CN101077995B - Mold cleaning composition - Google Patents
Mold cleaning composition Download PDFInfo
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- CN101077995B CN101077995B CN2007101045368A CN200710104536A CN101077995B CN 101077995 B CN101077995 B CN 101077995B CN 2007101045368 A CN2007101045368 A CN 2007101045368A CN 200710104536 A CN200710104536 A CN 200710104536A CN 101077995 B CN101077995 B CN 101077995B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
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Abstract
The present invention relates to a mold cleaning composition comprising an unvulcanized rubber, a cleaning agent, and a vulcanizing agent, in which the cleaning composition as a whole has a weight average molecular weight (Mw) within a range of from 200,000 to 460,000 according to the measurement by gel permeation chromatography (GPC). The mold cleaning composition has an excellent property of being filled in a mold and capable of exhibiting an excellent cleaning effect on contaminants of the mold due to the excellent filling property.
Description
Technical field
The present invention relates to a kind of mold cleaning composition, its be a kind of be used for to mould clean, the mould cleaning material of regeneration etc., the mould that is used for thermoplastic resin composition's moulding material that described mould is for example polluted by molded operation repeatedly, especially, this mold cleaning composition be used for to the mould that uses the transmission mechanography of epoxy molding material by transmitting mechanography molded semiconductor element in molded operation clean, regeneration etc.
Background technology
As traditional mould purging method, known method of carrying out the mould clean-out operation is by dismantling mould from molding equipment, for example sand-blast, spray dry ice method, spraying and highly basic washing out method.Yet, being undertaken in the situation of mould clean-out operation, needing the very long activity duration by dismounting mould from molding equipment, this operation needs a large amount of labor forces.Therefore more frequent employing is to being installed in the method that mould on the molding equipment carries out clean-out operation, studied the purging method, the purging method that uses UV-irradiation that use melamine resin, used the purging method of sheet cleaning combination etc. as this purging method.Wherein developed a kind of mould purging method of from mould, removing pollutent, this method has good working efficiency, it is by carrying out thermofixation and solidified sheet cleaning combination is removed being placed on sheet cleaning combination in the mould, thereby pollutent is transferred on the solidified sheet cleaning combination.
For this sheet cleaning combination, for example a kind ofly use the mold cleaning composition of unvulcanized rubber on the books (referring to patent document 1).In addition, a kind of compound that can moldedly be used to clean is coated in the mould cleaning material that forms on the flat substrates (referring to patent document 2) also on the books.
Patent document 1:JP-A-9-262843
Patent document 2:JP-T-63-502497
Summary of the invention
Yet, use the sheet cleaning combination and pollutent is transferred to the mould purging method that is used to remove pollutent on the sheet cleaning combination and have a problem, the shape or the cavity size that promptly depend on mould in molding process contain air in cavity, the air that accumulates in the cavity corner can cause the sheet cleaning combination can not be full of the situation in this corner, causes fully removing pollutent.For example, for disclosed mold cleaning composition among the JP-A-9-262843, need in clamping process, slightly open mould up and down, reserve about 1～1.5mm slit (at interval), be cut off with rubber sheet in the process that prevents to remove after in the mould hot sulfurization rubber sheet, and prevent that rubber sheet from staying in the mould.Yet in the mould cavity with reduced size and big degree of depth, air remains in the cavity corner, causes forming not filling part.Therefore the problem that pollutent in filling part not can not fully be removed has appearred.Similarly, disclosed mould cleaning material in JP-T-63-502497, because the whole surface of this cavity all is capped, so inner air can not leave cavity, formed not filling part, the problem that causes the pollutent in the filling part not fully not remove.
Therefore, because the sheet cleaning combination is not suitable for standing in the mould of the problems referred to above, therefore used purging method the method for removing this sheet cleaning combination of use for this mould.Yet aforesaid other purging method needs the long time, and a large amount of labor forces also is actual burdensome.
The present invention is owing to above-mentioned situation is finished, and its purpose is to provide a kind of mold cleaning composition with good mould filling properties, and the pollutent in the mould is reached good cleaning performance.
The accompanying drawing summary
Fig. 1 is the skeleton view according to the sheet mold cleaning composition of one embodiment of the present invention.
Fig. 2 is to form the diagram of the state of slit on the sheet mold cleaning composition.
Fig. 3 is the enlarged side view of a slit part.
Fig. 4 is to use the skeleton view of the state of this sheet mold cleaning composition.
Fig. 5 is to use the skeleton view of the state of this sheet mold cleaning composition.
Fig. 6 is to use the skeleton view of the state of this sheet mold cleaning composition.
Fig. 7 is the effect diagram that is used for semiconducter device is carried out to the sheet mold cleaning composition of type.
Fig. 8 is the effect diagram that is used for semiconducter device is carried out to the sheet mold cleaning composition of type.
The description of label and mark:
10: sheet material
11: slit
Embodiment
To achieve these goals, mold cleaning composition of the present invention is a kind ofly to be used for hot briquetting repeatedly and to make the used cleaning combination of moulding material forming mould, as necessary component, it comprises unvulcanized rubber, clean-out system and vulcanizing agent, wherein the weight-average molecular weight (Mw) of this cleaning combination integral body of measuring according to gel permeation chromatography (GPC) is set at 200, in 000～460,000 the scope.
The present inventor has carried out extensive studies, obtained a kind of cleaning combination that can be full of each part of mould cavity satisfactorily and effectively remove the pollutent in the mould cavity, it is by preventing to realize being full of cavity by the formed not filling part of dead air pocket that uses mold cleaning composition to produce in mould clean-out operation process.The inventor is absorbed in the filling properties of mould cavity, is primarily aimed in the process of filling cleaning combination to make the flowability of the minimized cleaning combination of dead air pocket in the mould cavity carry out a series of research.More specifically, in order to improve the filling properties of mould cavity, need reach a kind of flow state, it can minimize dead air pocket in filling the process of this cleaning combination and reduce the die clearance that is used to improve the mould cavity internal pressure in molded (clamping) process.Especially, according to the performance that adapts to mould cavity, preferably the viscosity of this cleaning combination can be lower, but when viscosity is too low can not push dead air pocket the time, the internal pressure in molding process in the mould cavity can reduce, and causes the not formation of filling part.On the other hand, when the viscosity of this cleaning combination is too high, can variation to the adaptability of mould cavity, make to be easy to form not filling part.The inventor has carried out further research on the basis of above-mentioned discovery, obtained a kind of cleaning combination with proper viscosity, the cleaning combination of weight-average molecular weight (Mw) in above-mentioned institute restricted portion that discovery is measured according to gel permeation chromatography (GPC) can have suitable viscosity and good filling property energy, therefore finished the present invention.
That is, the present invention relates to following content:
(1) a kind of mold cleaning composition, it comprises unvulcanized rubber, clean-out system and vulcanizing agent, and wherein the weight-average molecular weight (Mw) of this cleaning combination integral body of measuring according to gel permeation chromatography (GPC) is 200,000～460, in 000 scope.
(2) according to the mold cleaning composition of (1), wherein the weight-average molecular weight (Mw) of this cleaning combination integral body of measuring according to gel permeation chromatography (GPC) is 220,000～430, in 000 scope.
(3) according to the mold cleaning composition of (1) or (2), it has sheet or strip shape.
(4) according to each mold cleaning composition in (1)～(3), wherein this clean-out system be selected from following at least a: glycol ether, imidazoles, tetrahydroglyoxaline and amino alcohol.
(5) each mold cleaning composition in basis (1)～(4), wherein with respect to the unvulcanized rubber of 100 weight parts, the content of clean-out system is 10～60 weight parts.
(6) each mold cleaning composition in basis (1)～(5), it further comprises the water of 1～20wt.%.
(7) each mold cleaning composition in basis (1)～(6), it further comprises releasing agent.
(8) each mold cleaning composition in basis (1)～(7), wherein this mold cleaning composition has flake shape, wherein with predetermined space a plurality of wire slits is set parallel to each other also in a direction on its sheet surface.
(9) according to the mold cleaning composition of (8), the described sheet mold cleaning composition that is arranged so that of wherein said slit can be folded.
(10) according to the mold cleaning composition of (8), wherein the described sheet mold cleaning composition that is arranged so that of affiliated slit can be cut open along described slit.
(11) each mold cleaning composition in basis (1)～(10), it is to be used for the repetition thermoforming so that the used cleaning combination of moulding material forming mould.
As mentioned above, mold cleaning composition of the present invention comprises unvulcanized rubber, clean-out system and vulcanizing agent as necessary component, and its whole weight-average molecular weight (Mw) of measuring according to gel permeation chromatography (GPC) is in specified range.Therefore, this cleaning combination has suitable viscosity, has obtained the good performance that is packed in the mould.Therefore, when using mold cleaning composition cleaning die of the present invention surface, mould cavity evenly is full of by this mold cleaning composition, cause contamination adhesion on the die surface to this mold cleaning composition, so pollutent can remove along with mold cleaning composition whole removing from mould.For example utilizing composition epoxy resin to repeat the die surface of transmission mechanography molded, that be used for the molded semiconductor element, pollutent is incorporated in the moulded product that is formed by this mold cleaning composition so that it is effectively removed from mould, can carry out the cleaning of mould effectively like this.Therefore, has good surface appearance by the semiconducter device that uses this mould that utilizes mold cleaning composition of the present invention to clean to make.
Have at this mold cleaning composition under the situation of sheet or strip-like appearance, can easily place this mold cleaning composition and be used for the cleaning die cavity.
Further, use glycol ether, imidazoles, tetrahydroglyoxaline or amino alcohol, can obtain good mould cleaning performance as clean-out system.
When mold cleaning composition comprises the water of 1～20wt.% content, can reach better cleaning performance.
When this mold cleaning composition is molded so that it has the sheet profile and when the lip-deep direction setting of its sheet has a plurality of wire slit, can be by this sheet material is folding and easily pile up this sheet material along slit.In this case, owing to interconnected by the part of separated each the piece spare of this parallel slit below slit, so this sheet material can fitly pile up, and can not be shifted in folding process, and each piece spare can not exist intersection or alternate manner in accumulation.Therefore, the heap group that obtains not is erose.By the sheet cleaning combination that uses this neat accumulation mould is cleaned, can reduce under other situation for example owing to the not enough cleaning that causes of the contact pressure between unvulcanized rubber and the die surface was lost efficacy.In addition, owing to do not need to measure sheets of sizes this sheet material being cut into the fritter of same size, and, therefore can simplify cleaning operation owing to do not need the sheet material fritter of this incision is arranged the complex operations that is used to pile up.
In addition, when this mold cleaning composition has the sheet profile, and particularly when its lip-deep direction setting of sheet have a plurality of wire slits so that this sheet mould clean component can be when this slit cuts, can easily sheet material be cut and adapt to littler die size and do not have irregularity.
Below, embodiments of the present invention will be described.
Mold cleaning composition integral body of the present invention has specific weight-average molecular weight, can make as necessary component as unvulcanized rubber, clean-out system and the vulcanizing agent of base mateiral by using.
Comprise as the elastomeric material example of unvulcanized rubber but be not confined to especially: conventional rubber, for example divinyl rubber (BR), ethylene-propylene-dience rubber (EPDM), ethylene-propylene rubber (EPM) and styrene butadiene rubbers (SBR).These can use separately or two or more are used in combination.Each these unvulcanized rubber all vulcanizes in mould and becomes vulcanized rubber.
Wherein, can preferably use EPM, EPDM, BR or its mixture as unvulcanized rubber, because these rubber are less contaminated when using mould to carry out molding sulfuration, and the foul odour in sulfidation is less.
More specifically, EPDM is a kind of ter-polymers that comprises ethene, alpha-olefin (particularly propylene) and following listed multi-olefin monomer, the example of this multi-olefin monomer comprises Dicyclopentadiene (DCPD), 1,5-cyclooctadiene, 1,1-cyclooctadiene, 1,6-encircles 12 carbon diene, 1,7-encircles 12 carbon diene, 1,5,9-cyclododecatriene, 1,4-cycloheptadiene, 1,4-cyclohexadiene, norbornadiene, methene norbornene, 2-methylpentadiene-1,4,1,5-hexadiene, 1,6-heptadiene, methyl-tetrahydro-indenes and 1, the 4-hexadiene.
Each monomeric copolymerization ratio can be for example ethene 30～80mol% among the EPDM, propylene monomer 0.1～20mol%, and remaining is the alpha-olefin in the terpolymer.More preferably, ethene is 30～60mol%.Preferred use weight-average molecular weight (Mw) is 100,000～300,000 EPDM, and more preferably weight-average molecular weight (Mw) is 150,000～250,000.
For divinyl rubber (BR), can use 1,2-polyhutadiene, 1 or its mixture.The mooney viscosity ML of divinyl rubber
1+4(100 ℃) can be 20～80, more preferably 35～60.Preferred use weight-average molecular weight (Mw) is 200,000～600,000 divinyl rubber, and more preferably weight-average molecular weight is 400,000～600,000.
The example of clean-out system comprises glycol ether, imidazoles, tetrahydroglyoxaline and amino alcohol.These can use separately or two or more are used in combination.
Above-mentioned glycol ether is the compound shown in the following formula (1).
R
1O-(CH
2CH
2O)
n-R
2(1)
(in formula (1): n is a positive integer, R
1And R
2The hydrogen or alkyl of respectively doing for oneself.Work as R
1And R
2When one of them was hydrogen, another was an alkyl.Work as R
1And R
2When all being alkyl, R
1And R
2Can be identical or different.)
The example of glycol ether as the formula (1) comprises glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dme, tetraethyleneglycol dimethyl ether, Polyethylene glycol dimethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether.These can use separately or two or more are used in combination.
In above-mentioned glycol ether as the formula (1), preferably using repeat number n is 1～2, and R
1And R
2In one for having the alkyl of 1～4 carbon atom, and another is hydrogen those; Perhaps repeat number n is 1～2, and R
1And R
2Be those of alkyl, work as R
1And R
2It has 1～4 carbon atom separately when being alkyl.Herein, when repeat number n is 3 or when bigger, with the compatibility of rubber can variation.In addition, the carbonatoms in alkyl is 5 or more for a long time, and the perviousness of releasing agent in the oxidative degradation layer can variation.The boiling point of glycol ether preferably can be about 130 ℃～250 ℃.More specifically, because mould molding carries out under 150 ℃～185 ℃ usually, under some situation when the boiling point of glycol ether is lower than 130 ℃, the evaporation meeting in the cleaning process is accelerated greatly, causes the operating environment variation of cleaning.When its boiling point was higher than 250 ℃, the evaporation difficulty that becomes very made glycol ether remain in the vulcanized rubber, and the intensity of the vulcanized rubber after cleaning like this can reduce, in case from mould this cleaning combination of taking-up, vulcanized rubber just may break or or the like.Therefore, be difficult to satisfactorily the oxidative degradation layer of releasing agent etc. is peeled off from die surface, cause the deterioration of efficiency that makes cleaning operation easily.
Various glycol ethers can use separately, or and water, alcohols such as methyl alcohol, ethanol and n-propyl alcohol, perhaps organic solvent such as toluene and dimethylbenzene mix use.Mix under the situation about using at glycol ether and organic solvent, with respect to the glycol ether of 100 weight parts, the content of organic solvent is preferably set to 50 weight parts or lower, more preferably 20 weight parts or lower.
Can realize favourable effect as shown in the formula the imidazoles shown in (2) as above-mentioned imidazoles by using.
(in formula (2): each R is H, have substituting group and have 10 or the straight-chain alkyl of carbon atom still less, perhaps do not have substituting group and have 10 or the straight-chain alkyl of carbon atom still less, and perhaps be aryl, each R can be identical or different.)
The example of this imidazoles comprises glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-phenmethyl-glyoxal ethyline and 2,4-diamino-6[2 '-methylimidazolyl-(1) '] ethyl-s-triazine (triadine).These can use separately or two or more are used in combination.
Can realize favourable effect as shown in the formula the tetrahydroglyoxaline shown in (3) as above-mentioned tetrahydroglyoxaline by using.
(in formula (3): each R is H, have substituting group and have 10 or the straight-chain alkyl of carbon atom still less, perhaps do not have substituting group and have 10 or the straight-chain alkyl of carbon atom still less, and perhaps be aryl, each R can be identical or different.)
The example of this tetrahydroglyoxaline comprises glyoxal ethyline quinoline, 2-methyl-4-ethyl imidazol(e) quinoline, 2-benzylimidazoline, 1-phenmethyl-glyoxal ethyline quinoline, 2 phenyl 4 methyl 5 hydroxy methylimidazole quinoline, 2,4-diamino-6[2 '-Methylimidazole quinoline base-(1) '] ethyl-s-triazine (triadine), 2,4-diamino-6[2 '-methyl-4 '-imidazolinyl-(1) '] ethyl-s-triazine (triadine), 1-1-cyanoethyl-2-methylimidazole quinoline and 1-cyanoethyl-2-methyl-4-ethyl imidazol(e) quinoline.These can use separately or two or more are used in combination.
As the situation of glycol ether, each imidazoles and tetrahydroglyoxaline can use separately, or mix use with alcohols such as methyl alcohol, ethanol and n-propyl alcohol or organic solvent such as toluene and dimethylbenzene.Imidazoles and alcohols or organic solvent are being mixed under the situation about using, at least a with respect in the imidazoles of 100 weight parts and the tetrahydroglyoxaline, the content of alcohols and organic solvent can be preferably set to 50 weight parts or lower, more preferably 20 weight parts or lower.
For above-mentioned amino alcohol, following amino alcohol can be used to realize favourable effect.
The representative example of amino alcohol comprises Monoethanolamine MEA BASF, diethanolamine, trolamine, N-Mono Methyl Ethanol Amine, N, N-dimethylethanolamine, N, N-dibutyl thanomin, N, N-diethylethanolamine, N-methyl-N, N-diethanolamine, 2-amino-2-methyl propyl alcohol, 3-aminopropanol and 2-aminopropanol.These can use separately or two or more are used in combination.
As the situation of above-mentioned other clean-out system, amino alcohol can use separately, or mixes use with alcohols such as methyl alcohol, ethanol and n-propyl alcohol or organic solvent such as toluene and dimethylbenzene.Hydramine is being mixed with alcohols and organic solvent under the situation about using, with respect to the amino alcohol of 100 weight parts, the content of alcohols or organic solvent can be preferably set to 50 weight parts or lower, more preferably 20 weight parts or lower.
With respect to the unvulcanized rubber of 100 weight parts, the content of clean-out system (glycol ether, imidazoles, tetrahydroglyoxaline or amino alcohol) can be preferably set in the scope of 10～60 weight parts, more preferably 15～25 weight parts.When the content of clean-out system is lower than 10 weight parts, be difficult to mould is played gratifying cleaning performance.When its content surpassed 60 weight parts, in the situation that the mold cleaning composition that use is made like this cleans mould, said composition can adhere on the mould, therefore can reduce the operation efficiency that said composition is peeled off from mould.
Vulcanizing agent is not particularly limited, and conventional vulcanizing agent can adopt.The example of vulcanizing agent comprises sulphur and organo-peroxide, normal-butyl-4 for example, 4-two (t-butylperoxy) valerate (valelate) and 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane.These can use separately or two or more are used in combination.With respect to the unvulcanized rubber of 100 weight parts, the content of vulcanizing agent can be preferably set in the scope of 1～3 weight part.
Further, except unvulcanized rubber, clean-out system and vulcanizing agent, mold cleaning composition of the present invention can randomly comprise releasing agent, toughener etc.
Releasing agent is not particularly limited, and conventional releasing agent can adopt.The example of releasing agent comprises longer chain fatty acid, for example stearic acid and docosoic acid; The metal-salt of longer chain fatty acid, for example Zinic stearas and calcium stearate; Ester group wax, for example partly-hydrolysed ester of carnauba wax, montanin wax and montanic acid; Long-chain fat acid amides, for example stearyl-ethylene diamide; And paraffin, for example polyethylene wax.
With respect to the gross weight of mold cleaning composition, the content of releasing agent can be preferably set in the scope of 1～10 weight %.When releasing agent content during, be difficult to show enough stripping results less than 1 weight %.When its content surpasses 10 weight %, cleansing power meeting variation, the outward appearance of the moulded product that the use mould is made after regeneration also can variation.
The example of toughener comprises inorganic strengthening agent (filler), for example silicon-dioxide, aluminum oxide, carbon black, lime carbonate, Calucium Silicate powder, aluminium hydroxide, titanium dioxide and titanium oxide.With respect to the unvulcanized rubber of 100 weight parts, the content of toughener can be preferably set in the scope of 10～50 weight parts.
Further, when cleaning combination comprises unvulcanized rubber mud as base mateiral, can in unvulcanized rubber, add water.With respect to the gross weight of mold cleaning composition, the content of water can be preferably set in the scope of 1～20 weight %.
Mold cleaning composition of the present invention can adopt for example following method preparation.To mix with clean-out system, vulcanizing agent and other additive as the unvulcanized rubber of base mateiral, it is mixing to use the batch melting machine that mixture is carried out, and utilizes forcing machine or roller to form sheet or belt like shape then, obtains mold cleaning composition thus.When mold cleaning composition used with sheet-form, the thickness of this sheet material was set at 3～10mm usually.
The weight-average molecular weight (Mw) of the mold cleaning composition integral body that need will obtain thus is adjusted to 200,000～460,000, and this is recorded by gel permeation chromatography (GPC).Its particularly preferred weight-average molecular weight (Mw) is 220,000～430,000.When Mw less than 200,000 o'clock, the viscosity of mold cleaning composition reduces, in molding process, from the space of mould, understand leak pressure, because the mould cavity pressure inside reduces, and makes this mold cleaning composition can not be extended to each part of mould, causes the not formation of filling part.When its Mw greater than 460,000 o'clock, the viscosity of this mold cleaning composition improves, thus this mold cleaning composition reduces the conformability of mould cavity, causes the not formation of filling part.
The operation of gpc measurement is as described below.The mold cleaning composition that obtains is immersed in the chloroform, keep leaving standstill 3 days.Then, part heat drying and curing on hot-plate of chloroform will be dissolved in.Use tetrahydrofuran (THF) (THF) solution of 0.1wt.% to regulate this drying that obtains and curing material, keep leaving standstill 1 day.Then, use 0.45 μ m film filter that this solution is filtered, under predetermined condition, use predetermined analyser that filtrate is carried out gpc analysis.In gpc measurement, solvent for use is not defined as THF solution, can suitably select according to the component as the cleaning combination of measurement target.
Mold cleaning composition can be preferably light color, for example the light gray of white and approaching white.By regulating color, can be after mould cleans easily confirm from mould, to remove and be attached to pollutent on the mold cleaning composition by naked eyes, realize determining easily the effect of mould cleaning situation thus.
Under the situation of using mold cleaning composition of the present invention, the preferred use is shaped to flaky mold cleaning composition.When using the sheet mold cleaning composition, from using this sheet mold cleaning composition to carry out the convenience viewpoint of mould cleaning, suitable use sheet material 10 as shown in Figure 1 has with predetermined space and a plurality of wire slits 11 of being set parallel to each other in this sheet surface.More preferably, the sheet surface of this sheet material 10 has candy strip.By using 11 pairs of sheet materials 10 of slit to fold, can fitly pile up sheet material 10.
Further, as shown in Figure 3, the end of each slit 11 and the distance between the sheet surface of these slit 11 ends are preferably set to about 0.1～0.8mm, more preferably 0.2～0.5mm.When this distance during less than 0.1mm, piece spare 10a easily easily separately and when this distance during greater than 0.8mm, folds more unsmooth.
The sheet mold cleaning composition of the application of the invention carries out the method that mould cleans to the mould that is used for the molded semiconductor device.For example, the sheet material of sulfided state not is placed in the mould, hot sulfurization intactly is attached on the sheet material pollutent then.Then, from mould, take out and finish mould and clean by vulcanizing sheet material.
To describe the mould purging method that uses the sheet mold cleaning composition below in order in detail.
At first, prepare sheet mold cleaning composition of the present invention.Then, sheet mold cleaning composition 10 is placed on as shown in Figure 4 the mold 1 that forms depression 3a and forms between the bed die 2 of depression 3b, mold 1 and bed die 2 clampings are clipped in the middle this sheet mold cleaning composition 10, carry out pressure forming, as shown in Figure 5.Sheet material 10 is packed into by in the formed cavity 3 of the depression 3b that forms in depression 3a that forms in the mold 1 and the bed die 2, and the pressure of using by moulding makes itself and die surface reach pressure and contacts.In this state, make the unvulcanized rubber baking form vulcanized rubber with heating, make the oxidative degradation layer etc. of the releasing agent that forms in the cavity 3 combine with vulcanized rubber by moulding.Sometimes the burr around the cavity 3 also combines with vulcanized rubber.Then, as shown in Figure 6, open mold 1 and bed die 2 after the section at the fixed time, strip down from the sheet mold cleaning composition 10 that will become vulcanized rubber up and down between the mould 1 and 2, the oxidative degradation layer that will combine with sheet material 10 etc. gets off from the sur-face peeling of mould 1 up and down and 2 thus.So just finished the cleaning of mould.
As the sheet mold cleaning composition, can use sheet mold cleaning composition as shown in Figure 1, it has a plurality of wire slits 11 parallel to each other that with predetermined space being used to of forming sheet material 10 can be folded in sheet surface.
Under the situation of using this sheet cleaning combination, as shown in Figure 7, the piece spare 10a with desired number downcuts from sheet material 10 upper edge slits 11.This cutting can be by picking up sheet material 10 and repeating folding or by using cutter etc. to carry out along slit 11 with finger.Then, as shown in Figure 8, along slit 11 pleated sheets 10, the upper surface of sheet material 10 (forming the surface of slit 11) (, downcuts 4 piece spare 10a herein) outwardly in Fig. 8, this sheet material 10 is folding continuously, thereby contact with each other until its bottom surface and to pile up piece spare 10a, as shown in Figure 8.Sheet material 10a can not be separated from each other in folding process, because piece spare 10a is connected with each other at the base section 11a place of slit 11.Therefore, only by simple folding operation, just piece spare 10a fitly can be piled up, piece spare 10a is longitudinally with transversely arranged, and piece spare 10a can be not intersected with each other.Therefore, can eliminate the labor capacity that is used for sheet material 10 is cut into onesize fritter and sheet material 10 sizes are measured or the piece spare 10a that separates is arranged.
Although it is folding and two piece spare 10a are deposited in addition state on two 10a in this four piece spare 10a centers that four piece spare 10a that will downcut from sheet material have been shown among Fig. 8, but the present invention is not limited thereto, can be according to the size of mould that will clean or cavity, the piece spare 10a of cutting and folding proper amt is piled into suitable size (for example using 6 piece spare 10a that three piece spare 10a are deposited on other three piece spare 10a) with piece spare 10a.
Use a kind of example of the mould of mold cleaning composition of the present invention to be: for example a kind of mould that is used for type that semiconducter device is carried out to, utilize this mould, carry out the repetition moulding by using compositions of thermosetting resin.
In the mould that the semiconducter device moulding of a kind of mould example that adopts mold cleaning composition of the present invention is used, comprise as the compositions of thermosetting resin of molded resin material containing the composition epoxy resin of Resins, epoxy as main ingredient.
In this compositions of thermosetting resin, usually solidifying agent is used in combination with composition epoxy resin as main ingredient.
Because the mould that adopts mold cleaning composition of the present invention to clean does not have pollutent, die surface is returned to initial conditions, thereby before the use compositions of thermosetting resin carries out moulding as moulding stock to semiconductor packages, will apply releasing agent usually at die surface.For example, when comprising montanic acid wax and carry out moulding, preferably apply montanic acid wax as the moulding stock of releasing agent.For the method that applies montanic acid wax at die surface, the preferred use comprises montanic acid wax and is shaped to flaky unvulcanized rubber composition, for example can pass through aforesaid unvulcanized rubber and the mixed sheet material that gets of releasing agent.Adopt and the identical mode of cleaning process of using the sheet mold cleaning composition, will be placed in the mould by the sheet material that the unvulcanized rubber that comprises montanic acid wax is made and heating, make the montanic acid wax that wherein comprises be coated to die surface.Think by baking, the montanic acid wax fusing in the unvulcanized rubber composition, and spill into die surface, form uniform releasing agent film on its surface.
With respect to the elastomeric material of 100 weight parts in the unvulcanized rubber composition, the content of montanic acid wax can be preferably set to the scope of 15～35 weight parts, more preferably 20～30 weight parts.When the content of montanic acid wax is lower than 15 weight parts, can not show sufficient stripping result.When its content surpassed 35 weight parts, montanic acid wax was too much at the coated weight of die surface, caused the moulded product degraded appearance by using this mould to obtain after cleaning and regenerating.
Below embodiment and Comparative Examples will be described.
Embodiment 1～6 and Comparative Examples 1～5
The component of ratio that will be shown in table 1 and 2 is mixed, and it is mixing to use mixing roll that each mixture is carried out, and the applying pressure roller carries out roll-in and obtain the sheet material that thickness is 5mm, obtains required sheet mold cleaning composition thus.
The weight-average molecular weight (Mw) of each sheet mold cleaning composition of mensuration as described below.This sheet mold cleaning composition is immersed in the chloroform, keep leaving standstill 3 days.Then, the part that will be dissolved in chloroform is also solidified in 50 ℃ of heat dryings on hot-plate, uses tetrahydrofuran (THF) (THF) solution of 0.1wt.% to regulate this drying that obtains and curing material, keeps leaving standstill 1 day.Then, use 0.45 μ m film filter that this solution is filtered, under following test condition, use gpc analysis instrument (HLC-8120GPC is made by Tosoh Corporation) that the weight-average molecular weight (Mw) of filtrate is measured.
Measuring condition
Post: GMHXL+GMHXL+G3000HXL is made by Tosoh Corporation
Column dimension: the diameter of each post is 7.8mm * 30cm, overall size: 90cm
Column temperature: 40 ℃
Elute soln: THF
Flow velocity: 0.8ml/min
Inlet pressure: 2.3MPa
Injection volume: 100 μ l
Detector: differential refractometer (RI)
Standard: polystyrene (PS)
Data processing equipment: GPC-8020 is made by Tosoh Corporation
As described below to estimating by the filling properties of each routine sheet mold cleaning composition of the above-mentioned embodiment that obtains, Comparative Examples and routine.Be used for the mould [die size: 24mm * 91mm that filling properties is estimated by use; Mould cavity size: 4mm * 5mm * 2.0mm (total depth of cavity up and down)], estimate the packing ratio of the poorest cavity of filling properties in 16 kinds of cavitys, the results are shown in table 1 and table 2.
By floorage and the resulting moulded product cavity floorage partly of calculating mould cavity, calculate its packing ratio of detection recently between the above-mentioned floorage then.As shown in Figure 4, in the mould that is made of mold 1 and bed die 2, eight cavitys 3 are lined up two row parallel to each other.Space between the cavity 3 that is set parallel to each other as mentioned above is 10mm, and eight cavitys 3 arranging at each row are provided with the 1mm spacing.Size as the sheet mold cleaning composition 10 of sample is set at wide 10mm, long 91mm and thick 5mm, sample is arranged between the row of cavity 3 of the mould that is used for estimating, and closing molding carries out hot briquetting then.For condition of molding, this is molded over 175 ℃ and carried out 5 minutes, and the gap between the mould of clamping is 0.5mm.
Table 1 (umber)
*1: the copolymerization ratio of ethene (a), propylene (b) and ethylidene norbornene (c) is 67/31/2 mol ratio, and weight-average molecular weight (Mw) is 220,000.
*2:1, the 4-polyhutadiene; Mooney viscosity ML
1+4(100 ℃) are 45M; Weight-average molecular weight (Mw) is 490,000.
*3:2,4-diamino-6[2 '-Methylimidazole quinoline base-(1) '] ethyl-s-triazine (triadine).
*4:2-methyl-4-ethyl imidazol(e) quinoline.
*5: ethylene glycol monomethyl ether.
*6:2-amino-2-methyl propyl alcohol.
*7: normal-butyl-4,4-two (t-butylperoxy) valerate (valelate).
Table 2 (umber)
*1: the copolymerization ratio of ethene (a), propylene (b) and ethylidene norbornene (c) is 64/34/2 mol ratio, and weight-average molecular weight (Mw) is 180,000.
*2:1, the 4-polyhutadiene; Mooney viscosity ML
1+4(100 ℃) are 45M; Weight-average molecular weight (Mw) is 490,000.
*3:2,4-diamino-6[2 '-Methylimidazole quinoline base-(1) '] ethyl-s-triazine (triadine).
*4:2-methyl-4-ethyl imidazol(e) quinoline.
*5: ethylene glycol monomethyl ether.
*6:2-amino-2-methyl propyl alcohol.
*7: normal-butyl-4,4-two (t-butylperoxy) valerate (valelate).
Can see that from The above results the packing ratio that the embodiment sample of each the sheet cleaning combination of weight-average molecular weight (Mw) in specified range shows is 100%, it has obviously good filling properties.In contrast to this, weight-average molecular weight (Mw) the not packing ratio that shows of the comparative example of each the sheet cleaning combination in this specified range is lower than embodiment, because its filling properties is relatively poor, therefore is difficult to use in actual applications Comparative Examples.
The embodiment that uses the sheet mold cleaning composition with slit will be described below.
Embodiment 7
As shown in Figure 1, being cut into each the sheet mold cleaning composition (thickness (T among Fig. 1) is 5mm) that obtains in the foregoing description 1～6 separately, width (A among Fig. 1) is the sheet material 10 of 300mm for 230mm and length (B among Fig. 1).The degree of depth is the slit 11 of 4.5mm being formed parallel to each other separately with the interval (C among Fig. 1) of 15mm on sheet material 10 widths on the entire upper surface of sheet material 10.Be that each slit 11 end and the spacing (D among Fig. 3) between these terminal sheet material 10 surfaces are 0.5mm.In this sheet material 10, form 20 piece spare 10a.According to several transmission device for molding with different die sizes, cutting respectively has the sheet mold cleaning composition 10 of slit 11, and is folding at a part of slit 11 places, thereby its accumulation is placed in the mould.Closed mould carries out hot briquetting then, measures packing ratio.Found that similarly to aforementioned sheet mold cleaning composition, packing ratio is all higher, and filling properties is very good.
Mold cleaning composition of the present invention is used for for example those are used for the cleaning and the regeneration of the mould of thermoset rubber moulding material, for example is used for by using epoxy molding material to transmit molded semiconductor element being carried out to the cleaning and the regeneration of the used mould of the transfer moulding method of type.
Although the present invention is described in detail,, obviously can carry out various changes and variation to it without departing from the present invention for those skilled in the art with reference to its special embodiment.
The present invention is based on the Japanese patent application 2006-145544 that proposed on May 25th, 2006 and makes, and its whole contents is included in this as a reference.
Further, all reference papers cited herein all integral body be included in this.
Claims (9)
1. mold cleaning composition, it comprises unvulcanized rubber, clean-out system and vulcanizing agent, wherein measure the weight-average molecular weight (Mw) of described cleaning combination integral body 220 according to gel permeation chromatography (GPC), 000～430, in 000 scope, and wherein with respect to the unvulcanized rubber of 100 weight parts, the content of clean-out system is in the scope of 10～60 weight parts.
2. according to the mold cleaning composition of claim 1, it has sheet or belt like shape.
3. according to the mold cleaning composition of claim 1, wherein said clean-out system be selected from following at least a: glycol ether, imidazoles, tetrahydroglyoxaline and amino alcohol.
4. according to the mold cleaning composition of claim 1, it further comprises the water of 1～20wt.%.
5. according to the mold cleaning composition of claim 1, it further comprises releasing agent.
6. according to the mold cleaning composition of claim 1, wherein said mold cleaning composition has flake shape, wherein also arranges a plurality of wire slits in a direction parallel to each other with predetermined space on its sheet surface.
7. according to the mold cleaning composition of claim 6, the layout of wherein said slit makes described sheet mold cleaning composition to be folded.
8. according to the mold cleaning composition of claim 6, wherein the layout of affiliated slit makes described sheet mold cleaning composition to be cut open along described slit.
9. according to each mold cleaning composition in the claim 1,7 and 8, said composition is applied to clean and repeats thermoforming so that the moulding material forming mould.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006145544 | 2006-05-25 | ||
| JP2006145544 | 2006-05-25 | ||
| JP2006-145544 | 2006-05-25 |
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| Publication Number | Publication Date |
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| CN101077995A CN101077995A (en) | 2007-11-28 |
| CN101077995B true CN101077995B (en) | 2011-05-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101045368A Active CN101077995B (en) | 2006-05-25 | 2007-05-25 | Mold cleaning composition |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR20070114036A (en) |
| CN (1) | CN101077995B (en) |
| MY (1) | MY148591A (en) |
| SG (1) | SG137816A1 (en) |
| TW (1) | TWI373521B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI499668B (en) * | 2009-07-17 | 2015-09-11 | Nitto Denko Corp | Mold cleaning composition and mold cleaning material, and method for cleaning mold using the same |
| US9999994B2 (en) * | 2010-06-07 | 2018-06-19 | Mitsubishi Chemical Corporation | Method for producing product having uneven microstructure on surface thereof, mold release treatment method, and active energy ray curable resin composition for mold surface release treatment |
| JP5741398B2 (en) * | 2011-11-21 | 2015-07-01 | 日立化成株式会社 | Mold cleaning sheet |
| CN103205032A (en) * | 2013-03-14 | 2013-07-17 | 西北工业大学 | Mold cleaning rubber for in-place mold cleaning and preparation method of mold cleaning rubber |
| CN104450302A (en) * | 2014-11-17 | 2015-03-25 | 厦门市钰林丰橡塑科技有限公司 | Flame-retardant high-temperature resistant environment-friendly cleaning product |
| CN105773882A (en) * | 2016-04-19 | 2016-07-20 | 上海东恒化工有限公司 | Composition for die cleaning and die cleaning method |
| CN107011553A (en) * | 2017-05-04 | 2017-08-04 | 天津德高化成新材料股份有限公司 | A kind of rubber mould exempts from dismounting mold cleaning material and preparation method thereof with online |
| CN112553009A (en) * | 2020-11-28 | 2021-03-26 | 无锡市科宇橡胶模具厂 | Cleaning agent for rubber mold and using method thereof |
| CN112662489B (en) * | 2020-12-15 | 2021-10-26 | 广东红日星实业有限公司 | Resin lens cleaning agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184848A (en) * | 1996-12-10 | 1998-06-17 | 日东电工株式会社 | Cleaning composition for mold for molding semiconductor device and method of cleaning mold using same |
| JP3585631B2 (en) * | 1996-03-29 | 2004-11-04 | 日東電工株式会社 | Mold cleaning method |
-
2007
- 2007-05-24 MY MYPI20070819A patent/MY148591A/en unknown
- 2007-05-25 TW TW096118800A patent/TWI373521B/en active
- 2007-05-25 CN CN2007101045368A patent/CN101077995B/en active Active
- 2007-05-25 KR KR1020070050840A patent/KR20070114036A/en not_active Application Discontinuation
- 2007-05-25 SG SG200703779-9A patent/SG137816A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3585631B2 (en) * | 1996-03-29 | 2004-11-04 | 日東電工株式会社 | Mold cleaning method |
| CN1184848A (en) * | 1996-12-10 | 1998-06-17 | 日东电工株式会社 | Cleaning composition for mold for molding semiconductor device and method of cleaning mold using same |
Non-Patent Citations (4)
| Title |
|---|
| 权艳、纪波.GB/T 1232.1-2000《未硫化橡胶用圆盘剪切粘度计进行测定 第1部分：门尼粘度的测定》相关技术问题.化工标准• |
| 权艳、纪波.GB/T 1232.1-2000《未硫化橡胶用圆盘剪切粘度计进行测定 第1部分:门尼粘度的测定》相关技术问题.化工标准•计量•质量.2002,(7),11-16. * |
| 计量• |
| 质量.2002,(7),11-16. |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070114036A (en) | 2007-11-29 |
| SG137816A1 (en) | 2007-12-28 |
| MY148591A (en) | 2013-05-15 |
| TWI373521B (en) | 2012-10-01 |
| TW200806785A (en) | 2008-02-01 |
| CN101077995A (en) | 2007-11-28 |
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