CN101955858B - Mold cleaner composition and mold cleaning material, and method of cleaning using the same - Google Patents
Mold cleaner composition and mold cleaning material, and method of cleaning using the same Download PDFInfo
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- CN101955858B CN101955858B CN201010233007XA CN201010233007A CN101955858B CN 101955858 B CN101955858 B CN 101955858B CN 201010233007X A CN201010233007X A CN 201010233007XA CN 201010233007 A CN201010233007 A CN 201010233007A CN 101955858 B CN101955858 B CN 101955858B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
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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
- C11D7/50—Solvents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention relates to a mold cleaner composition which is the mold cleaner composition for the mold for heating and molding by using molding material to repeatedly mold, comprising synthetic rubber and/or a synthetic resin as base metal, alkali metal salt and/or alkali metal hydroxides, and water and/or an organic solvent.
Description
Technical field
The present invention relates to because repeatedly carry out injection forming or transmit the forming operation such as shapings and contaminated mould, such as for die cleaning agent composition and the mould cleaning material of the uses such as cleaning and regeneration of the semiconductor device molding die of the forming operation of compositions of thermosetting resin etc. and the mould cleaning method that uses it.
Background technology
Generally speaking, because the operations such as injection forming repeatedly or transmission shaping, the volatile component that when the die surface of mould is attached with the heating shaped material, produces, the exudate on molding surface, the releasing agent that uses when being shaped etc., and these dirt settlings are owing to oxidation is gone bad, and mould is contaminated thus.When mould is contaminated like this, finish size, outward appearance, the release property etc. of molding are had a negative impact, therefore not preferred.
Therefore, for the disadvantageous effect that prevents from being caused by contaminated like this mould, the mould that is used for injection forming or transmission shaping need to regularly carry out clean-out operation, and above-mentioned pollutent is removed from die surface.As existing mould purging method, known such as: from building mortion, take apart a die and the method for cleaning with strong base solution or solvent etc.
But, from building mortion, take apart a die and need the operation such as cooling, intensification, desorption, cleaning of mould with the method that strong base solution or solvent clean, the problem that exists is need for a long time to clean, labor capacity is large, and exist since the use of strong base solution or solvent and liquid waste disposal after the operator had a negative impact, cleans etc. to the large such problem of load of people or environment.
Therefore, use thermoset melamine resin shaped material, unvulcanized rubber class mixture etc. have been proposed, use these materials in mould, to form, thus will be integrated at pollutent and molding that die surface generates, and this molding is taken out the method on cleaning die surface from mould, and part is implemented (for example, referring to Patent Document 1).
Patent documentation 1: Japanese kokai publication hei 10-226799 communique
Summary of the invention
For example, the semiconductor device molding die that uses in the forming operation of compositions of thermosetting resin cleans by aforesaid method, but, above-mentioned compositions of thermosetting resin is grouped into difference according to the one-tenth that its desired characteristic consists of, multiple kind is arranged, therefore, the state of the mold fouling that repeatedly produces by forming operation and the composition of pollutent also are varied.Wherein, use and removed with lead or the halogen pollution substance carrying capacity of environment material, that form at mould when the corresponding phenol resin molding material of without halide environment is shaped repeatedly as representative, sintering (the baked I is paid け) especially severe to die surface, existing purging method by aforesaid use thermoset melamine resin shaped material or unvulcanized rubber class mixture can not be removed pollution substance fully, also needs the cleaning material that also can clean such pollution substance.
The present invention carries out in view of such situation, and its purpose is to provide for by forming operation repeatedly and contaminated mould has die cleaning agent composition and the mould cleaning material of good cleaning performance and the mould cleaning method that uses it.
To achieve these goals, of the present invention first will be intended to a kind of die cleaning agent composition, it uses the cleansing composition of mould for the hot briquetting of using formed material to carry out repeatedly moulding, wherein contain: as synthetic rubber and/or the synthetic resins of mother metal, an alkali metal salt and/or alkali metal hydroxide, and water and/or organic solvent.
In addition, of the present invention second will be intended to a kind of mould cleaning material, and it obtains by using the die cleaning agent composition to be configured as sheet.
And, the of the present invention the 3rd will be intended to a kind of cleaning method of mould, it comprises following operation: the mould cleaning material that will comprise described die cleaning agent composition is placed into the operation on the profile of mould of unlatching, described mould and clip described mould cleaning material and carry out heating and pressurizing closes, make thus the pollutent and the integrated operation of described mould cleaning material that form at die surface, and cleaning mold is surperficial with the integrated mould cleaning material of pollutent by peeling off from mould.
Namely, even the cleansing composition that the pollution substance that the inventor forms at mould when obtaining using as previously mentioned the corresponding phenol resin molding material of Halogen environment repeatedly to be shaped also can effective cleaning be removed, carried out extensively and profoundly research, found that, when the synthetic rubber and/or the synthetic resins that contain as mother metal, an alkali metal salt and/or alkali metal hydroxide, during with water and/or organic solvent, produce dissolving or the Decomposition of dirt by the effect of water or organic solvent, and by making above-mentioned an alkali metal salt and/or alkali metal hydroxide and depositing, can realize promoting the dissolving of dirt or the effect of Decomposition, therefore, by their synergy, can realize than existing better cleaning performance, thereby finish the present invention.
As mentioned above, die cleaning agent composition of the present invention contains synthetic rubber and/or the synthetic resins as mother metal, an alkali metal salt and/or alkali metal hydroxide, and water and/or organic solvent.Therefore, even the pollutent that forms for repeatedly forming operation, particularly be difficult to fully clean with existing composition for cleaning, use got rid of the thermosetting resin shaped material with lead or halogen, antimony is the pollution substance that the corresponding phenol resin molding material of the Halogen environment behind the carrying capacity of environment material of representative forms at die surface when repeatedly forming operation, owing to having synergy, namely produce dissolving or the Decomposition of dirt by the effect of water or organic solvent, and by making above-mentioned an alkali metal salt and/or alkali metal hydroxide and depositing the dissolving that promotes dirt or the effect of Decomposition, remove effect and bring into play good cleaning.Therefore, the die cleaning agent composition of the application of the invention carries out the cleaning of die surface, the pollutent that forms at die surface is attached on this die cleaning agent composition also integrated, thereby pollutent can be removed from mould effectively, for example, the semiconductor element encapsulation that uses composition epoxy resin repeatedly to be shaped is integrated with the molding that comprises this die cleaning agent composition with the pollutent of die surface, can effectively remove pollutent from mould, the effective cleaning mould.As a result, the semiconductor device that uses the mould after die cleaning agent composition of the present invention cleans to form obtains the no problem good goods of outward appearance.And, after the mould cleaning material that will comprise die cleaning agent composition of the present invention is placed on the profile of mould of unlatching, described mould and clip described mould cleaning material and carry out heating and pressurizing closes, make thus the pollutent and the described mould cleaning material that form at die surface integrated, can the cleaning mold surface by peeling off from mould with the integrated mould cleaning material of pollutent.
When particularly above-mentioned synthetic rubber was ethylene-propylene class rubber and/or divinyl rubber, the processing ease when mould cleans can be realized the raising of clean-out operation.
In addition, the content of above-mentioned an alkali metal salt and/or alkali metal hydroxide when being set as specified proportion as the synthetic rubber of mother metal and/or synthetic resins 100 weight parts, can be obtained better cleanup action.
In addition, contain organic solvent and water when simultaneously, and with the content of water when being set as specified proportion as the synthetic rubber of mother metal and/or synthetic resins 100 weight parts, can obtain better cleanup action.
Embodiment
Below, describe embodiments of the present invention in detail.
Die cleaning agent composition of the present invention uses as the synthetic rubber of mother metal and/or synthetic resins, an alkali metal salt and/or alkali metal hydroxide and water and/or organic solvent to obtain as neccessary composition.
Above-mentioned synthetic rubber, be so-called unvulcanized rubber, can enumerate such as the ethene-alpha-olefin rubber such as natural rubber (NR), divinyl rubber (BR), paracril (NBR), ethylene-propylene rubber(EPR) (EPR), styrene butadiene rubbers (SBR), polyisoprene rubber (IR), isobutylene-isoprene copolymer (IIR), silicon rubber (Q), fluorine-containing rubber (FKM) etc.These rubber may be used singly or two or more in combination.In addition, among the present invention, above-mentioned ethene-alpha-olefin rubber also comprises ethylene-propylene-ethylene-alpha-olefin-polyene rubber such as polyenoid rubber (EPDM).In addition, these unvulcanized rubbers vulcanize in mould and become vulcanized rubber.
In the above-mentioned synthetic rubber, the few viewpoint of foul smell when using mould to form during the few and sulfuration of contaminative considers, preferably uses separately EPR (comprising EPDM), BR or uses their mixture.
Above-mentioned EPDM is elaborated.EPDM be by ethene, alpha-olefin (particularly propylene) and below the terpolymer that consists of of the polyenic monomer enumerated, as above-mentioned polyenic monomer, can enumerate: dicyclopentadiene, 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 norbornylene, 2-methyl isophthalic acid, 4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, methyltetrahydro indenes, Isosorbide-5-Nitrae-hexadiene etc.
The copolymerization ratio optimal ethylene of each monomer is that 30～80 % by mole, polyenic monomer are 0.1～20 % by mole, all the other are the terpolymer of alpha-olefin among the above-mentioned EPDM.More preferably ethene is 30～60 % by mole.
In addition, as above-mentioned BR, can use separately respectively 1,2-polyhutadiene, 1，4-polybutadiene or its combination is used as mixture.
As above-mentioned synthetic resins, can enumerate such as the polyamide resins such as nylon 6 or nylon 66, the vibrin such as polyethylene terephthalate or polybutylene terephthalate, polycarbonate resin, polyarylester (polyarylate) resin, vinyl chloride resin, chlorinated vinyl chloride resin, polyvinyl resin, chlorinated polyethylene resin, chlorinated polypropylene, acrylic resin, polystyrene resin, the acrylonitrile-styrene resinoid, vinylidene resin, vinyl acetate resin, polyacrylate resin, polyimide resin, butadiene resin, polyacetal resin, ionomer resin, the ethylene-vinyl chloride copolymer resins, ethylene-vinyl acetate copolymer resin, ethane-acetic acid ethyenyl ester-vinylchlorid graft polymerization resin, polyphenylene resin, polysulfone resin, methacrylic resin, acrylic acid or the like-fluorine resin, acrylic acid or the like-siloxane oligomer, silicone resin, contain epoxy group(ing) silicone-acrylic resinoid, vinylester resin, furane resin, resol, melamine resin, guanamine resin, urea resin, urethane resin, the diallyphthalate acid ester resin, ketone resin, Resins, epoxy, xylene resin, maleic acid resin, phenoxy resin, coumarone resin, vinyl-formal resin, polyvinyl butyral resin etc.These resins may be used singly or two or more in combination.In these synthetic resins, the few viewpoint of pollution during from the use die forming is considered, preferably uses polyvinyl resin, Resins, epoxy, melamine resin.
And in the mother metal that comprises these synthetic rubber and/or synthetic resins, synthetic rubber or synthetic resins can use separately separately, also synthetic rubber and synthetic resins can be used in combination, also can be with separately multiple combination use.Wherein, from carry out mould when cleaning maneuverable viewpoint consider, preferably use synthetic rubber, polyvinyl resin, Resins, epoxy, melamine resin.Particularly preferably use above-mentioned synthetic rubber, in this synthetic rubber, as previously mentioned, the preferred mixture that uses separately EPR or use this EPR and BR.
As mother metal, EPR (x) preferably is set in the scope of x/y=100/0～20/80 in weight ratio with the blending ratio (x/y) of BR (y) when stating in the use the mixture of EPR and BR.The scope of x/y=70/30～30/70 particularly preferably.That is, this be because: about both blending ratios, when EPR is lower than 20 (BR is more than 80), when when forming operation, removing the rubber molding product, therefore easily the strength degradation of molding produces the problem such as break, and has the tendency that the operation of removing from mould becomes difficulty.
Comprise these synthetic rubber and/mother metal of synthetic resins, when the removing of dirt, when mould takes out, be preferably solid state.As the curing of realizing above-mentioned solid state, can enumerate be heating and curing, the cooling curing of thermoplastic resin etc. etc., for example, when being cured by heating, use solidifying agent.
Above-mentioned solidifying agent is so long as can make the material that mother metal solidifies get final product, for example, can enumerate organo-peroxide etc. for synthetic rubber or polyvinyl resin, in the situation that Resins, epoxy can be enumerated phenolic compound, aminated compounds, imidazoles, acid anhydride type curing agent, organic phosphoric acid compound etc.
As above-mentioned organo-peroxide, for example can enumerate: 1,1-bis(t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 1, the 1-bis(t-butylperoxy) cyclohexane, the peroxy maleic acid tert-butyl ester, the peroxide oleic acid tert-butyl ester, 3,3, the 5-trimethylammonium peroxy caproic acid tert-butyl ester, Cyclohexanone peroxides, the t-butyl peroxy aryl carbonate, t-butyl peroxy isobutyl carbonate propyl ester, 2,5-dimethyl-2,5-two (benzoyl peroxy) hexane, 2,2-bis(t-butylperoxy) octane, tert-butyl peroxy acetate, 2,2-bis(t-butylperoxy) butane, t-butyl per(oxy)benzoate, 4,4-bis(t-butylperoxy) n-butyl pentanoate, peroxide m-phthalic acid di tert butyl carbonate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, α, isopropyl benzene between α '-bis(t-butylperoxy), the tert-butyl peroxide cumyl, diisopropylbenzenehydroperoxide, di-t-butyl peroxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane-the organo-peroxides such as 3-alkynes.
As above-mentioned phenolic compound, for example can enumerate: as Resorcinol, Resorcinol, the pyrocatechol of monocycle difunctionality phenol; As the dihydroxyphenyl propane of many rings difunctionality phenol, Bisphenol F, naphthalenediol class, biphenyl phenols etc.; And the multifunctional phenols such as their halides, alkyl substituent.
As above-mentioned aminated compounds, for example can enumerate: N, the N-benzyldimethylamine, 2-(dimethylamino methyl) phenol, 2,4,6-three (dimethylamino methyl) phenol, tetramethyl guanidine, trolamine, N, N '-lupetazin, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0]-7-undecylene, 1,5-diazabicyclo [4.4.0]-5-nonene, vulkacit H, pyridine, picoline, piperidines, tetramethyleneimine, dimethylcyclohexylamine, dimethylhexylamine, hexahydroaniline, diisobutylamine, Di-n-Butyl Amine, pentanoic, methylphenylamine, Tri-n-Propylamine, tri-n-octyl amine, tri-n-butylamine, triphenylamine, tetramethyl ammonium chloride, 4 bromide, Tetramethylammonium iodide, Triethylenetetramine (TETA), diaminodiphenyl-methane, diaminodiphenyl oxide, Dyhard RU 100, OTBG o tolylbiguanide, the guanidine radicals urea, dimethyl urea etc.
As above-mentioned imidazoles, for example can enumerate: imidazoles, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, glyoxal ethyline, the 2-phenylimidazole, the 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 4, the 5-diphenyl-imidazole, the glyoxal ethyline quinoline, the 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2-heptadecyl tetrahydroglyoxaline, 2 isopropyl imidazole, 2, the 4-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl imidazol(e) quinoline, 2-phenyl-4-methylimidazole quinoline, benzoglyoxaline, 1-cyano ethyl imidazoles, 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')] the ethyl s-triazine etc.
As above-mentioned acid anhydride type curing agent, can enumerate such as acid anhydrides such as Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydrides.
As above-mentioned organic phosphoric acid compound, can enumerate such as the organo phosphorous compounds such as HMPA, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chloropropyl) ester, triphenyl phosphite, trimethyl phosphite 99, phenyl-phosphonic acid, triphenylphosphine, tri-n-butyl phosphine, diphenylphosphine and their halogenide etc.
These solidifying agent can use separately, also can two or more arbitrary combination use.
The use level of these solidifying agent can suitably be set, for example, if synthetic rubber then preferably sets in 1～3 part scope with respect to synthetic rubber 100 weight parts (hereinafter to be referred as " part ").
In addition, these solidifying agent not only have the function of the thermofixation of synthetic rubber or synthetic resins, also have the function as the clean-out system of mould, as required except as also may be fitted to the purpose of solidifying agent in the die cleaning agent composition of the present invention.The use level of the solidifying agent in such situation is preferably set to 5～60 parts, particularly preferably 5～25 parts with respect to 100 parts of synthetic rubber and/or synthetic resins.
An alkali metal salt that cooperates in the above-mentioned mother metal and/alkali metal hydroxide in, as above-mentioned an alkali metal salt, can enumerate the metal-salt of lithium, sodium, potassium, rubidium, caesium etc.
In addition, as such an alkali metal salt, for example can enumerate: boric acid, phosphoric acid, metaphosphoric acid, diphosphanetetroic acid, phosphorous acid (phosphonic acid), Hypophosporous Acid, 50 (phosphinic acid), tetra-sodium, the trimerization metaphosphoric acid, four poly-metaphosphoric acids, the phosphoric acid salt such as pyrophosphorous acid, carbonate, vitriol, nitrate, hydrochloride, vinylformic acid, hexanodioic acid, xitix, aspartic acid, benzaminic acid, Lalgine, phenylformic acid, oleic acid, formic acid, citric acid, oxyacetic acid, glyconic acid, L-glutamic acid, styracin, succsinic acid, acetic acid, Whitfield's ointment, oxalic acid, tartrate, toluenesulphonic acids, nicotinic acid, lactic acid, uric acid, halogenated acetic acids, phthalic acid, Phenylsulfonic acid, propanedioic acid, butyric acid, the organic acid salts such as oxysuccinic acid etc.
These an alkali metal salts are in the situation of polyprotonic acid, also can use part to form the material of an alkali metal salt, for example, in the phosphatic situation as triprotic acid, can be dihydrogen phosphate, the hydrophosphate with two metals and a hydrogen with a metal and two hydrogen, in the phosphoric acid salt with three metals any one.In addition, also can be any one of acid-salt, basic salt, neutral salt.Wherein, consider preferred basic salt, neutral salt from corrosive viewpoint of mould.In addition, the viewpoint of solubleness is considered from water, and these an alkali metal salts preferably use hydrate.
As above-mentioned alkali metal hydroxide, can enumerate such as sodium hydroxide, potassium hydroxide etc.
These an alkali metal salts, alkali metal hydroxide can use separately, also can be used in combination.
In addition, above-mentioned an alkali metal salt and/or alkali metal hydroxide, with respect to as the synthetic rubber of mother metal and/or 100 parts of preferred settings of synthetic resins in 0.1～10 part scope, particularly preferably 0.1～5 part.This be because: when use level is very few, the removability of the pollution substance that forms at die surface significantly descends, and has to be difficult to tendency that the mould dirt is removed fully, and is opposite too much the time, an alkali metal salt, alkali metal hydroxide are easily separated out at die surface, have on the contrary the tendency of polluting mould.
In addition, the water as cooperating in the present invention can preferably use tap water, remove the RO water (water after anti-seepage membrane is processed), ion exchanged water of impurity etc.
The use level of above-mentioned water is with respect to as the synthetic rubber of mother metal and/or 100 parts of preferred settings of synthetic resins scope at 3～30 parts, particularly preferably 5～20 parts.This be because: when use level was very few, the removability of the pollution substance that forms at die surface significantly descended, and had to be difficult to tendency that the mould dirt is removed fully, opposite too much the time, cleaning performance does not improve, and also increase the man-hour of cooperation, therefore has the tendency of waste.
In addition, the organic solvent as using in the present invention can use various organic solvents, for example, state in the use in the situation of an alkali metal salt, consider from its deliquescent viewpoint, can use amide solvent, alcoholic solvent, ketones solvent, ether solvent etc.These solvents can use separately, also can be used in combination.
As above-mentioned amide solvent, preferably example is such as methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, N, N-diethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N, N, N ', N '-tetramethyl-urea, 2-Pyrrolidone, METHYLPYRROLIDONE, hexanolactam, carbamate etc.
As above-mentioned alcoholic solvent, for example can enumerate: methyl alcohol, ethanol, the 1-propyl alcohol, the 2-propyl alcohol, n-butyl alcohol, the 2-butanols, isopropylcarbinol, the trimethyl carbinol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, tertiary amyl alcohol, 3-methyl-2-butanols, neopentyl alcohol, the 1-hexanol, 2-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-ethyl-n-butyl alcohol, 1-heptanol, the 2-enanthol, the 3-enanthol, hexalin, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 4 methyl cyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, Diethylene Glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, TEG, polyoxyethylene glycol (weight-average molecular weight 200～400), 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 2, the 3-butyleneglycol, 1,5-PD, glycerine, propylene glycol, dipropylene glycol etc.
As above-mentioned ketones solvent, can enumerate such as acetone, methylethylketone, 2 pentanone, propione, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), 2-heptanone, dipropyl ketone, diisobutyl ketone, pimelinketone, methylcyclohexanone, sym.-diisopropylideneacetone, isophorone etc.
As above-mentioned ether solvent, for example can enumerate: dipropyl ether, diisopropyl ether, dibutyl ether, two hexyl ethers, methyl-phenoxide, phenyl ethyl ether, dioxane, tetrahydrofuran (THF), 1,1-diethoxyethane, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.
And, except above-mentioned organic solvent, also can use hydrocarbon, halohydrocarbon, phenols, acetal, lipid acid, acid anhydrides, ester cpds, nitrogen compound, amine compound (Monoethanolamine MEA BASF etc.), sulphur compound (methyl-sulphoxide etc.) equal solvent or have the solvent (ester and ether, pure and mild ether etc.) of two above functional groups.These solvents can use separately, also can two or morely make up (for example, between the amide solvent, the solvent beyond amide solvent and the amide solvent) and use.In addition, also can be used in combination other solvent with these solvents, for example, also can mix ammonia as inorganic solvent etc.
Among the present invention, use in the situation of an alkali metal salt, consider from the deliquescent viewpoint of this an alkali metal salt, preferably above-mentioned organic solvent is used with above-mentioned illustrative water.In addition, when above-mentioned an alkali metal salt uses with the hydrate forms that is combined with crystal water, contain micro-moisture so solvability improves by this crystal water, still, consider from the viewpoint of workability, preferably hydrous water and accelerate dissolution rate on one's own initiative.
Above-mentioned organic solvent is preferably liquid when cleaning die, in addition, do not have volatile organic solvent during particularly preferably in mold heated.For example, preferably use polyalcohols, polyol alkyl ether class.Particularly, for the semiconductor device molding die that uses compositions of thermosetting resin as sealing material, generally in approximately 180 ℃ of lower uses of die temperature, the solvent that therefore uses as this moment preferably uses the solvent of boiling point more than 180 ℃ for it.Be solvent more than 180 ℃ as boiling point, can enumerate such as ethylene glycol monobutyl ether (boiling point: 188 ℃), propylene glycol (boiling point: 187 ℃), dipropylene glycol monomethyl ether (boiling point: 190 ℃), diethylene glycol monomethyl ether (194 ℃ of boiling points) etc.
The use level of above-mentioned organic solvent (the total use level when each solvent is used in combination), with respect to as the synthetic rubber of mother metal and/or 100 parts of preferred settings of synthetic resins in 3～30 parts scope, particularly preferably 5～20 parts.This be because: when use level was very few, the removability of the pollution substance that forms at die surface significantly descended, and had to be difficult to tendency that the mould dirt is removed fully, opposite too much the time, cleaning performance does not improve, and also increase the man-hour of cooperation, therefore has the tendency of waste.
In the die cleaning agent composition of the present invention, except above-mentioned each gradation composition as neccessary composition, also can suitably cooperate releasing agent, toughener etc. as required.
As above-mentioned releasing agent, can enumerate such as longer chain fatty acids such as stearic acid, docosoics, long-chain fat acid metal salt take Zinic stearas, calcium stearate etc. as representative, ester type waxes take partly-hydrolysed ester of carnauba wax, montanic acid wax, montanic acid etc. as representative, long chain fatty acids amides take ethylene bis stearamide etc. as representative, paraffin class take polyethylene wax etc. as representative etc.These materials can use separately, also can be used in combination.
The content of above-mentioned releasing agent, with respect to as the synthetic rubber of mother metal and/100 parts of preferred settings of synthetic resins are 5～20 parts scope, particularly preferably 8～16 parts.This be because: when content is very few, be difficult to bring into play sufficient stripping result, opposite too much the time, have that cleansing power descends and the tendency of the degraded appearance of this molding when using mould after the regeneration to make molding.
As above-mentioned toughener, can enumerate such as inorganic fillers such as SiO 2 powder, talcum powder, aluminum oxide, calcium carbonate, aluminium hydroxide, titanium oxide.These materials can use separately, perhaps are used in combination.As above-mentioned toughener, preferably use median size to be the about toughener of 0.01～approximately 100 μ m.
The content of above-mentioned toughener, with respect to as the synthetic rubber of mother metal and/100 parts of preferred settings of synthetic resins are 10～50 parts scope, particularly preferably 15～40 parts.This be because: when content is very few, thereby enhancement descends and to have the tendency that causes physical strength to descend, and is opposite too much the time, still has the tendency that physical strength descends thereby become fragile.
In addition, in die cleaning agent composition of the present invention, as the additive except above-mentioned, can for example suitably cooperate as required: aromatic hydrocarbon oil, cycloalkanes wet goods tenderizer, vulcanizing agent or the vulcanization accelerators such as sulphur, antiaging agent, the flowers of zinc etc.
Die cleaning agent composition of the present invention for example can followingly be made.That is, can will comprise that each gradation composition of above-mentioned each neccessary composition carries out mechanically milling and makes by using banbury mixers, kneader, mill (roll mixer), forcing machine etc.
The die cleaning agent composition of the present invention of making like this, for example the form of the mould cleaning material of, drug sheet Powdered to form, sheet or short strip shape is used for mould and cleans.The thickness of sheet is set as 3～10mm usually when making the sheet use.
In addition, as die cleaning agent composition of the present invention, be preferably formed into white to the such light color of its grey that approaches.By setting like this, has following effect: after mould cleans, can easily estimate to confirm from mould and remove and be attached to dirt on the die cleaning agent composition, and can easily confirm the cleaning situation of mould.
When using the mould cleaning material that obtains from die cleaning agent composition of the present invention, after being in the elastomeric situation, generally being preferably shaped to sheet, uses mother metal.In addition, mother metal is in the situation of synthetic resins, for example, if be the thermoset melamine resin, uses after then being preferably shaped to Powdered or drug sheet.
Use the cleaning method of the mould of the die cleaning agent composition that forms sheet of the present invention, carry out after in being loaded into the semiconductor device molding die.For example, be in the elastomeric situation at mother metal, above-mentioned is in not sulfided state certainly, it is loaded into carries out baking in the molding die, pollutent is attached on the sheet and integrated with it.Then, the sheet after the sulfuration is taken out from mould, carry out thus the cleaning of mould.
Use the mould cleaning method of above-mentioned sheet die cleaning agent composition when being synthetic rubber about mother metal, below progressively be elaborated.
At first, prepare to comprise the sheet mould cleaning material of die cleaning agent composition of the present invention.Then, the mould cleaning material (cleaning foil) of above-mentioned sheet is configured between the upper die and lower die that are formed with respectively recess of mould, begins upper die and lower die are closed from this state and clamp sheet mould cleaning material and carry out compression molding.In addition, the pressure when being shaped, above-mentioned sheet mould cleaning material are filled in the chamber that is made of the recess that forms in patrix and the recess that forms in counterdie, and are crimped onto on the die surface.Heat when under this state, being shaped, synthetic rubber (unvulcanized rubber) baking and become vulcanized rubber, the oxidative degradation layers of the releasing agent that form this moment in chamber etc. and vulcanized rubber form one.At this moment, according to circumstances, the burr that forms around chamber is also integrated.Then, through after the scheduled time, upper die and lower die are opened, from two moulds sheet mould cleaning material of vulcanized rubber being peeled off up and down, will be peeled off from two die surfaces up and down with the integrated oxidative degradation layer of above-mentioned sheet mould cleaning material etc. (pollutent) thus.Like this, carry out the cleaning of mould.
As clamping that above-mentioned sheet mould cleaning material carries out compression molding and condition when heating, suitably set according to mother metal kind etc.For example, in the elastomeric situation, be preferably set to 160～190 ℃ * 1～5 minute scope, in the situation that use thermosetting resin as synthetic resins, be preferably set to 160～190 ℃ * 1～5 minute scope.
Use object as die cleaning agent composition of the present invention is an example of mould, for example can enumerate: the semiconductor device that uses compositions of thermosetting resin repeatedly to be shaped seals the molding die of usefulness.
In the semiconductor device molding die as the example of use object of die cleaning agent composition of the present invention, as the compositions of thermosetting resin of sealing resin materials'use, for example can enumerate: the composition epoxy resin take Resins, epoxy as principal constituent.
And, as compositions of thermosetting resin, usually suitably cooperate the additives such as solidifying agent and inorganic filler as required, curing catalyst with the Resins, epoxy as above-mentioned principal constituent.
Then, with the mould after the die cleaning agent composition cleaning of the present invention, be removed the die surface of getting back to original state owing to pollutent, therefore, usually when using compositions of thermosetting resin as shaped material to carry out the shaping of semiconductor packages, in advance releasing agent is applied to die surface.For example, when containing montanic acid wax as the shaping of the shaped material of releasing agent, same preferred coating carnauba wax.And as the method at die surface coating releasing agent, the preferred unvulcanized rubber composition of preparing to contain releasing agent uses after it is configured as sheet.For example, can enumerate the sheet that releasing agent is cooperated with aforesaid unvulcanized rubber and obtain.In addition, will be loaded in the mould by the sheet that the unvulcanized rubber composition that contains this releasing agent is made equally with the matting of using above-mentioned sheet die cleaning agent composition and heat, contained releasing agent is applied to die surface thus.This can think: the releasing agent melting during baking in the unvulcanized rubber composition and being exuded on the die face, thus form from the teeth outwards uniform releasing agent film.
In addition, the content of above-mentioned releasing agent is for example with respect to the ratio of 100 parts of preferred settings of the elastomeric material in the unvulcanized rubber composition at 15～35 parts, particularly preferably 20～30 parts.This be because: if the content of releasing agent is lower than 15 parts, then can not bring into play sufficient stripping result, if opposite surpass 35 parts, then excessively coat die surface and use and cleaning, during mould forming shaped product after the regeneration, having the tendency of the degraded appearance of this molding.
Embodiment
Below, embodiment and comparative example are described in the lump.But, the invention is not restricted to these embodiment.
At first, each composition of composition of preparation die cleaning agent composition.
1) BR:[divinyl rubber: JSR company system, BR-01 (cis Isosorbide-5-Nitrae combination: 95%)]
2) EPR[ethylene-propylene-elastoprene: Mitsui Chemicals, Inc. system, EPT4045 (ethylene content: 54 % by mole, diene component content: 8.1 % by mole)]
3) talcum powder: median size 9 μ m
4) SiO 2 powder: median size 9 μ m
5) titanium oxide: median size 0.25 μ m
6) carnauba wax: No. 1, カ Le Na バ (emerging リ カ of day company system)
7) imidazoles: 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')] the ethyl s-triazine
8) two (t-butyl peroxy) n-butyl pentanoates of organo-peroxide: 4,4-
9) water: ion exchanged water
10) PEG: polyoxyethylene glycol (day oily company system, #200; Weight-average molecular weight 200)
11) PG: propylene glycol (boiling point: 187 ℃)
12) DGMM: diethylene glycol monomethyl ether (boiling point: 194 ℃)
(embodiment 1～8, comparative example 1～2)
Each composition shown in table 1 described later～table 2 is cooperated with the ratio shown in this table, use mixing roller that it is mixing.Then, use stack to be configured as sheet (thickness 5mm), make the sheet die cleaning agent composition (mould cleaning material) of target.
(embodiment 9)
To 100 parts of sprayings of crushed material of the Clean-thermoset melamine resin of commercially available mould (Japanese カ one バ ィ ト industrial system, ニ カ レ ッ ト ECR-T) 1 part of K as the clean-out system composition
3PO
4With 4 parts of water, it is adhered to, obtain thus pulverous die cleaning agent composition (mould cleaning material).
(comparative example 3)
Use the tablet of the Clean-thermoset melamine resin of commercially available mould (Japanese カ one バ ィ ト industrial system, ニ カ レ ッ ト ECR-T), as the die cleaning agent composition (mould cleaning material) of drug sheet.
The embodiment product that use obtains like this and each die cleaning agent composition (mould cleaning material) of comparative example product, the removability of the pollutent that forms on the following evaluation mould.Namely, use is as the corresponding Resins, epoxy of environment (eastern electrician of the day company system of sealing material, GE-7470) repeatedly be shaped, in carrying out 800 surperficial contaminated molding dies after (シ ョ ッ ト), use above-mentioned each die cleaning agent composition (mould cleaning material) to clean shaping.In addition, will from mould, take out the removability of the pollutent of visual assessment die surface by the molding that cleaning forms.In this was estimated, the forming operation number of times that can remove pollutent fully was that the average evaluation below 5 times is good, and it is bad that removing of pollutent needed the average evaluation of the forming operation more than 6 times.
In addition, in the evaluation of embodiment 1～8 product and comparative example 1～2 product, the die cleaning agent composition (mould cleaning material) of sheet is clipped in the molding die, carries out heating in 5 minutes at 175 ℃ and be shaped.On the other hand, in the evaluation of embodiment 9 product, use pulverous die cleaning agent composition (mould cleaning material), in the evaluation of comparative example 3 product, use the die cleaning agent composition (mould cleaning material) of drug sheet, transmit shaping, carry out heating in 3 minutes at 175 ℃ and be shaped.
Above-mentioned evaluation result is shown in following table 1～table 2.
Table 1
(part)
Table 2
(part)
Can find out from the above results, do not contain as the two comparative example product of an alkali metal salt of clean-out system composition and/or alkali metal hydroxide and water, the cleaning of its mould is evaluated as bad, and is relative therewith, and all the mould cleaning of embodiment product is evaluated as very.
The change of＜sealing material (1) 〉
In addition, will be as above-mentioned environment correspondence Resins, epoxy (eastern electrician of the day company system of sealing material, GE-7470) change to the corresponding Resins, epoxy GE-1030 of environment that is all the manufacturing of eastern electrician of day company, for with above-mentioned molding die (after 800 times) after similarly repeatedly being shaped, by using the contaminant removal of each die cleaning agent composition (mould cleaning material) of embodiment 1～9 product and comparative example 1～3 product with above-mentioned same method visual assessment.As a result, with above-mentioned same, the mould cleaning of comparative example product is evaluated as bad, and is relative therewith, and all the mould cleaning of embodiment product is evaluated as very.
The change of＜sealing material (2) 〉
In addition, will be as above-mentioned environment correspondence Resins, epoxy (eastern electrician of the day company system of sealing material, GE-7470) change to the corresponding Resins, epoxy GE-100 of environment that is all the manufacturing of eastern electrician of day company, for with above-mentioned molding die (after 800 times) after similarly repeatedly being shaped, by using the contaminant removal of each die cleaning agent composition (mould cleaning material) of embodiment 1～9 product and comparative example 1～3 product with above-mentioned same method visual assessment.As a result, with above-mentioned same, the mould cleaning of comparative example product is evaluated as bad, and is relative therewith, and all the mould cleaning of embodiment product is evaluated as very.
(embodiment 10～18, comparative example 4 and 5)
Each composition shown in table 3 described later～table 4 is cooperated with the ratio shown in this table, use mixing roller that it is mixing.Then, use stack to be configured as sheet (thickness 5mm), make the sheet die cleaning agent composition (mould cleaning material) of target.
(embodiment 19)
To 100 parts of sprayings of crushed material of the Clean-thermoset melamine resin of commercially available mould (Japanese カ one バ ィ ト industrial system, ニ カ レ ッ ト ECR-T) 1 part of K as the clean-out system composition
3PO
44 parts of PEG and 1 part of water with as organic solvent adhere to it, obtain thus pulverous die cleaning agent composition (mould cleaning material).
(comparative example 6) (※ is identical with aforementioned comparative example 3)
Use the tablet of the Clean-thermoset melamine resin of commercially available mould (Japanese カ one バ ィ ト industrial system, ニ カ レ ッ ト ECR-T), as the die cleaning agent composition (mould cleaning material) of drug sheet.
The embodiment product that use obtains like this and each die cleaning agent composition (mould cleaning material) of comparative example product, the removability of the pollutent that forms on the following evaluation mould.Namely, use is as the corresponding Resins, epoxy of environment (eastern electrician of the day company system of sealing material, GE-7470) repeatedly be shaped, in the surperficial contaminated molding die that carries out after 800 times, use above-mentioned each die cleaning agent composition (mould cleaning material) to clean shaping.In addition, will from mould, take out the removability of the pollutent of visual assessment die surface by the molding that cleaning forms.In this was estimated, the forming operation number of times that can remove pollutent fully was that the average evaluation below 3 times is good, and it is bad that removing of pollutent needed the average evaluation of the forming operation more than 4 times.
In addition, in the evaluation of embodiment 10～18 product and comparative example 4 and 5 product, the die cleaning agent composition (mould cleaning material) of sheet is clipped in the molding die, carries out heating in 5 minutes at 175 ℃ and be shaped.On the other hand, in the evaluation of embodiment 19 product, use pulverous die cleaning agent composition (mould cleaning material), in the evaluation of comparative example 6 product, use the die cleaning agent composition (mould cleaning material) of drug sheet, transmit shaping, carry out heating in 3 minutes at 175 ℃ and be shaped.
Above-mentioned evaluation result is shown in following table 3～table 4.
Table 3
(part)
The ※ cleaning is good, but because hydrous water not, therefore for composition evenly need to slightly be taken time
Table 4
(part)
Can find out from the above results, do not contain as an alkali metal salt of clean-out system composition and/or the comparative example product of alkali metal hydroxide, the cleaning of its mould is evaluated as bad, relative therewith, the mould cleaning that contains whole embodiment product of mother metal, an alkali metal salt and/or alkali metal hydroxide and organic solvent or organic solvent and water is evaluated as very.
The change of＜sealing material (1) 〉
In addition, will be as above-mentioned environment correspondence Resins, epoxy (eastern electrician of the day company system of sealing material, GE-7470) change to the corresponding Resins, epoxy GE-1030 of environment that is all the manufacturing of eastern electrician of day company, for with above-mentioned molding die (after 800 times) after similarly repeatedly being shaped, by using the contaminant removal of each die cleaning agent composition (mould cleaning material) of embodiment 10～19 product and comparative example 4～6 product with above-mentioned same method visual assessment.As a result, with above-mentioned same, the mould cleaning of comparative example product is evaluated as bad, and is relative therewith, and all the mould cleaning of embodiment product is evaluated as very.
The change of＜sealing material (2) 〉
In addition, will be as above-mentioned environment correspondence Resins, epoxy (eastern electrician of the day company system of sealing material, GE-7470) change to the corresponding Resins, epoxy GE-100 of environment that is all the manufacturing of eastern electrician of day company, for with above-mentioned molding die (after 800 times) after similarly repeatedly being shaped, by using the contaminant removal of each die cleaning agent composition (mould cleaning material) of embodiment 10～19 product and comparative example 4～6 product with above-mentioned same method visual assessment.As a result, with above-mentioned same, the mould cleaning of comparative example product is evaluated as bad, and is relative therewith, and all the mould cleaning of embodiment product is evaluated as very.
With reference to specific embodiment the present invention is had been described in detail, still, it is obvious to the skilled person that in the situation that do not break away from the spirit and scope of the present invention and can carry out various changes or correction.
The application is based on the Japanese patent application 2009-169331 of the Japanese patent application 2009-169330 that proposed on July 17th, 2009 and proposition on July 17th, 2009, and the content of these two applications is incorporated this specification sheets as a reference into.
Die cleaning agent composition of the present invention, can be used for various shaping dies that the thermosetting resin shaped material uses etc., such as use epoxy resin molding material with semiconductor element by injection forming or transmit the cleaning and regeneration etc. of the molding die of use when repeatedly carrying out resin-sealed shaping of being shaped.
Claims (7)
1. die cleaning agent composition, said composition are used for cleaning the hot briquetting mould that uses formed material to carry out repeatedly moulding, wherein contain:
As synthetic rubber and/or the synthetic resins of mother metal,
An alkali metal salt and/or alkali metal hydroxide, and
Water and/or organic solvent;
The content of an alkali metal salt and/or alkali metal hydroxide is 0.1～10 weight part with respect to synthetic rubber and/or synthetic resins 100 weight parts as mother metal, the content of water is 3～30 weight parts with respect to synthetic rubber and/or synthetic resins 100 weight parts as mother metal, and the content of organic solvent is 3～30 weight parts with respect to synthetic rubber and/or synthetic resins 100 weight parts as mother metal.
2. die cleaning agent composition as claimed in claim 1, wherein,
Synthetic rubber is ethylene-propylene class rubber and/or divinyl rubber.
3. die cleaning agent composition as claimed in claim 1, wherein,
Organic solvent is to be selected from least a in the group that is comprised of polyalcohols and polyol alkyl ether class.
4. die cleaning agent composition as claimed in claim 3, wherein,
The content of organic solvent is 3～30 weight parts with respect to synthetic rubber and/or synthetic resins 100 weight parts as mother metal.
5. a mould cleaning material is configured as sheet by each described die cleaning agent composition in the right to use requirement 1～4 and obtains.
6. mould cleaning method comprises following operation:
The mould cleaning material that will comprise each described die cleaning agent composition in the claim 1～4 is placed into the operation on the profile of mould of unlatching,
Close described mould and clip described mould cleaning material and carry out heating and pressurizing makes the pollutent and the integrated operation of described mould cleaning material that form at die surface thus, and
Cleaning mold is surperficial with the integrated mould cleaning material of pollutent by peeling off from mould.
7. mould cleaning method as claimed in claim 6, wherein,
The mould cleaning material is the die cleaning agent composition to be formed sheet and the material that obtains.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009169331A JP5604822B2 (en) | 2009-07-17 | 2009-07-17 | Semiconductor device molding die cleaning composition, semiconductor device molding die cleaning material, and semiconductor device molding die cleaning method using the same |
| JP2009-169331 | 2009-07-17 | ||
| JP2009-169330 | 2009-07-17 | ||
| JP2009169330A JP6116789B2 (en) | 2009-07-17 | 2009-07-17 | Semiconductor device molding die cleaning sheet and semiconductor device molding die cleaning method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101955858A CN101955858A (en) | 2011-01-26 |
| CN101955858B true CN101955858B (en) | 2013-01-30 |
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| CN201010233007XA Active CN101955858B (en) | 2009-07-17 | 2010-07-16 | Mold cleaner composition and mold cleaning material, and method of cleaning using the same |
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| Country | Link |
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| KR (2) | KR101788859B1 (en) |
| CN (1) | CN101955858B (en) |
| MY (1) | MY177272A (en) |
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| CN103702813B (en) * | 2011-07-15 | 2016-03-30 | 日本电石工业株式会社 | Resin composition for cleaning mold |
| KR101334251B1 (en) * | 2012-03-08 | 2013-11-29 | 재단법인 대구테크노파크 | Composition for EMC mold cleaning comprising nano sized inorganic filler |
| KR101334249B1 (en) * | 2012-03-08 | 2013-11-29 | 재단법인 대구테크노파크 | Composition for EMC mold cleaning comprising cleaning agent grafted inorganic filler |
| CN102864458B (en) * | 2012-08-31 | 2014-04-16 | 昆山艾森半导体材料有限公司 | Environment protection type weakly acidic deburring softening solution and preparation method and use method thereof |
| CN104955627B (en) * | 2013-01-31 | 2018-02-13 | 日本电石工业株式会社 | Resin composition for cleaning mold and cleaning mold method |
| CN103526214B (en) * | 2013-09-05 | 2015-12-09 | 汉中锌业有限责任公司 | The method for cleaning of zinc ingot metal mould in a kind of zinc hydrometallurgy |
| 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 |
| JP6715627B2 (en) * | 2016-03-18 | 2020-07-01 | 日本カーバイド工業株式会社 | Mold cleaning resin composition |
| 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 |
| CN108431197B (en) * | 2016-08-25 | 2021-06-29 | 化研科技株式会社 | Cleaning agent composition and cleaning method |
| CN109735116B (en) * | 2019-01-04 | 2021-03-30 | 山西大学 | Oil stain cleaning cotton and preparation method thereof |
| CN111423630A (en) * | 2020-04-23 | 2020-07-17 | 江苏多肯新材料有限公司 | Rubber mixture for cleaning self-adhesive mold, preparation method and use method thereof |
| CN112080347B (en) * | 2020-07-27 | 2023-12-08 | 中国电力科学研究院有限公司 | Cleaning agent for cleaning dirt on silicon rubber insulating surface and preparation method thereof |
| CN112847973A (en) * | 2021-01-06 | 2021-05-28 | 珠海格力新元电子有限公司 | Mold cleaning method |
| CN114456884A (en) * | 2021-12-30 | 2022-05-10 | 安莱博医药(苏州)有限公司 | ICP component cleaning agent |
| CN115093620A (en) * | 2022-06-30 | 2022-09-23 | 江阴鼎言密封件有限公司 | Mold washing glue for rubber vulcanization forming mold and processing technology thereof |
| CN115181612A (en) * | 2022-08-05 | 2022-10-14 | 惠州市百世杰喜庆用品有限公司 | Mahjong cleaning agent and preparation method thereof |
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- 2010-07-16 TW TW099123559A patent/TWI499668B/en active
- 2010-07-16 SG SG201005167-0A patent/SG168489A1/en unknown
- 2010-07-16 KR KR1020100069108A patent/KR101788859B1/en active IP Right Grant
- 2010-07-16 MY MYPI2010003374A patent/MY177272A/en unknown
- 2010-07-16 CN CN201010233007XA patent/CN101955858B/en active Active
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| 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 |
| CN101077995A (en) * | 2006-05-25 | 2007-11-28 | 日东电工株式会社 | Mold cleaning composition |
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| TWI499668B (en) | 2015-09-11 |
| MY177272A (en) | 2020-09-10 |
| SG168489A1 (en) | 2011-02-28 |
| KR101788859B1 (en) | 2017-10-20 |
| TW201107462A (en) | 2011-03-01 |
| KR20110007983A (en) | 2011-01-25 |
| CN101955858A (en) | 2011-01-26 |
| KR20170091558A (en) | 2017-08-09 |
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