CN101821075B - Mold cleaning rubber compositon - Google Patents
Mold cleaning rubber compositon Download PDFInfo
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- CN101821075B CN101821075B CN2008801106985A CN200880110698A CN101821075B CN 101821075 B CN101821075 B CN 101821075B CN 2008801106985 A CN2008801106985 A CN 2008801106985A CN 200880110698 A CN200880110698 A CN 200880110698A CN 101821075 B CN101821075 B CN 101821075B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention provides a mold cleaning rubber composition for removing soiling on the surface of a mold produced in a curable resin molding process. An unvulcanized rubber is used as a base material resin. The unvulcanied rubber comprises an ethylene-propylene rubber and a butadiene rubber at a mixing ratio of 90/10 to 50/50 on the basis of parts by weight. After the vulcanization curing of the unvulcanized rubber, the elongation is 80 to 800%, the tensile strength is 3 to 10 MPa, and the rubber hardness (durometer hardness) is A60 to 95. The 90% vulcanization time (proper vulcanization point) tc (90) at a mold temperature of 175 DEG C is 50 to 100 sec or 200 to 400 sec. When the mold cleaning rubber composition is used for cleaning for molds for the production of small-size packages having a large cavity depth, for example, PDIP or SOIC, and molds for the production of small packages, particularly small packages with a small number of pins, preferably, the mold cleaning rubber composition contains a release agent in addition to the unvulcanized rubber having a tc (90) value of 200 to 400 sec.
Description
Technical field
The present invention relates to a kind of mold cleaning rubber compositon, specifically, this cleaning rubber compositon is used for removing the dirt of the die surface that the forming process at curable resin produces, and it is characterized in that, uses specific half finished rubber as substrate resin.
Background technology
In the past, when heat-curing resins such as utilizing epoxy resin carries out the shaping of seal molding thing of integrated circuit etc., if be shaped for a long time, the mould inside surface is contaminated, if still continue to be shaped, the seal molding thing is surperficial contaminated, or the seal molding thing is attached on mould, make forming operation not continue, this situation is a lot.Therefore, be necessary mould is carried out cleaned at regular intervals, proposed following method: come the Clean-resin of shaping dies so that mould is cleaned moulding material is carried out every hundreds of injection mouldings with regard to the ratio of carrying out injection for several times, for example disclosing by being shaped by amino in Japanese Patent Publication 52-788 communique is the method that the Clean-resin combination of mould that resin, organic base material and/or inanimate matter base material, releasing agent form cleans mould.
On the other hand, proposed following method: using the half finished rubber that contains cleaning ingredients is that elastomeric compound replaces above-mentioned Thermocurable melamine resin moulding material, make its sulfuration and while forming vulcanized rubber in mould, the oxidative degradation layers such as releasing agent that die surface existed by cleaning ingredients decompose and are integrated with vulcanized rubber, then take out vulcanized rubber from mould, thus die surface is cleaned.In addition, the butadiene rubber/EP rubbers composition that has also proposed as the half finished rubber composition is set to the rubber series composition (reference example such as Japanese kokai publication sho 63-227308 communique, Japanese kokai publication hei 4-357007 communique) of 90/10～50/50 weight portion.
As the cleaning material of mould, can roughly be divided into these two types of die-casting die and compression-types, it is phenol resin molding material that die-casting die is used melamine, it is phenol resin molding material and rubber series cleaning material that compression-type uses melamine.
In recent years, be accompanied by highly integrated, the slimming of (being abbreviated as IC, LSI) such as integrated circuits, surperficial actual installation, the diversified development of the shape of formed products, structure, therefore, designed high liquidation or the environment replyization of semiconductor-encapsulating material.
Therefore, the epoxy sealing material of high liquidation type is because the resin that the steam vent part easily occurs stops up, and if these obstructions occur, venting quality variation, resin can not flow, so can produce and fill in mould cavity part, become unfavorable condition, thereby progressive forming becomes difficult.So,, for fear of these situations, be necessary to implement cleaning, but while using the cleaning material of die-casting die, due to above-mentioned reason, resin can not proper flow, so be difficult to remove the resin that stops up in steam vent.
In order to solve the obstruction of above-mentioned steam vent, can use the cleaning material of compression-type, if but use melamine, be phenol resin molding material, although can eliminate the obstruction of steam vent part, but can not fully exert pressure due to the outflow of resin near the mould periphery, so the peripheral part of molding has the tendency that becomes fragile, the operation of removing the molding after curing from mould becomes numerous and diverse.By comparison, in the situation that use rubber series cleaning material, the cleaning material is whole equally to be solidified, and can be used as a laminar molding from the demoulding on mould, so workability makes moderate progress.But, aspect mobility,, because rubber series cleaning material is that phenol resin molding material is poor than melamine,, so the fillibility in die cavity is poor, exist the problem of the dirt that can not remove die cavity turning etc.
In addition, when in the encapsulation die for manufacturing that rubber series is cleaned material and be used for the darker compact package die for manufacturing of the die cavitys such as plastics dual-in-line (below be abbreviated as PDIP) or little outline packages integrated circuit (below be abbreviated as SOIC) or the less compact of compact package pin number, because the demoulding number change of encapsulation is many, so the molding after easily solidifying is attached to the phenomenon on mould.When being removed, exist following problem: laminar molding fracture and produce the residual chip (chipping) of rubber series cleaning material in die cavity.If produce chip in these moulds, because the die cavity number is more, for the molding of removing the chip position just requires a great deal of time.
In order to address the above problem, wish following rubber series cleaning material, its workability (release property), have excellent moldability, the die cavity turning can not occur not fill or owing to having extensibility and intensity high, thereby the phenomenon such as chip can not occur when mold releasability.
Patent documentation 1: Japanese Patent Publication 52-788 communique
Patent documentation 2: Japanese kokai publication sho 63-227308 communique
Patent documentation 3: Japanese kokai publication hei 04-357007 communique
Summary of the invention
Problem of the present invention as mentioned above,, although be that to solve workability (release property) good, can produce the shortcoming in the rubber series cleaning material in the past of pore or chip, and a kind of rubber series cleaning material that can not produce pore or chip is provided.
In addition, problem of the present invention is: although it is good to solve workability (release property), although but can produce pore or chip or not produce pore but workability (release property) differs from and produces shortcoming in the rubber series cleaning material in the past of chip, in the encapsulation die for manufacturing of the less compact of pin number, also can not produce the rubber series cleaning material of pore or chip even provide simultaneously a kind of in the darker compact package die for manufacturing of the die cavitys such as PDIP or SOIC or compact package.
The present invention has solved above-mentioned problem by the mold cleaning rubber compositon that following (1), (2) and (3) are provided.
(1) a kind of mold cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 90/10～50/50 weight portion as substrate resin, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness (shore hardness) is A60～95, 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ is the scope of the value of 50～100 seconds.(below, be called the 1st mold cleaning rubber compositon)
(2) a kind of mold cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 90/10～50/50 weight portion as substrate resin, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness (shore hardness) is A60～95, 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ is the scope of the value of 200～400 seconds.(below, be called the 2nd mold cleaning rubber compositon)
(3) a kind of mold cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 90/10～50/50 weight portion as substrate resin, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness (shore hardness) is A60～95, 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ is the scope of the value of 200～400 seconds, and described mold cleaning rubber compositon contains at least a releasing agent.(below, be called the 3rd mold cleaning rubber compositon)
The the 1st, the 2nd and the 3rd mold cleaning rubber compositon of the present invention not only workability (release property) is good, and formability and intensity are also good, even can not produce pore or chip.
the of the present invention the 1st, in the 2nd and the 3rd mold cleaning rubber compositon, the percentage elongation of half finished rubber after sulfuration is solidified that uses as substrate resin is 80～800%, hot strength is 3～10MPa, rubber hardness (shore hardness) is A60～95, 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ is the scope of the value of 50～100 seconds or 200～400 seconds, consequently, become following rubber series composition, namely, this rubber series composition can easily be implemented the cleaning of discharge portion, and then can keep the workability (release property) that cleans the feature of material as rubber series, formability and intensity are also good simultaneously.
In addition, the rubber series composition of the cleaning of the encapsulation die for manufacturing of the 3rd mold cleaning rubber compositon of the present invention by containing at least a releasing agent, become in the darker compact package die for manufacturing such as the die cavity that is suitable for PDIP or SOIC or compact package the less compact of pin number.
The specific embodiment
Below, at first the 1st mold cleaning rubber compositon of the present invention is elaborated.
The half finished rubber that uses in the present invention mixes and uses EP rubbers and butadiene rubber.
EP rubbers (the following EPM that sometimes is abbreviated as) comprises the two implication of common EP rubbers (EPM) and ethylene propylene diene rubber (the following EPDM that sometimes is abbreviated as).
As above-mentioned EPM, the copolymerization ratio of optimal ethylene and alpha-olefin (particularly propylene) take molar ratio computing as ethylene/alpha-olefin=55/45～83/17, Mooney viscosity ML
1+4(100 ℃) are 5～300 EPM, be particularly preferably above-mentioned copolymerization ratio take molar ratio computing as ethylene/alpha-olefin=55/45～61/39, Mooney viscosity ML
1+4(100 ℃) are 36～44 EPM.
In addition, above-mentioned EPDM is by ethene, alpha-olefin and has the ring of unconjugated double bond or the terpolymer that the non-annularity thing forms.Specifically, be the terpolymer that is formed by ethene, alpha-olefin (particularly propylene) and polyenic monomer.
As above-mentioned polyenic monomer, can list bicyclopentadiene, 5-cyclo-octadiene, 1,7-encircles 12 carbon diene, 1,5,9-cyclodoecatriene, 1,4-cycloheptadiene, 1,4-cyclohexadiene, norbornadiene, methene norbornene, 2-methylpentadiene-Isosorbide-5-Nitrae, 1,5-hexadiene, 1,6-heptadiene, methyl-tetrahydroindene, Isosorbide-5-Nitrae-hexadiene etc.The copolymerization ratio of each monomer in above-mentioned terpolymer is preferably, and ethene is 30～80 % by mole, and polyenic monomer is 0.1～2 % by mole, and remainder is alpha-olefin.More preferably, ethene is 30～60 % by mole.And,, as above-mentioned terpolymer EPDM, preferably use Mooney viscosity ML
1+4(100 ℃) are 20～70 copolymer.
In addition, as above-mentioned butadiene rubber (the following BR that sometimes is abbreviated as), the content that preferably has cis Isosorbide-5-Nitrae key is the above high-cis structures of 90 % by weight, and Mooney viscosity ML
1+4(100 ℃) are 20～60, are particularly preferably 30～45 butadiene rubber.
In addition, the mixing ratio of above-mentioned EP rubbers and butadiene rubber is counted 90/10～50/50 weight portion with weight ratio, is preferably 80/20～60/40 weight portion.
If the proportioning of EP rubbers surpasses 90 weight portions, mold releasability variation, the cleaning operation time is elongated, thereby not preferred.If the proportioning of butadiene rubber surpasses 50 weight portions, although mold releasability becomes well, the molding hardening after sulfuration becomes fragile, thus easily produce chip, thereby not preferred.
The percentage elongation of above-mentioned half finished rubber after sulfuration is solidified is 80～800%, is preferably 100～300%.If percentage elongation is below 80%, formability variation, thereby not preferred.
The hot strength of above-mentioned half finished rubber after sulfuration is solidified is 3～10MPa, is preferably 5～8MPa.If hot strength is below 3MPa, can produce chip, thereby not preferred.
The rubber hardness (shore hardness) of above-mentioned half finished rubber after sulfuration is solidified is A60～95, is preferably A70～90.If rubber hardness exceeds this scope, can produce chip or pore, thereby not preferred.
90% cure time (sulfurizing point) tc (90) of above-mentioned half finished rubber when mold temperature is 175 ℃ is 50～100 seconds, is preferably 70～100 seconds.Tc (90) if value be in this scope, curingprocess rate can be not too fast, can make resin filling each corner to die cavity, thus can implement under the condition of rough sledding such as not adhering to the cleaning.In addition, with rubber series cleaning material in the past, compare, can clean with efficient hardening time, so can reduce total cleaning time.
Rubber series composition of the present invention except containing above-mentioned half finished rubber, can also contain filler, washing agent, washing assisant, vulcanizing agent, vulcanization aid, vulcanization accelerator, vulcanization accelerator additive etc.
, as filler (reinforcing agent), can list silica, aluminium oxide, calcium carbonate, aluminium hydroxide, titanium oxide etc.The use amount of above-mentioned filler is to be preferably 10～70 weight portions with respect to half finished rubber 100 weight portions, more preferably 30～60 weight portions.
, as washing agent, can list for example MEA, diethanol amine, triethanolamine, N methyldiethanol amine, N, the amines such as N-di-n-butyl monoethanolamine; The glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether; Imidazoles and imidazolines.The use amount of above-mentioned washing agent is to be preferably 5～50 weight portions with respect to half finished rubber 100 weight portions, more preferably 5～30 weight portions.In addition, can also use the washing assisants such as surfactant.
As vulcanizing agent, can list for example di-tert-butyl peroxide, two t-amyl peroxy things, dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-diallyl peroxide organic peroxides such as hexane, for example 1, two (tert-butyl hydroperoxides) 3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (tert-butyl hydroperoxide) cyclohexanes, 2 of 1-, two (tert-butyl hydroperoxide) octanes of 2-, normal-butyl 4, two (tert-butyl hydroperoxide) valerates, 2 of 4-, the ketal peroxide class organic peroxides such as two (tert-butyl hydroperoxide) butane of 2-.Generally with the diallyl peroxide, compare, the ketal peroxide class has the longer half-life, but they can use separately according to the design of composition, also can and be used for adjusting curingprocess rate with the compound of long half time and short compound.The use amount of above-mentioned vulcanizing agent is to be preferably 1～6 weight portion with respect to half finished rubber 100 weight portions, more preferably 2～4 weight portions.In addition, can also use the vulcanization aids such as acrylic monomers or sulphur.
As vulcanization accelerator, can list the system such as the guanidine such as diphenylguanidine, triphenyl guanidine, such as formaldehyde-para-totuidine condensation product, acetaldehyde-aldehyde such as aniline reaction thing-amine system or aldehyde-ammonia system, the systems such as the thiazole such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide etc., can use the vulcanization accelerator additives such as magnesia, lead monoxide, lime.
Except above-mentioned complex, can also and use as required such as the inorganic or organic pigment class such as iron oxide red, Prussian blue, iron black, ultramarine, carbon black, lithopone, titan yellow, cobalt blue, hansa yellow, quinoline Azone be red in rubber series composition of the present invention; Metallic soap base lubricants such as zinc stearate, Zinc tetradecanoate, aluminum stearate, calcium stearate, fatty acid ester base lubricants such as butyl stearate, butyl laurate, stearic stearolactone, the base lubricant such as the acid amides such as ethylenebisstearamide, erucyl amide, oleamide, stearic amide, behenamide etc.
Below, the 2nd mold cleaning rubber compositon of the present invention is described.
In the 2nd mold cleaning rubber compositon of the present invention, except the half finished rubber that uses as substrate resin is that 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ is 200～400 seconds, is preferably this point of half finished rubber of 250～350 seconds, identical with the 1st mold cleaning rubber compositon of the present invention.
The kind of the kind of the kind that the adjustment of the value of above-mentioned tc (90) can be by diene or the kind of amount, peroxide or amount, vulcanization accelerator or amount, co-crosslinker or amount etc. are carried out suitable adjustment.
The tc of above-mentioned half finished rubber (90) if value be in the scope of 200～400 seconds, curingprocess rate can be not too fast, during matched moulds, the rubber series composition follows mold shape lentamente, so can make resin filling can not produce pore to each corner of die cavity.In addition, can not occur by not filling or pore produces under the condition of the rough sledding such as adhesion of bringing and implements cleaning.
Below, the 3rd mold cleaning rubber compositon of the present invention is described.
The 3rd mold cleaning rubber compositon of the present invention contains at least a releasing agent and obtains in the 2nd mold cleaning rubber compositon.
As above-mentioned releasing agent, can list metallic soap and be releasing agent, fatty acid ester and be releasing agent, synthetic wax, fatty acid amide is releasing agent etc.
Be the example of releasing agent as metallic soap, can list such as calcium stearate, zinc stearate, Zinc tetradecanoate etc.be releasing agent as fatty acid ester, synthetic wax, fatty acid amide is releasing agent, (Clariat Japan Co., Ltd. makes can to exemplify LicowaxOP, the partly-hydrolysed ester of montanic acid), (Cognis Japan Co., Ltd. makes LoxiolG-78, the macromolecule complex ester), (Clariat Japan Co., Ltd. makes Licolub H-4, the modification hydrocarbon), (Cognis Japan Co., Ltd. makes LoxiolVPN881, Dormant oils is synthetic wax), (Kao Corp makes aliphatic acid Amides S, fatty acid amide), (Kao Corp makes KAO WAXEB-P, fatty acid amide), (NOF Corp makes Alflow HT-50, fatty acid amide) etc.
The use level of above-mentioned releasing agent is to be preferably 3～15 weight portions with respect to half finished rubber 100 weight portions, more preferably 5～10 weight portions.
, if the amount of releasing agent is not enough, in the darker compact package of the die cavitys such as PDIP or SOIC, especially sell in the encapsulation die for manufacturing of the less compact of number, because the die cavity number that configures on mould becomes many, so mold releasability relatively descends.If the amount of releasing agent is too much, although mold releasability is good, the spatter property variation, thereby not preferred.
As the of the present invention the 1st and the preparation method of the 2nd mold cleaning rubber compositon, be not particularly limited, can adopt known method.For example, drop into EPM and BR sizing material in the compression type kneader with chuck, then start mixing, Yi Bian Yi Bian to observe aptly the sizing material temperature mixing, until the blend glue stuff of EPM and BR becomes the rice cake shape.Then, reach the moment of 70～100 ℃ in the temperature of this blend glue stuff, add white carbon, amino alcohol based compound, cyclic amide compound, processing oil, non-ionic surface active agent, stearic acid etc., mixing several minutes.Then add organic peroxide and sulphur etc., take out after it is disperseed rapidly, be configured as required such as the suitable shape such as laminar, thereby become mold cleaning rubber compositon of the present invention.
The preparation of relevant the 3rd mold cleaning rubber compositon of the present invention, for example in the preparation method of the 2nd above-mentioned mold cleaning rubber compositon, get final product adding above-mentioned releasing agent in the blend glue stuff of EPM and BR together with other additive.
, as kneading device, except above-mentioned pressurization kneader, can also list such as closed mixing machine, roll-type mixing roll etc.
The form of the 1st, the 2nd and the 3rd mold cleaning rubber compositon of the present invention is not particularly limited, if but the resin combination after mixing is not cooling rapidly, preheating meeting when mixing promotes sulfuration, can't obtain stable performance, so, as the form of mold cleaning rubber compositon of the present invention, be preferably at short notice easily cooling laminar.
Embodiment
Below, enumerate embodiment etc. and further describe the present invention, but the present invention is not subjected to any restriction of these embodiment etc.
Test method
The test method of the various evaluation of physical property of putting down in writing in embodiment and comparative example is as described below.
[percentage elongation and hot strength]
The assay method of the percentage elongation during according to the hot strength in JIS K6251 and cut-out is measured.
The manufacturing conditions of＜test film 〉
Using the 37T automatic press, is that 175 ℃, forming pressure are that 10MPa (gauge pressure), curring time are to be shaped and not vulcanize sample under the condition of 5 minutes in mold temperature.Test film after shaping is of a size of the laminar of 80 * 160 * 2mm, and is with No. 3 dumbbell cut-off knives, that it is die-cut to make the test film of measuring use.
[rubber hardness]
Use is measured based on the method for JIS K6253 " the hardness test method of vulcanized rubber and thermoplastic elastomer ".
Overlapping 3 of 80 * 160 * 2mm test film that will obtain under above-mentioned test film manufacturing conditions, use the Shore durometer that is suitable for the rubber hardness type to measure shore hardness.
[curingprocess rate]
Use " obtains the method for vulcanization characteristics " based on JIS K6300-2 with the oscillatory type vulcanzing tester method, 90% cure time (sulfurizing point) tc (90) when the mensuration mold temperature is 175 ℃.
[spatter property test]
Using commercially available biphenyl is epoxy resin molding material (Sumitomo Bakelite Co., Ltd. system, EME-7351T), realizes the pollution of mould in the mould of PDIP-14L (8 barrel-48 die cavitys) by the shaping of 500 injections.Use the mould after this pollution, the Clean-resin combination of shaping dies, until die surface is cleaned clean, is estimated thus repeatedly.In embodiment 9～12, with the mould of PDIP-8L (8 barrel-96 die cavitys), estimate.
Embodiment 1 (the 1st mold cleaning rubber compositon of the present invention)
Add EPDM sizing material (Mooney viscosity ML in the kneader of the compression type with chuck of 3000ml
1+4(100 ℃) are 23) 1050g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) 450g, on one side mixing about 3 minutes of cooling one side pressurization, the blend glue stuff of EPDM and BR becomes the rice cake shape, and its temperature becomes about 80 ℃.then add MEA 150g (blend glue stuff 100 weight portions with respect to EPDM and BR are 10 weight portions), the polyoxyalkylene decyl ethers is surfactant 75g (blend glue stuff 100 weight portions with respect to EPDM and BR is 5 weight portions), stearic acid 15g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1 weight portion), white carbon 750g (blend glue stuff 100 weight portions with respect to EPDM and BR are 50 weight portions), calcium carbonate 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), titanium oxide 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions) and zinc oxide 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), mixing about 3 minutes.Finally, add two (tert-butyl hydroperoxide) cyclohexane 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) of 1,1-, continued mixing about 1 minute.The mixing thing temperature of regulating during this is no more than 100 ℃.Allow the mixing thing that obtains rapidly by backer roll, be processed into laminarly, be cooled to simultaneously below 25 ℃, obtaining thus thickness is the laminar mold cleaning rubber compositon A of 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon A that obtains are shown in Table 1.Can judge from result of the test, laminar mold cleaning rubber compositon A shows good spatter property.
Embodiment 2 (the 1st mold cleaning rubber compositon of the present invention)
In embodiment 1, except the use level with substrate resin becomes EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 23) 900g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) beyond 600g, according to same step, obtain the laminar mold cleaning rubber compositon B that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon B that obtains are shown in Table 1.Can judge from result of the test, laminar mold cleaning rubber compositon B shows good spatter property.
Embodiment 3 (the 1st mold cleaning rubber compositon of the present invention)
In embodiment 1, except using the alternative MEA 150g (blend glue stuff 100 weight portions with respect to EPDM and BR are 10 weight portions) of (±)-1-amino-2-propyl alcohol 450g (blend glue stuff 100 weight portions with respect to EPDM and BR are 30 weight portions), according to same step, obtain the laminar mold cleaning rubber compositon C that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon C that obtains are shown in Table 1.Can judge from result of the test, laminar mold cleaning rubber compositon C shows good spatter property.
Embodiment 4 (the 1st mold cleaning rubber compositon of the present invention)
In embodiment 1, except substrate resin being become EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 23) 825g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 35,1,4 cis linkage contents are 95 % by weight) 675g, and the use level of white carbon is become 450g (blend glue stuff 100 weight portions with respect to EPDM and BR are 30 weight portions) in addition from 750g (blend glue stuff 100 weight portions with respect to EPDM and BR are 50 weight portions), obtain according to same step the laminar mold cleaning rubber compositon D that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon D that obtains are shown in Table 1.Can judge from result of the test, laminar mold cleaning rubber compositon D shows good spatter property.
Comparative example 1
In embodiment 1, except the use level with substrate resin becomes EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 23) 600g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) beyond 900g, according to same step, obtain the laminar mold cleaning rubber compositon E that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon E that obtains are shown in Table 1.Can judge from result of the test, the not filling of mould cavity part or the chip in mould etc. have occurred, need a large amount of cleaning operation time.In addition, spatter property is also bad, needs many injection numbers till cleaning finishes.
Table 1
The metewand of formability
Zero: unfilled incidence is lower than 3%
△: unfilled incidence is more than 3% but lower than 10%
*: unfilled incidence is more than 10%
The metewand of mold releasability
Zero: the incidence of chip is lower than 3%
△: the incidence of chip is more than 3% but lower than 10%
*: the incidence of chip is more than 10%
Embodiment 5 (the 2nd mold cleaning rubber compositon of the present invention)
In embodiment 1, except using dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) to substitute 1, two (tert-butyl hydroperoxide) cyclohexane 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) of 1-, and regulate mixing thing temperature so that it is no more than beyond 110 ℃, obtain according to same step the laminar mold cleaning rubber compositon F that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon F that obtains are shown in Table 2.Can judge from result of the test, laminar mold cleaning rubber compositon F shows good formability and spatter property.
Embodiment 6 (the 2nd mold cleaning rubber compositon of the present invention)
In embodiment 5, except the use level with substrate resin becomes EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 23) 900g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) beyond 600g, according to same step, obtain the laminar mold cleaning rubber compositon G that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon G that obtains are shown in Table 2.Can judge from result of the test, laminar mold cleaning rubber compositon G shows good formability and spatter property.
Embodiment 7 (the 2nd mold cleaning rubber compositon of the present invention)
in embodiment 5, except using (±)-1-amino-2-propyl alcohol 300g (blend glue stuff 100 weight portions with respect to EPDM and BR are 20 weight portions) to substitute MEA 150g (blend glue stuff 100 weight portions with respect to EPDM and BR are 10 weight portions), and use dicumyl peroxide 28g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1.9 weight portions) and normal-butyl 4, two (tert-butyl hydroperoxide) valerate 20g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1.3 weight portions) of 4-substitute dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) in addition, obtain according to same step the laminar mold cleaning rubber compositon H that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon H that obtains are shown in Table 2.Can judge from result of the test, laminar mold cleaning rubber compositon H shows good formability and spatter property.
Embodiment 8 (the 2nd mold cleaning rubber compositon of the present invention)
In embodiment 5, except with BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) 450g becomes BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 35,1,4 cis linkage contents are 95 % by weight) 450g, and dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) is become 1, two (tert-butyl hydroperoxide) cyclohexane 13g (blend glue stuff 100 weight portions with respect to EPDM and BR are 0.9 weight portion) of 1-and dicumyl peroxide 35g (blend glue stuff 100 weight portions with respect to EPDM and BR are 2.3 weight portions) in addition, obtain according to same step the laminar mold cleaning rubber compositon I that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon I that obtains are shown in Table 2.Can judge from result of the test, laminar mold cleaning rubber compositon I shows good formability and spatter property.
Comparative example 2
In embodiment 5, except the use level with substrate resin becomes EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 23) 600g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) beyond 900g, according to same step, obtain the laminar mold cleaning rubber compositon J that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon J that obtains are shown in Table 2.Can judge from result of the test, the not filling of mould cavity part or the chip in mould etc. have occurred, need a large amount of cleaning operation time.In addition, spatter property is also bad, needs many injection numbers till cleaning finishes.
Table 2
The metewand of pore
Zero: the incidence of pore is lower than 3%
△: the incidence of pore is more than 3% but lower than 10%
*: the incidence of pore is more than 10%
Embodiment 9 (the 3rd mold cleaning rubber compositon of the present invention)
Add EPDM sizing material (Mooney viscosity ML in the kneader of the compression type with chuck of 3000ml
1+4(100 ℃) are 23) 1050g and BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) 450g, on one side mixing about 3 minutes of cooling one side pressurization, the blend glue stuff of EPDM and BR becomes the rice cake shape, and its temperature becomes about 80 ℃.then add MEA 150g (blend glue stuff 100 weight portions with respect to EPDM and BR are 10 weight portions), the polyoxyalkylene decyl ethers is surfactant 75g (blend glue stuff 100 weight portions with respect to EPDM and BR is 5 weight portions), stearic acid 15g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1 weight portion), white carbon 650g (blend glue stuff 100 weight portions with respect to EPDM and BR are 43 weight portions), calcium carbonate 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), titanium oxide 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), zinc oxide 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), (Cognis Japan Co., Ltd. makes LoxiolG-78, the macromolecule complex ester) 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions) and Licolub H-4 (the modification hydrocarbon that Clariat Japan Co., Ltd. makes) 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), mixing about 3 minutes.Finally, add dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions), continued mixing about 1 minute.Regulate mixing thing temperature during this so that it is no more than 110 ℃.Allow the mixing thing that obtains rapidly by backer roll, be processed into laminarly, be cooled to simultaneously below 25 ℃, obtaining thus thickness is the laminar mold cleaning rubber compositon K of 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon K that obtains are shown in Table 3.Can judge from result of the test, laminar mold cleaning rubber compositon K shows good formability and spatter property.
Embodiment 10 (the 3rd mold cleaning rubber compositon of the present invention)
In embodiment 9, use EPDM sizing material (Mooney viscosity ML
1+4(100 ℃) are 8) alternative EPDM sizing material (the Mooney viscosity ML of 900g
1+4(100 ℃) are 23), with BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42,1,4 cis linkage contents are 95 % by weight) use level become 600g, the use level of Loxiol G-78 is become 30g (blend glue stuff 100 weight portions with respect to EPDM and BR are 2 weight portions), the use level of Licolub H-4 is become 15g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1 weight portion), the new zinc stearate 15g (blend glue stuff 100 weight portions with respect to EPDM and BR are 1 weight portion) that adds, in addition, obtain according to same step the laminar mold cleaning rubber compositon L that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon L that obtains are shown in Table 3.Can judge from result of the test, laminar mold cleaning rubber compositon L shows good formability and spatter property.
Embodiment 11
in embodiment 9, the use level of white carbon is become 700g (blend glue stuff 100 weight portions with respect to EPDM and BR are 47 weight portions), the use level of Loxiol G-78 is become 45g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3 weight portions), (Kao Corp makes to use aliphatic acid Amides S, fatty acid amide) 30g (blend glue stuff 100 weight portions with respect to EPDM and BR are 2 weight portions) substitutes the Licolub H-4 (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions) of 75g, and then newly add zinc stearate 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions), use 2,5-dimethyl-2,5-di-t-butyl hexane peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) substitutes dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions), in addition, obtain according to same step the laminar mold cleaning rubber compositon M that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon M that obtains are shown in Table 3.Can judge from result of the test, laminar mold cleaning rubber compositon M shows good formability and spatter property.
Embodiment 12
In embodiment 10, with BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 42, Isosorbide-5-Nitrae cis linkage content is 95 % by weight) 600g becomes BR sizing material (Mooney viscosity ML
1+4(100 ℃) are 35,1,4 cis linkage contents are 95 % by weight) 600g, and, use white carbon 700g (blend glue stuff 100 weight portions with respect to EPDM and BR are 47 weight portions) to substitute white carbon 650g (blend glue stuff 100 weight portions with respect to EPDM and BR are 43 weight portions), use zinc stearate 75g (blend glue stuff 100 weight portions with respect to EPDM and BR are 5 weight portions) to substitute zinc stearate 30g (blend glue stuff 100 weight portions with respect to EPDM and BR are 2 weight portions), use the Loxiol G-78 (blend glue stuff 100 weight portions with respect to EPDM and BR are 2 weight portions) of the alternative 30g of Loxiol G-78 (blend glue stuff 100 weight portions with respect to EPDM and BR are 4 weight portions) of 60g, use two (tert-butyl hydroperoxides)-diisopropyl benzene 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions) to substitute dicumyl peroxide 48g (blend glue stuff 100 weight portions with respect to EPDM and BR are 3.2 weight portions), in addition, obtain according to same step the laminar mold cleaning rubber compositon N that thickness is 6mm.
Characteristic value and the spatter property result of the test of the laminar mold cleaning rubber compositon N that obtains are shown in Table 3.Can judge from result of the test, laminar mold cleaning rubber compositon M shows good formability and spatter property.
Table 3
as mentioned above, the mold cleaning rubber compositon that contains following half finished rubber by use, can make workability (release property) good, and can not produce chip or pore, not only can easily remove die cavity and runner, the dirt of cast gate, but also can easily remove the dirt of steam vent and mould mould closing section, in described half finished rubber, the mixing ratio of EP rubbers and butadiene rubber is set to 90/10～50/50 weight portion, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness (shore hardness) is A60～95, 90% cure time (sulfurizing point) tc (90) when mold temperature is 175 ℃ shows the value of 50～100 seconds or 200～400 seconds.
In mold cleaning rubber compositon of the present invention, particularly the 3rd mold cleaning rubber compositon of the present invention is owing to containing releasing agent, so be suitable in the darker compact package die for manufacturing of the die cavitys such as PDIP or SOIC or compact package selling the cleaning of the less compact encapsulation die for manufacturing of number.
Claims (6)
1. compact package die for manufacturing cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 80/20～60/40 weight portion as substrate resin, described butadiene rubber has cis 1, the content of 4 keys is the above high-cis structures of 90 % by weight, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness is that shore hardness is A60～95, 90% cure time sulfurizing point tc(90 when mold temperature is 175 ℃) be the scope of the value of 50～100 seconds.
2. compact package die for manufacturing cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 80/20～60/40 weight portion as substrate resin, described butadiene rubber has cis 1, the content of 4 keys is the above high-cis structures of 90 % by weight, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness is that shore hardness is A60～95, 90% cure time sulfurizing point tc(90 when mold temperature is 175 ℃) be the scope of the value of 200～400 seconds.
3. compact package die for manufacturing cleaning rubber compositon, it is used for removing the dirt of the die surface that the forming process at curable resin produces, it is characterized in that, use the mixing ratio of EP rubbers and butadiene rubber to be set to the half finished rubber of 80/20～60/40 weight portion as substrate resin, described butadiene rubber has cis 1, the content of 4 keys is the above high-cis structures of 90 % by weight, and, the percentage elongation of this half finished rubber after sulfuration is solidified is 80～800%, hot strength is 3～10MPa, rubber hardness is that shore hardness is A60～95, 90% cure time sulfurizing point tc(90 when mold temperature is 175 ℃) be the scope of the value of 200～400 seconds, and described mold cleaning rubber compositon contains at least a releasing agent.
4. compact package die for manufacturing cleaning rubber compositon according to claim 3, wherein, the mixing ratio of described substrate resin and described releasing agent is that with respect to substrate resin 100 weight portions, releasing agent is 3～15 weight portions.
5. the described compact package die for manufacturing of any one cleaning rubber compositon according to claim 1～4, it is compression-type.
6. mould clean method, it has used the described compact package die for manufacturing of any one cleaning rubber compositon in claim 1～4.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007279837 | 2007-10-29 | ||
| JP2007-279837 | 2007-10-29 | ||
| JP2008-075045 | 2008-03-24 | ||
| JP2008075044 | 2008-03-24 | ||
| JP2008075045 | 2008-03-24 | ||
| JP2008-075044 | 2008-03-24 | ||
| JP2008-242103 | 2008-09-22 | ||
| JP2008242103 | 2008-09-22 | ||
| PCT/JP2008/069029 WO2009057479A1 (en) | 2007-10-29 | 2008-10-21 | Mold cleaning rubber compositon |
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| Publication Number | Publication Date |
|---|---|
| CN101821075A CN101821075A (en) | 2010-09-01 |
| CN101821075B true CN101821075B (en) | 2013-11-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008801106985A Expired - Fee Related CN101821075B (en) | 2007-10-29 | 2008-10-21 | Mold cleaning rubber compositon |
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|---|---|
| JP (1) | JP5391072B2 (en) |
| KR (1) | KR101491757B1 (en) |
| CN (1) | CN101821075B (en) |
| HK (1) | HK1143565A1 (en) |
| MY (1) | MY155143A (en) |
| TW (1) | TWI428384B (en) |
| WO (1) | WO2009057479A1 (en) |
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| CN101945746B (en) * | 2008-03-31 | 2013-09-18 | 日本碳化物工业株式会社 | Rubber composition for recovering mold releasability |
| JP5604822B2 (en) * | 2009-07-17 | 2014-10-15 | 日立化成株式会社 | Semiconductor device molding die cleaning composition, semiconductor device molding die cleaning material, and semiconductor device molding die cleaning method using the same |
| MY177272A (en) * | 2009-07-17 | 2020-09-10 | Nitto Denko Corp | Mold cleaner composition and mold cleaning material, and mold cleaning method using the same |
| CN103596738A (en) * | 2011-06-13 | 2014-02-19 | 日本电石工业株式会社 | Resin composition for die cleaning |
| CN103304901B (en) * | 2012-03-14 | 2017-03-01 | 日本电石工业株式会社 | Resin composition for cleaning mold and cleaning mold method |
| CN102775656B (en) * | 2012-07-15 | 2015-06-03 | 湖州师范学院 | Rubber composition used for cleaning integrated circuit (IC) die |
| JP6188697B2 (en) * | 2012-09-14 | 2017-08-30 | 日本カーバイド工業株式会社 | Mold release recovery resin composition and mold release recovery method |
| KR102161835B1 (en) * | 2013-01-31 | 2020-10-05 | 닛뽕 카바이도 고교 가부시키가이샤 | Resin composition for mold cleaning, and mold cleaning method |
| 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 |
| KR101656255B1 (en) * | 2014-04-04 | 2016-09-12 | (주)휴이노베이션 | Eco-friendly and high functional Rubber Composition for Cleaning and Releasing Mold of Enhanced detergency |
| CN107022424A (en) * | 2017-03-08 | 2017-08-08 | 安徽国晶微电子有限公司 | A kind of cleaning reagent for integrated circuit packaging mould |
| CN109957186A (en) * | 2017-12-22 | 2019-07-02 | 四川素恩吉科技有限公司 | A kind of mold composition |
| KR102304403B1 (en) | 2019-12-18 | 2021-09-17 | 황진상 | Resin composition for mold cleaning and manufacturing method thereof |
| KR102325676B1 (en) | 2019-12-18 | 2021-11-11 | 황진상 | Resin composition for mold cleaning and manufacturing method thereof |
| CN114456504A (en) * | 2022-01-28 | 2022-05-10 | 厦门市麦华橡胶制品有限公司 | Environment-friendly peroxide vulcanized EPDM material suitable for automatic demolding and preparation method thereof |
Citations (1)
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069827B2 (en) * | 1987-07-24 | 1994-02-09 | 日東電工株式会社 | Mold cleaning composition |
| JPH0381110A (en) * | 1989-08-24 | 1991-04-05 | Matsushita Electric Works Ltd | Molding material and method for cleaning of die |
| JP2974267B2 (en) * | 1991-09-30 | 1999-11-10 | 日本カーバイド工業株式会社 | Rubber composition for mold cleaning |
| JP2967842B2 (en) * | 1991-10-24 | 1999-10-25 | 日本カーバイド工業株式会社 | Rubber material for mold cleaning |
| JPH09262842A (en) * | 1996-03-28 | 1997-10-07 | Nitto Denko Corp | Cleaning of mold |
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2008
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| 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 |
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| Title |
|---|
| JP特开平9-262842A 1997.10.07 |
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| Publication number | Publication date |
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| WO2009057479A1 (en) | 2009-05-07 |
| TW200930757A (en) | 2009-07-16 |
| KR101491757B1 (en) | 2015-02-11 |
| JP5391072B2 (en) | 2014-01-15 |
| MY155143A (en) | 2015-09-15 |
| TWI428384B (en) | 2014-03-01 |
| HK1143565A1 (en) | 2011-01-07 |
| KR20100085025A (en) | 2010-07-28 |
| CN101821075A (en) | 2010-09-01 |
| JPWO2009057479A1 (en) | 2011-03-10 |
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