then with above-mentioned (2) in supply molten aluminium alloy for the same way of hot retentivity to it.Then, allow steel plate 7 to leave standstill and reach one minute and the disc aluminium shaped article 30 [seeing Fig. 3 (c)] removing cylindrical mold 20 and solidification.Then, be certainly connected to the blow-out nozzle 40 [seeing Fig. 3 (d)] of the pipeline c of Fig. 1, blow air (see the air 40a of blowout in Fig. 3 (d) and the coating 10a of removing) at coating 10 place.As the result evaluating rippability, the coating that whole surface can be easily moved away is rated A.Have and to contact with motlten metal and the part that can be easily moved away needs the coating of the part of longer time to be rated B with not contacting with motlten metal and being removed compared with A level coating.There is the part that contacts with motlten metal and not contact with motlten metal and wherein each coating of longer time removed part that needs compared with B level coating is rated C.The result display evaluated in table 5.

Table 5

As can be seen from Table 5, use synthetic wax as in each in the embodiment 1 to 4,6,7,9 and 10 of polymer compound wherein, because the temperature of steel plate is higher, so stripping performance improves.It can also be seen that, use polybutene as in each in the embodiment 5 and 8 of polymer compound wherein, because the temperature of steel plate is lower, stripping performance is more excellent.Therefore, be apparent that, depend on the combination of polymer compound type and steel billet temperature, stripping performance is different.On the other hand, wherein use synthetic wax, graphite and phenol resin as the embodiment 6 of polymer compound, kollag and thermosetting resin respectively and wherein use synthetic wax and graphite and to be also used as by urea resin in the embodiment 7 of thermosetting resin each has excellent stripping performance, and have nothing to do with the temperature of pipe steel plate, and can find out, these mold release compositions can use when not considering the temperature of steel plate.

(4) about the type of thermosetting resin

Embodiment 11 to 18

Use the mineral oil used in embodiment 1 as mineral oil, the wax used in embodiment 1 is as polymer compound, the boron nitride used in embodiment 5 is as kollag, with there is the phenol resin of Four types of different mean molecule quantity as thermosetting resin, and use the melmac with two types of different mean molecule quantity, diallyl phthalate ester resin, and urea resin, prepare mold release compositions in the same manner as in example 1.Similarly, in the evaluation of above-mentioned adhesion property, the ceiling temperature that film thickness is not less than the mold temperature of 10 μm is be evaluated as the ceiling temperature allowing to adhere to.In addition, in the evaluation of the stripping performance of each coating, the lower limit obtaining the mold temperature of A grading or B grading is be evaluated as the lower limit temperature allowing to peel off.The result evaluated is presented in table 6.

As can be seen from Table 6, available mold temperature range depends on the type of thermosetting resin and different.Therefore, will understand, preferably according to using the mold temperature of releasing agent optionally to use dissimilar thermosetting resin.Such as, when product has large thickness and therefore mold temperature is inevitably high, preferably use the phenol resin with large mean molecule quantity in embodiment 13 or 14.On the other hand, when mold temperature low (under these circumstances, the cooling wherein carrying out strengthening is to reduce shaping cycle time), preferably use the urea resin etc. in embodiment 18.Therefore, can find out, can obtain separately according to adhesion property and the stripping performance of mold temperature simultaneously.

(5) about the mean molecule quantity of the phenol resin as thermosetting resin

Embodiment 19 to 26

Use the mineral oil used in embodiment 1 as mineral oil, the wax used in embodiment 1 is as polymer compound, the boron nitride used in embodiment 5 is as kollag, and phenol resin is as thermosetting resin, prepares mold release compositions in the same manner as in example 1.As phenol resin, use and there is different mean molecule quantity and the resin of the Four types used in embodiment 11 to 14.Particularly, number-average molecular weight is used to be 6000 (embodiments 19 and 23), 10,000 (embodiment 20 and 24), 45,000 (embodiment 21 and 25) and 300, the phenol resin of 000 (embodiment 22 and 26), prepares as the sample shown in Fig. 4 each and the iron plate and its bonding of heating two pieces.Use tensile machine, measure the destruction shear stress serving as each sample of adhesiveness index in 350 DEG C (embodiments 19 to 22) or 500 DEG C (embodiment 23 to 26).Measurement result is presented in table 7 and Fig. 5.

SUS304 for the preparation of each material in two pieces of iron plate Fa and Fb of the sample in Fig. 4.In two pieces of iron plate Fa and Fb, each size comprises the length of 35mm, the width of 10mm, and the thickness of 2mm.The length that the phenol resin layer P formed in an end of iron plate Fa measures is about 10mm, and width is about 10mm, and thickness is about 0.2mm (see Fig. 4 (a)).By being placed on the phenol resin layer P top of iron plate Fa the end being heated to the iron plate Fb of 350 DEG C or 500 DEG C in room temperature (25 to 30 DEG C), iron plate Fa and Fb is then made to naturally cool to room temperature and prepare sample.Measure in the following manner and destroy shear stress: utilize another end of clamp iron plate Fa and Fb of tensile machine and rate of extension with 0.1mm/ second on the direction shown in arrow in Fig. 4 (c) pulls iron plate Fa and Fb.

Table 7

As can be seen from table 7 and Fig. 5, in each in embodiment 19 to 26, no matter tack temperature how, and adhesion strength increases with mean molecule quantity and declines.Thus, will be appreciated that and preferably optionally use the phenol resin with different mean molecule quantity according to forming method.Namely, in the forming method (as low pressure casting) that the flowing of molten aluminum is more weak, the thermosetting resin with relatively large mean molecule quantity is used can easily to be peeled off by air blowing after demoulding to allow the release agent coating be not stripped under the flowing of molten aluminum wherein.On the other hand, in the forming method (as compression casting or warm and hot forging) of high adhesion strength needing release agent coating, use the thermosetting resin with less mean molecule quantity to allow the adhesion strength needed for acquisition.

Take the result of the evaluation of the type about thermosetting resin described in above (4) and the evaluation of the mean molecule quantity about phenol resin described in above (5) into consideration, think, usually, when the mean molecule quantity of thermosetting resin is larger, the higher and thermosetting resin of the viscosity of thermosetting resin when melting is unlikely sprawled on the mold surface.Also think, when mean molecule quantity is larger, thermosetting resin solidifies in the short period of time and therefore thermosetting resin is unlikely sprawled on the mold surface.Therefore, when mean molecule quantity is larger, the less and thermosetting resin of bond area solidifies in the short period of time.As a result, enough adhesion strengths are not provided and the destruction shear stress serving as the index of adhesion strength is tending towards declining.

Based on above-mentioned discovery, it is upper and measure the adhered area ratio of adhesive surface that the phenol resin powder with different mean molecule quantity is spread in the iron plate of the high temperature being in 500 DEG C respectively separately.Measurement result is presented in table 7 and Fig. 6.In this test, thermosetting resin is by independent spreading.Therefore, measurement result may be different from when thermosetting resin is as containing the mold release compositions of other components separately by the result obtained during spreading.But as can be seen from table 7 and Fig. 6, when the mean molecule quantity of phenol resin is larger, adhered area is lower, and it is less therefore to destroy shear stress.Therefore, will understand, phenol resin has totally identical trend.

Note, adhered area ratio (%) refers to [(the actual area adhering to iron plate of phenol resin)/spreading has the area of phenol resin powder)] x100.Can think, when temperature is 350 DEG C and mean molecule quantity is 45, when 000, cure retardation and reduce viscosity, increases adhered area ratio, and increases and destroy shear stress.On the other hand, can think, when mean molecule quantity is 300, when 000, cure retardation, but due to original high viscosity, adhered area increases than not increasing and destroying shear stress, but only in slight extent.

Understandably, for thermosetting resin commonly, when mean molecule quantity is larger, the viscosity of thermosetting resin when shaping is higher and the time that is solidification is shorter.Therefore, can think, the another kind of thermosetting resin being different from phenol resin also has identical trend.That is, can think, not only phenol resin, and another kind of thermosetting resin such as melmac or urea resin also have identical trend.By selecting the type of thermosetting resin according to forming method and condition of molding such as mold temperature, and carry out regulation mean molecule quantity according to required adhesion strength, desirable mold release compositions can be provided.

Industrial applicibility

The present invention may be used for the technical field in metal mould forming, and especially may be used for the low pressure casting of technical field as aluminium alloy etc. or the squeeze casting method for it or die forging.

The explanation of letter or number

1; There is the two-fluid mixing nozzle 21,22,23 of needle-valve; Port magnetic valve (magnetic valve) 31,32,33,34; Pressure-control valve 4; Head tank 5; Solenoid control timer 6; Connector 7; Steel plate 8; Thermocouple 9; The releasing agent 10 sprayed; The coating 10a of releasing agent; The coating 20 of removing; Cylindrical mold 30; Formed body 40; Blow-out nozzle 40a; The air Fa of blowout; One piece of iron plate Fb; Another block iron plate P; Phenol resin layer.

Claims

1. a mold release compositions, described mold release compositions comprises:

Mineral oil or artificial oil;

Kollag;

Thermosetting resin; With

Polymer compound,

Wherein said mold release compositions is used by the inner surface being applied to the mould for casting or forging,

The average grain diameter of wherein said kollag the scope of 0.5 micron to 30 microns, and

Wherein when the total content of described mineral oil or described artificial oil, described kollag, described thermosetting resin and described polymer compound is 100 mass percent, the content of described kollag is in the scope of 1 mass percent to 10 mass percent.

2. mold release compositions according to claim 1,

Wherein said kollag is at least one in talcum, boron nitride, graphite, mica, molybdenum bisuphide and fullerene.

3. mold release compositions according to claim 1,

Wherein said thermosetting resin is at least one in phenol resin, epoxy resin, urea resin, melmac, alkyd resins and unsaturated polyester resin.

4. mold release compositions according to claim 1,

Wherein when described mold release compositions is applied to described mould, described thermosetting resin provides adhesive, and

Be decomposed at the temperature of wherein said thermosetting resin between shaping period.

5. mold release compositions according to claim 1,

Wherein, when the number-average molecular weight of described thermosetting resin is 5,000 to 500, the scope of 000 and forming temperature are when the scope of 300 to 550 DEG C, and adhesion strength is in the scope of 0.1MPa to 5.0MPa.

6. mold release compositions according to any one of claim 1 to 5,

Wherein said polymer compound is at least one in synthetic wax and native paraffin.

7. mold release compositions according to any one of claim 1 to 5,

Wherein said polymer compound is at least one in synthetic wax and polybutene.

8. mold release compositions according to claim 7,

Wherein, during being applied to described mould at described mold release compositions, the temperature of described mould be equal to or higher than 250 DEG C and lower than 400 DEG C time, use described polybutene, and

Wherein, during being applied to described mould at described mold release compositions, when the temperature of described mould is equal to or higher than 400 DEG C and is equal to or less than 550 DEG C, use described synthetic wax.