CN103304901A - Resin composition for cleaning mold and method for cleaning mold - Google Patents
Resin composition for cleaning mold and method for cleaning mold Download PDFInfo
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- CN103304901A CN103304901A CN2013100778649A CN201310077864A CN103304901A CN 103304901 A CN103304901 A CN 103304901A CN 2013100778649 A CN2013100778649 A CN 2013100778649A CN 201310077864 A CN201310077864 A CN 201310077864A CN 103304901 A CN103304901 A CN 103304901A
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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
- B29C33/722—Compositions for cleaning moulds
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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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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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
- C08K5/16—Nitrogen-containing compounds
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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
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2220/00—Type of materials or objects being removed
- B08B2220/04—Polymers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Moulds For Moulding Plastics Or The Like (AREA)
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Abstract
The present invention provides a resin composition which is used for cleaning a mold for cleaning mold dirt caused by various kinds of thermosetting resins and has high cleaning performance. The resin composition for cleaning the mold comprises the following components: ethylene-propylene rubber; butadiene rubber; at least one detergent selected from a group which is composed of urea, derivatives thereof, monocyclic monoterpene, ethyl acetate comprising alkyls with 4-6 carbon atoms, an alcohol with 4-6 carbon atoms, and a compound represented by a formula 1. In the formula 1, X represents oxygen atom or NR'; R and R' respectively represent hydrogen atom, alkyls with 1-4 carbon atoms, or hydroxyalkyl with 2-4 carbon atoms.
Description
Technical field
The present invention relates to a kind of resin composition for cleaning mold and cleaning mold method.
Background technology
When using the seal molding thing such as Resins, epoxy and die forming integrated circuit component, if repeatedly be shaped for a long time then can be made dirty in the inner surface of shaping dies.Continue to be shaped if keep intact continuously, then in most cases can be made dirty in the surface of seal molding thing or make the seal molding thing to be attached on the mould and bring obstacle to shaping operation.Therefore, need termly cleaning mold.As one of cleaning method of cleaning mold, proposed to use cleaning mold with the method (for example, with reference to Japanese Unexamined Patent Application Publication 2009-057479 communique) of rubber-like composition.
Summary of the invention
Using in the raw-material situation of Resins, epoxy as the seal molding thing, as resin composition for cleaning mold, various researchs have been carried out.
But, in recent years, use the thermosetting resin except Resins, epoxy to increase as the raw-material situation of seal molding thing, expect to develop the resin composition for cleaning mold of the cleaning that can be used in the mould dirt that the thermosetting resin by the various kinds that comprise Resins, epoxy causes.
The present invention In view of the foregoing finishes, and its purpose is to provide resin composition for cleaning mold cleaning, that cleaning performance is good and the cleaning mold method that can be used in the mould dirt that the thermosetting resin by various kinds causes.
As follows for the concrete means that address the above problem.
＜1〉a kind of resin composition for cleaning mold, it contains: ethylene-propylene rubber(EPR) and divinyl rubber, be selected from by urea and derivative, monocyclic monoterpene, to have carbonatoms be that ethyl acetate, the carbonatoms of 4～6 alkyl is at least a clean-out system and the vulcanizing agent in the group that forms of 4～6 alcohol and the compound shown in the following formula (1)
In the formula (1), X represents Sauerstoffatom or NR ', and R and R ' represent that independently of one another hydrogen atom, carbonatoms are that 1～4 alkyl or carbonatoms are 2～4 hydroxyalkyl.
＜2〉according to＜1〉described resin composition for cleaning mold, wherein, described clean-out system is for being selected from by 2-morpholine ethanol, urea, 1, at least a in the group that 3-dimethyl urea, limonene, Isoamyl Acetate FCC, pentyl acetate, 1-amylalcohol, morpholine, 4-methylmorpholine, 4-ethyl morpholine and 1-methylpiperazine form.
＜3〉according to＜1〉or＜2〉described resin composition for cleaning mold, wherein, described vulcanizing agent is superoxide, 1 minute half life temperature of this superoxide is 100 ℃～190 ℃.
＜4〉according to＜3〉described resin composition for cleaning mold, wherein, described superoxide is for being selected from by 1,1-two (uncle's hexyl peroxy) hexanaphthene, 1,1-two (uncle's hexyl peroxy)-3,3,5-trimethyl-cyclohexane and 2, at least a in the group that the 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane forms.
＜5〉a kind of cleaning mold method, it comprises: will＜1 〉～＜4 in each described resin composition for cleaning mold operation of being applied to the inner lip-deep operation of shaping dies and the mould that is applied with described resin composition for cleaning mold being heated.
In this specification sheets, the numerical value that the front and back of using the numerical range of "～" expression to refer to be included in "～" are put down in writing is as the scope of lower value and higher limit.
About the amount of each composition in the composition, in composition, exist in the situation of the multiple material that is equivalent to each composition, if not otherwise specified, then represent the total amount of this many kinds of substance of existing in the composition.
In this specification sheets, " operation " this term not only refers to independently operation, even can not be clearly and the situation of other operations differences, as long as but can reach the purpose of the expectation of this operation, then be also included within this term.
In this specification sheets, for example, in the situation that do not specify the alkyl of " alkyl " expression " straight chain, side chain and ring-type ".In addition, in the expression method of the group in this specification sheets (atomic group), record replaces and unsubstituted expression method comprises simultaneously and do not have substituent group and have substituent group.For example, " alkyl " not only comprises and do not have substituent alkyl (not substituted alkyl), also comprises to have substituent alkyl (substituted alkyl).
Among the present invention, " shaping dies inner surface " refers to the zone that contacts with the thing that is formed that is shaped by shaping dies.
According to the present invention, can provide resin composition for cleaning mold cleaning, that cleaning performance is good and the cleaning mold method that can be used in the mould dirt that the thermosetting resin by various kinds causes.
Embodiment
Below, resin composition for cleaning mold of the present invention and cleaning mold method are elaborated.
" resin composition for cleaning mold "
Resin composition for cleaning mold of the present invention contains ethylene-propylene rubber(EPR) and divinyl rubber, be selected from by urea and derivative, monocyclic monoterpene, to have carbonatoms be that ethyl acetate, the carbonatoms of 4～6 alkyl is at least a clean-out system and the vulcanizing agent in the group that forms of 4～6 alcohol and the compound shown in the formula (1).This resin composition for cleaning mold also contains other compositions such as lubricant, packing material or other additives as required.
Among the present invention, by adopting the cleaning mold that in ethylene-propylene rubber(EPR) and divinyl rubber, makes up specific clean-out system and vulcanizing agent to form with resin, be attached to that the inner lip-deep dirt of shaping dies decomposes or by affine and efficiently dirt is absorbed resin composition for cleaning mold inside with dirt, demonstrate thus good cleanup action thereby make.In addition, resin composition for cleaning mold of the present invention can easily be followed the shape of mould, therefore by adopting above-mentioned composition when cleaning mold, can clean to the corner on the inner surface of shaping dies, clean thereby can carry out mould with good operability.Therefore, resin composition for cleaning mold of the present invention comprises that in use cleaning performance is also good in the raw-material situation of thermosetting resin as the seal molding thing of various kinds of Resins, epoxy.
Below, each composition that consists of resin composition for cleaning mold of the present invention is elaborated.
＜rubber constituent 〉
Resin composition for cleaning mold of the present invention contains at least a ethylene-propylene rubber(EPR) and at least a divinyl rubber as rubber constituent.Among the present invention, mix and with ethylene-propylene rubber(EPR) and divinyl rubber.
Ethylene-propylene rubber(EPR) (following sometimes also brief note for " EPM ") comprise common ethylene-propylene rubber(EPR) (EPM) and ethylene-propylene-elastoprene (following sometimes also brief note be " EPDM ") the two, represent at least a in ethylene-propylene rubber(EPR) and the ethylene-propylene-elastoprene.
As above-mentioned ethylene-propylene rubber(EPR), the copolymerization ratio of optimal ethylene and the alpha-olefin that comprises at least propylene take molar ratio computing as ethylene/alpha-olefin=55/45-83/17, mooney viscosity ML
1+4(100 ℃) are the ethylene-propylene rubber(EPR) of 5-300, 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 ethylene-propylene rubber(EPR).
As above-mentioned alpha-olefin, except propylene, can also enumerate iso-butylene, 1-butylene, 1-amylene, 1-hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.
Ethylene/propene ratio in the above-mentioned ethylene-propylene rubber(EPR) can pass through
1The resonant frequency of H is under the condition of 500MHz resin composition for cleaning mold to be carried out
1H-NMR (proton magnetic resonance (PMR)) spectrum is measured and is calculated.In addition, also can use HPLC (high performance liquid chromatography) from resin composition for cleaning mold, to isolate ethylene-propylene rubber(EPR), then similarly measure by ordinary method
1H-NMR composes and more clearly calculates the ethylene/propene ratio.
In this specification sheets, as mooney viscosity ML
1+4The measuring method of (100 ℃) is measured according to JIS K6300-1 " do not add sulphur go system-physical property-the 1st one: system ー ニ ー viscosity Meter To I Ru viscosity and び ス コ ー チ タ イ system are asked め side ".Particularly, can be by the automatic mooney's viscosimeter SMV-300RT of Shimadzu that uses Shimadzu Scisakusho Ltd to make, the determination test temperature is that 100 ℃, warm up time are that 1 minute, the torque value of rotor after 4 minutes are obtained.
Above-mentioned ethylene-propylene-elastoprene represents to comprise by ethene, at least the alpha-olefin of propylene and the terpolymer that consists of as the diene monomers of the ring with 2 unconjugated double bonds or non-annularity thing.
Particularly, can enumerate the terpolymer that is consisted of by the alpha-olefins such as ethene, propylene and diene monomers.
As above-mentioned diene monomers, can enumerate: ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 1,7-octadiene, 1,9-decadiene, 1,11-12 carbon diene, 1,13-14 carbon diene, 1,15-, 16 carbon diene, 1,17-, 18 carbon diene, 1,19-20 carbon diene, 3,6-dimethyl-1, the 7-octadiene, 4,5-dimethyl-1, the 7-octadiene, the 5-methyl isophthalic acid, the 8-nonadiene, dicyclopentadiene, 1,5-cyclooctadiene, 1,7-encircles 12 carbon diene, 1,5, the 9-cyclododecatriene, Isosorbide-5-Nitrae-cycloheptadiene, 1，4-cyclohexadiene, norbornadiene, methene norbornene, the 2-methyl isophthalic acid, the 4-pentadiene, 1, the 5-hexadiene, 1,6-heptadiene, the methyl tetrahydroindene, Isosorbide-5-Nitrae-hexadiene etc.
In the total mass of ethylene-propylene rubber(EPR), the content that derives from the structural unit of diene composition in above-mentioned ethylene-propylene rubber(EPR)-elastoprene is preferably 6.5 quality %～9.5 quality %, more preferably 7.0 quality %～9.0 quality %, more preferably 7.5 quality %～8.5 quality %.In addition, the iodine number of above-mentioned ethylene-propylene rubber(EPR)-elastoprene is preferably 12～22, and more preferably 14～18.
As the copolymerization ratio of each monomer in this terpolymer, optimal ethylene is that 30 % by mole～80 % by mole, diene monomers are 0.1 % by mole～2 % by mole, all the other are the situation of alpha-olefin.
More preferably enumerate ethene and be 30 % by mole～60 % by mole terpolymer.And, as above-mentioned terpolymer EPDM, preferably use mooney viscosity ML
1+4(100 ℃) are 20～70 terpolymer.
About the content of above-mentioned ethylene-propylene rubber(EPR), from the viewpoint of clean-up performance, preferably be 10 quality %～50 quality % in the total mass of resin composition for cleaning mold, 20 quality %～40 quality % more preferably.Above-mentioned resin composition for cleaning mold can contain separately a kind of ethylene-propylene rubber(EPR), perhaps also can make up and contain two or more ethylene-propylene rubber(EPR).
Resin composition for cleaning mold contains at least a of divinyl rubber.Above-mentioned divinyl rubber (following sometimes also brief note the by abridging is " BR ") is not particularly limited, and can suitably select from normally used divinyl rubber.Wherein, from the viewpoint of cleaning performance, as divinyl rubber, the content that preferably has cis Isosorbide-5-Nitrae-key is above high-cis structure and mooney viscosity ML of 90 quality %
1+4(100 ℃) are 20～60 divinyl rubber, more preferably mooney viscosity ML
1+4(100 ℃) are 30～45 divinyl rubber.
And the mixing ratio of above-mentioned ethylene-propylene rubber(EPR) and above-mentioned divinyl rubber is preferably 90/10～50/50 by quality ratio, more preferably 80/20～55/45.
If ethylene-propylene rubber(EPR) is below 90 mass parts in total amount 100 mass parts of ethylene-propylene rubber(EPR) and divinyl rubber, then can keep good mold releasability, the clean operation time can be not elongated yet.In addition, if divinyl rubber is that then mold releasability is good below 50 mass parts, and can keep the flexibility of the molding after the sulfuration.Therefore, from the viewpoint of cleaning performance, more preferably the mixing ratio of above-mentioned ethylene-propylene rubber(EPR) and above-mentioned divinyl rubber is in above-mentioned scope.
The mass ratio of the content of the above-mentioned ethylene-propylene rubber(EPR) in the above-mentioned resin composition for cleaning mold and the content of above-mentioned divinyl rubber can pass through
1Under the condition of the resonant frequency of H: 500MHz resin composition for cleaning mold is measured
1H-NMR (proton magnetic resonance (PMR)) spectrum is calculated.
In addition, among the present invention, sulfuration is to comprise to add sulphur and make rubber constituent crosslinked and use superoxide to make crosslinked the two the concept of rubber constituent.
It is 80%～800% rubber constituent that above-mentioned rubber constituent is preferably vulcanized elongation after the curing, and the elongation after more preferably sulfuration is solidified is 100%～300% rubber constituent.Elongation is 80% when above, can keep the plasticity after the sulfuration, therefore from the viewpoint of cleaning performance more preferably.
The tensile strength that above-mentioned rubber constituent is preferably vulcanized after the curing is the rubber constituent of 3MPa～10MPa, and more preferably the tensile strength after the sulfuration sclerosis is the rubber constituent of 5MPa～8MPa.If tensile strength is more than the 3MPa, what then break is reduced, from the viewpoint of cleaning performance more preferably.
The rubber hardness (durometer hardness) that above-mentioned rubber constituent is preferably vulcanized after the curing is the rubber constituent of A60～95, and the rubber hardness after more preferably sulfuration is solidified is the rubber constituent of A70～90.Rubber hardness is in this scope the time, break and the occurrence frequency in space all low, therefore from the viewpoint of cleaning performance more preferably.
In addition, resin composition for cleaning mold of the present invention can contain other rubber constituents such as natural rubber, urethanes, nitrile rubber, organo-silicone rubber except containing ethylene-propylene rubber(EPR) and divinyl rubber.
As the content of above-mentioned rubber constituent, in the contained whole compositions of resin composition for cleaning mold, be preferably 20 quality %～90 quality % in quality criteria, more preferably 35 quality %～75 quality %, more preferably 40 quality %～65 quality %.
＜clean-out system 〉
Resin composition for cleaning mold of the present invention contain be selected from by urea and derivative, monocyclic monoterpene, to have carbonatoms be that ethyl acetate, the carbonatoms of 4～6 alkyl is at least a clean-out system (following sometimes also brief note be " specific clean-out system ") in the group that forms of 4～6 alcohol and the compound shown in the following formula (1).Owing to containing specific clean-out system, therefore, can not damage die main body or the coating metal on the inner surface of shaping dies is peeled off, can effectively act on the mould dirt, and can suppress to remain in because of clean-out system the bad order of the inner surperficial molded article that causes of shaping dies.
In the formula (1), X represents Sauerstoffatom or NR '.R and R ' represent that independently of one another hydrogen atom, carbonatoms are that 1～4 alkyl or carbonatoms are 2～4 hydroxyalkyl.
Above-mentioned urea and derivative thereof specifically can be enumerated urea, 1,3-dimethyl urea, 1,1-dimethyl urea, phenylurea, 1,3-dicyclohexylurea (DCU) etc.When making resin composition for cleaning mold, can be fully mixing and obtain stable mould cleaning performance in order to make above-mentioned ethylene-propylene rubber(EPR) and divinyl rubber and above-mentioned clean-out system, preferred urea or 1,3-dimethyl urea.
Above-mentioned monocyclic monoterpene specifically can be enumerated limonene, menthol, iridoid, piperitone, pulegone, eucalyptol etc.When making resin composition for cleaning mold, can be fully mixing and obtain stable mould cleaning performance, preferably limonene in order to make above-mentioned ethylene-propylene rubber(EPR) and divinyl rubber and above-mentioned clean-out system.
It is above-mentioned that to have carbonatoms be that the ethyl acetate of 4～8 alkyl specifically can be enumerated Isoamyl Acetate FCC, n-amyl acetate (pentyl acetate), acetic acid n-octyl, isobutyl acetate etc.During the making of resin composition for cleaning mold, can be fully mixing and obtain stable mould cleaning performance, preferred Isoamyl Acetate FCC or pentyl acetate in order to make above-mentioned ethylene-propylene rubber(EPR) and divinyl rubber and above-mentioned clean-out system.
Above-mentioned carbonatoms is that 4～8 alcohol specifically can be enumerated 1-amylalcohol, 1,2-hexylene glycol, primary isoamyl alcohol, 2-amylalcohol, BDO etc.Preparation is during resin composition for cleaning mold, can be fully mixing and obtain stable mould cleaning performance, preferably 1-amylalcohol in order to make above-mentioned ethylene-propylene rubber(EPR) and divinyl rubber and above-mentioned clean-out system.
As the compound shown in the above-mentioned formula (1), particularly, can enumerate 2-morpholine ethanol, morpholine, 4-methylmorpholine, 4-ethyl morpholine, 1-methylpiperazine, 1-piperazine-1-propylamine, 1-(p-methoxyphenyl) piperazine, 1-piperazine-1-propyl alcohol etc.During the preparation resin composition for cleaning mold, in order to make above-mentioned ethylene-propylene rubber(EPR) and divinyl rubber and the above-mentioned clean-out system can be fully mixing and obtain stable mould cleaning performance, preferably enumerate 2-morpholine ethanol, morpholine, 4-methylmorpholine, 4-ethyl morpholine or 1-methylpiperazine.
As above-mentioned specific clean-out system, from to the effect at the interface of mould dirt and with the viewpoint of the affinity of dirt, more preferably for example under the Heating temperature when using resin composition for cleaning mold of the present invention to clean as melted state and the thermosetting resin as the cleaning object is demonstrated the clean-out system of swelling or solvency action.In addition, as above-mentioned specific clean-out system, boiling point can excessively not store up close to the clean-out system of the Heating temperature in when cleaning clean-out system when the cleaning mold to be stayed on the mould thereby mould does not have dirt, therefore preferred.
As above-mentioned specific clean-out system, particularly, be preferably and be selected from by 1-methylpiperazine, 2-morpholine ethanol, urea, 1, at least a in the group that 3-dimethyl urea, limonene, Isoamyl Acetate FCC, pentyl acetate, 1-amylalcohol, morpholine, 4-methylmorpholine and 4-ethyl morpholine form, more preferably be selected from least a in the group that is formed by 1-methylpiperazine, 2-morpholine ethanol, limonene, Isoamyl Acetate FCC, pentyl acetate, morpholine, 4-methylmorpholine and 4-ethyl morpholine, more preferably the 1-methylpiperazine.
In addition, in the resin composition for cleaning mold of the present invention, above-mentioned specific clean-out system can be used alone, and also may be used two or more.
About the content of the above-mentioned specific clean-out system in the resin composition for cleaning mold among the present invention, when contained above-mentioned rubber constituent is made as 100 mass parts in resin composition for cleaning mold, be preferably 3 mass parts～35 mass parts.By being set as more than 3 mass parts, has the tendency that the mould cleaning performance is further improved, by being set as below 35 mass parts, has further inhibition remains in the bad order of the inner surperficial seal molding thing that causes of shaping dies because of clean-out system tendency.
In addition, the content of above-mentioned specific clean-out system is with respect to above-mentioned rubber constituent 100 mass parts more preferably 4 mass parts～32 mass parts, more preferably 5 mass parts～30 mass parts.
In addition, in the resin composition for cleaning mold among the present invention, except containing above-mentioned specific clean-out system, can contain other clean-out systems such as aniorfic surfactant, nonionic surface active agent, metallic soap.
＜vulcanizing agent 〉
Resin composition for cleaning mold of the present invention contains at least a vulcanizing agent.As above-mentioned vulcanizing agent, as long as can make above-mentioned rubber constituent crosslinked, sulfur-containing molecules not in the compound.
As above-mentioned vulcanizing agent, can enumerate: sulphur, sulfur monochloride, selenium, tellurium, zinc oxide, magnesium oxide, yellow lead oxide, organic compounds containing sulfur, dithiocar-bamate, oximes, chloranil, dinitroso compound, modified phenolic resins, polyamines, superoxide etc.Wherein, as above-mentioned vulcanizing agent, preferred superoxide.In addition, as superoxide, can be that organo-peroxide also can be inorganic peroxide, more preferably organo-peroxide.If contain organo-peroxide, the corrosive nature of the mould in incidental when cleaning when then not having the vulcanizing agent that uses sulfur-bearing, can promote at short notice the crosslinked of unvulcanized rubber that the demoulding is required, and make and crosslinkedly suitably carry out, therefore can be easily remove resin composition for cleaning after the cleaning from mould.
As above-mentioned organo-peroxide, as long as the superoxide structure with at least a divalence (O-O-) and at least a alkyl.
As above-mentioned superoxide, preferred 1 minute half life temperature is 100 ℃～190 ℃ superoxide.When half life temperature was higher than 190 ℃ in 1 minute, curring time became superfluous during cleaning mold.In addition, in the situation that do not improve die temperature during cleaning mold, therefore not tight cure and becoming fragile of resin composition for cleaning mold has the tendency that the operability of cleaning reduces.When half life temperature was lower than 100 ℃ in 1 minute, when the mfg. moulding die resin composition for cleaning, sulfuration aggravation during mixed refining process, so have the tendency that can't fully follow the shape of mould during cleaning mold.
In addition, more preferably 140 ℃～190 ℃ of 1 minute half life temperatures of above-mentioned superoxide, more preferably 145 ℃～180 ℃.
Among the present invention, above-mentioned superoxide half life temperature was 1 minute in 1 minute the time make the concentration of superoxide be reduced to half temperature of initial value.
Particularly, can followingly obtain 1 minute half life temperature.At first, make above-mentioned superoxide when the lower generation of certain temperature (T) thermolysis, the starting point concentration of above-mentioned superoxide is made as a, the decomposition amount of above-mentioned superoxide is made as x, time (t) and the relation of ln a/ (a-x) are mapped, obtain thus the gradient constant k of resulting straight line.Then, the transformation period under the temperature (T) can be by obtaining among the formula kt1/2=ln2 of k substitution as its definition that will obtain before.And then, repeat same step, obtain respectively transformation period (t1/2) under this temperature according to different temperature thus, lnt1/2 and the 1/T that obtains mapped.
The straight line that obtains is like this extrapolated, and thus, can obtain the transformation period (t1/2) by this figure that makes is 1 minute temperature, namely 1 minute half life temperature.
As above-mentioned organo-peroxide, be preferably and be selected from by 1,1-two (t-butylperoxy) hexanaphthene, 1,1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, new peroxide tert-butyl caprate, two (3,5, the 5-trimethyl acetyl) superoxide, 2,5-dimethyl-2,5-two (2-ethyl hexanoyl peroxy) hexane, two (4-toluyl) superoxide, benzoyl peroxide, the peroxidation tert-butyl acetate, 1,1-two (t-butylperoxy) hexanaphthene, uncle's hexyl peroxidation sec.-propyl monocarbonate, tert-butyl hydroperoxide 2-ethylhexyl monocarbonate, normal-butyl 4,4-two (t-butylperoxy) valerate, dicumyl peroxide, ditertiary butyl peroxide and 1,1,3, at least a in the group that the 3-tetramethyl butyl hydroperoxide forms, more preferably be selected from the hexanaphthene by 1,1-two (uncle's hexyl peroxy), 1,1-two (uncle's hexyl peroxy)-3,3, at least a in the group that 5-trimethyl-cyclohexane and 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane form.
From the viewpoint of 1 minute half life temperature, these organo-peroxides preparation can not vulcanize during resin composition for cleaning mold and operability during cleaning mold also good, therefore preferred.
In the resin composition for cleaning mold of the present invention, as above-mentioned superoxide, can consider the half life temperature of superoxide and cooperate the design of resin composition for cleaning mold and be used alone, also may be used the two or more vulcanization rates etc. of regulating.
In the resin composition for cleaning mold of the present invention, above-mentioned vulcanizing agent can be used alone, and also may be used two or more.
About the content of the above-mentioned vulcanizing agent in the resin composition for cleaning mold among the present invention, when contained above-mentioned rubber constituent is made as 100 mass parts in resin composition for cleaning mold, be preferably 1 mass parts～20 mass parts.By content being set as below 20 mass parts, the resin composition for cleaning mold after can preventing from cleaning becomes fragile, thereby can make the operation of removing from shaping dies become easy.By content being set as more than 1 mass parts, can making sulfuration carry out fully preventing that resin composition for cleaning mold from standing on the mould when cleaning, thereby can improve cleaning operation.
In addition, as the content of the above-mentioned vulcanizing agent in the resin composition for cleaning mold among the present invention, with respect to above-mentioned rubber constituent 100 mass parts more preferably 3 mass parts～10 mass parts, more preferably 4 mass parts～8 mass parts.
Except containing above-mentioned vulcanizing agent, resin composition for cleaning mold of the present invention can also contain vulcanization aid.As above-mentioned vulcanization aid, can enumerate such as Acrylic Acid Monomer, sulphur, zinc oxide etc.Particularly in the situation that the use superoxide as above-mentioned vulcanizing agent, can use sulphur or zinc oxide as vulcanization aid.
Resin composition for cleaning mold of the present invention can also contain vulcanization accelerator.
As above-mentioned vulcanization accelerator, can enumerate vulcanization accelerators such as guanidine system, aldehyde-amine system, aldehyde-ammonia system, thiazole system.
Be vulcanization accelerator as above-mentioned guanidine, can enumerate such as diphenylguanidine, triphenyl guanidine etc.
Be vulcanization accelerator as above-mentioned aldehyde-amine, can enumerate such as formaldehyde-para-totuidine condenses, acetaldehyde aniline condensate etc.
Be vulcanization accelerator as above-mentioned thiazole, can enumerate such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide etc.
In addition, except containing above-mentioned vulcanization accelerator, resin composition for cleaning mold of the present invention can also contain vulcanization accelerator additive.As above-mentioned vulcanization accelerator additive, can enumerate such as magnesium oxide, yellow lead oxide, lime etc.
The kind of above-mentioned vulcanization aid, above-mentioned vulcanization accelerator or above-mentioned vulcanization accelerator additive and amount can cooperate the design of resin composition for cleaning mold suitably to select.
(other compositions)
Resin composition for cleaning mold among the present invention can further contain other compositions such as lubricant, packing material, releasing agent or other additives as required.
(lubricant)
Resin composition for cleaning mold among the present invention can contain lubricant.By containing lubricant, the Synergist S-421 95 in the resin composition for cleaning mold is disperseed in adding man-hour mixing well, therefore preferred.
As above-mentioned lubricant, can enumerate metallic soap base lubricant, fatty acid ester base lubricant, fatty acid series lubricant, acid amides base lubricant, hydrocarbon system lubricant, aniorfic surfactant etc.
As above-mentioned metallic soap base lubricant, can enumerate such as Zinic stearas, Zinc tetradecanoate, aluminum stearate, calcium stearate etc.
As above-mentioned fatty acid ester base lubricant, can enumerate such as butyl stearate, butyl laurate, stearic stearolactone etc.
As the fatty acid series lubricant, can enumerate stearic acid, behenic acid, montanic acid etc.
As above-mentioned acid amides base lubricant, can enumerate such as ethylenebisstearamide, erucicamide, oleylamide, stearylamide, behenic acid acid amides etc.
As the hydrocarbon system lubricant, can enumerate whiteruss, paraffin, synthetic polyethylene waxes etc.
In order to make the good dispersion of the mixing middle Synergist S-421 95 that adds man-hour, as above-mentioned lubricant, more preferably stearic acid, behenic acid or montanic acid, further preferred stearic acid.
In the resin composition for cleaning mold of the present invention, above-mentioned lubricant can be used alone, and also may be used two or more.
As the content of above-mentioned lubricant, in the contained whole compositions of resin composition for cleaning mold, be preferably 0.1 quality %～20 quality % in quality criteria, more preferably 0.3 quality %～15 quality %.In addition, the content of lubricant is preferably more than 0.1 mass parts with respect to elastomeric content 100 mass parts and below 20 mass parts, and more preferably 0.5 mass parts is above and below 10 mass parts.
(packing material)
Resin composition for cleaning mold among the present invention can contain packing material.By containing packing material, during pressurization when cleaning mold resin composition for cleaning mold is fully exerted pressure, therefore, can make resin composition for cleaning mold spread all over the corner of mould, and can be in the situation that the soil release of mould with the inner surface of shaping dies of not wearing and tearing.
As above-mentioned packing material, can be any in organic filler material or the inorganic filling material, preferred inorganic filling material is because it can be in the situation that the soil release of mould with the inner surface of shaping dies of not wearing and tearing.
As above-mentioned inorganic filling material, can enumerate such as silicon-dioxide, aluminum oxide, calcium carbonate, aluminium hydroxide, titanium oxide etc.From the viewpoint of the dispersiveness resin composition for cleaning mold, as above-mentioned silicon-dioxide, preferred moisture amorphous silica, anhydrous amorphous silica, crystallinity silicon-dioxide etc.
As above-mentioned packing material, be preferably and be selected from least a in the group that is formed by moisture amorphous silica, titanium oxide and calcium carbonate, because its have can in the situation that the mould that do not wear and tear with the suitable hardness of the soil release on the inner surface of shaping dies, fully exert pressure during pressurization that thus can be when cleaning mold.
In the resin composition for cleaning mold of the present invention, above-mentioned packing material can be used alone, and also may be used two or more.
As the content of above-mentioned packing material, in the contained whole compositions of resin composition for cleaning mold, be preferably 10 quality %～80 quality % in quality criteria, more preferably 15 quality %～60 quality %, more preferably 20 quality %～40 quality %.
(releasing agent)
Resin composition for cleaning mold among the present invention can contain releasing agent.By containing releasing agent, the mold releasability effect of resin composition for cleaning mold after shaping is good, thereby the operability when making cleaning improves, and be therefore preferred.
As above-mentioned releasing agent, can enumerate such as metallic soap is that releasing agent, fatty acid ester are that releasing agent, synthetic wax, fatty amide are releasing agent etc.
Be releasing agent as above-mentioned metallic soap, can enumerate such as calcium stearate, Zinic stearas, Zinc tetradecanoate etc.
Be releasing agent as above-mentioned fatty acid ester, above-mentioned synthetic wax, above-mentioned fatty acyl amide releasing agent for example can be enumerated: Licowax OP (the partly-hydrolysed ester of montanic acid that Clariant Amada Co., Ltd. makes), Loxiol G-78 (the polymer complex ester that Emery Oleochemicals Amada Co., Ltd. makes), Licolub H-4 (the modification hydrocarbon that Clariant Amada Co., Ltd. makes), Loxiol VPN881 (the mineral oils synthetic wax that Emery Oleochemicals Amada Co., Ltd. makes), FATTY AMIDE S (fatty amide that Kao Corp makes), KAO WAX EB-P (fatty amide that Kao Corp makes), Alflow HT-50 (fatty amide that Japan Oil Co makes) etc.
The kind of above-mentioned releasing agent and amount can cooperate the design of resin composition for cleaning mold suitably to select.
(other additives)
Resin composition for cleaning mold of the present invention can contain the known additives such as softening agent, tackifier, whipping agent, coupling agent, antiscorch(ing).
(preparation method)
Preparation method as resin composition for cleaning mold of the present invention is not particularly limited, and can adopt known method.
For example, use compression type kneader with sleeve, banbury mixers, mixing roll mill etc., various mentioned components are carried out the mixing mixing thing that obtains.Thereby can make resulting mixing thing be configured as the shapes such as sheet by backer roll.
Shape can suitably be selected according to the mould of usefulness.
When being configured as sheet, the thickness of sheet is not particularly limited, and can be set as the scopes such as 3mm～10mm.
(purposes)
Resin composition for cleaning mold of the present invention can be used in the dirt cleaning of shaping dies.The kind of shaping dies is not particularly limited.As shaping dies, can enumerate such as the optical component sealing sealing with mould, rubber molding mould etc. with mould, semiconductor material.Particularly, can enumerate photodiode (LED) sealed mold, semiconductor-sealing-purpose sealed mold, rubber seal shaping dies, thermosetting resin parts shaping dies etc.From the forming temperature of mould and the viewpoint of set time, the preferred LED of shaping dies sealed mold, semiconductor packages sealed mold etc.
In addition, utilize the kind of the resin (following sometimes also brief note the by abridging is " cleaning object resin ") of above-mentioned shaping dies shaping to be not particularly limited.As resin, can enumerate such as silicone resin, Resins, epoxy, melamine resin, urea resin etc.Since light and heat are had stability, therefore, as the resin especially for optical component, preferred silicone resin, Resins, epoxy etc.
In addition, cleaning mold method during as the use resin composition for cleaning mold, roughly be divided into transmission type cleaning method and compression-type cleaning method, resin composition for cleaning mold of the present invention can be applicable to any cleaning method in transmission type and the compression-type.In addition, from improving operability, the viewpoint of shortening cleaning operation time, more preferably be applied to the compression-type cleaning method.
In addition, resin composition for cleaning mold of the present invention gets final product to using with the corresponding temperature of forming temperature of above-mentioned cleaning object resin by the mold heated that will be applied with resin composition for cleaning mold.Forming temperature is different because of the difference of the kind of above-mentioned cleaning object resin, for example in the situation that cleaning object resin is silicone resin, with mold heated to approximately 120 ℃ get final product, in the situation that cleaning object resin is Resins, epoxy, with mold heated extremely approximately 170 ℃ get final product.
In addition, resin composition for cleaning mold of the present invention is particularly suitable for the cleaning of the mould that uses in the shaping of optical component purposes.Usually, in the shaping of optical component purposes, require goods to have smoothness.Therefore, for the mould of optical component purposes, the temperature during for the cleaning of the shaping that makes goods and mould keeps low temperature and makes the inner surface of shaping dies keep level and smooth, need to not use physical property to grind or the cleaning of highly basic to mould.For example in the situation that cleaning object resin is silicone resin, even resin composition for cleaning mold of the present invention also demonstrates good cleaning performance under lower temperature in using the die forming of about 120 ℃ of such thermosetting resins.
" cleaning mold method "
Cleaning mold method of the present invention is used above-mentioned resin composition for cleaning mold of the present invention, has the operation that resin composition for cleaning mold is applied to the inner lip-deep operation of shaping dies (following sometimes also brief note be " applying operation ") and the mould that is applied with above-mentioned resin composition for cleaning mold is heated (following sometimes also brief note be " heating process ") and consists of.Cleaning mold method of the present invention can have as required other operations and consist of.
Cleaning mold method of the present invention has the formation of using resin composition for cleaning mold of the present invention, and therefore cleaning mold method cleaning, that easy and cleaning performance is good that can be used for the mould dirt that the thermosetting resin by various kinds causes can be provided.
In addition, shaping dies and utilize the resin that shaping dies is shaped kind etc. details as previously mentioned.
(applying operation)
The operation that applies among the present invention is that resin composition for cleaning mold of the present invention is applied to the inner lip-deep operation of shaping dies.The details of the formation of the resin composition for cleaning mold that uses in this operation and optimal way etc. as previously mentioned.
Be not particularly limited as resin composition for cleaning mold of the present invention being applied to the inner lip-deep method of shaping dies, can adopt known method.As the method that applies, can be by carrying out such as known methods such as the resin composition for cleaning mold that is configured as sheet being carried out compression molding, transmission shaping.
Resin composition for cleaning mold of the present invention was applied to the inner surface of shaping dies when upper, can applies with a part of surface of the chamber portion of drape forming mould or the mode of all surfaces.In the cleaning mold method of the present invention, spread all over equably the inner surface of whole shaping dies in order to make resin when being shaped, preferably the mode with the whole surface of the chamber portion of drape forming mould applies the metal resin composition for cleaning.
(heating process)
Heating process among the present invention is the operation that heats being applied to the inner lip-deep above-mentioned resin composition for cleaning mold of shaping dies.
Heating means, heating condition (temperature, time or number of times etc.) are not particularly limited, and can suitably select known method and condition according to the kind of the kind of above-mentioned cleaning object resin, resin composition for cleaning mold of the present invention.
In the above-mentioned heating condition, as Heating temperature, for example, from the viewpoint of simplicity, under the same method of the method when utilizing mould with above-mentioned cleaning object ester moulding and temperature and equal temperature, above-mentioned resin composition for cleaning mold is heated in the preferred heating process in the present invention.Thus, do not need for carry out cleaning mold make mould overheated or the cooling, can behind cleaning mold, carry out immediately die forming.
As the temperature in the heating process, particularly, in the situation that above-mentioned cleaning object resin is silicone resin, preferably be heated to 100 ℃～190 ℃, more preferably be heated to 120 ℃～160 ℃.
As heat-up time, as long as make the resin composition for cleaning mold tight cure and spread all over equably the inner surface of whole shaping dies, then be not particularly limited.For example, in the situation that above-mentioned cleaning object resin is silicone resin, preferably repeated 2 times～9 times with 200 seconds～500 seconds, more preferably repeated 2 times～7 times with 200 seconds～500 seconds, further preferably repeated 3 times～5 times with 240 seconds～360 seconds.
In the cleaning mold method, can will apply operation and heating process repeatedly.Apply preferred 2 times～9 times of the multiplicity (hereinafter referred to as " injection (shot) number of times ") of operation and heating process, more preferably 2 times～7 times, further preferred 2 times～5 times.In the cleaning mold method of the present invention, by using above-mentioned resin composition for cleaning mold, can dirt be removed from this mould with less multiplicity.
(other operations)
Cleaning mold method of the present invention can arrange as required other operations and consist of.As other operations, can enumerate such as preheating procedure, precharge operation etc.
Embodiment
Below, be described more specifically the present invention by embodiment.But the present invention only otherwise exceed its purport just can not be subjected to the restriction of following examples.In addition, if not otherwise specified, " part " and " % " is quality criteria.
＜embodiment 1 〉
The making of resin composition for cleaning mold
Make the resin composition for cleaning mold of embodiment 1 according to following step.
In the compression type kneader with sleeve of 3000ml, add ethylene-propylene rubber(EPR) (trade(brand)name EPT#4021, Mitsui Chemicals, Inc, the ethene: the ratio of components=55:45 of propylene, mooney viscosity ML of 780g
1+4(100 ℃) are 24, and diene content (%) is 8.1) and the divinyl rubber of 520g (commodity are called BR01, JSR Corp., mooney viscosity ML
1+4(100 ℃) are 45, and proportion is 0.9, and cis Isosorbide-5-Nitrae-linkage content is 95%), in cooling, pressurizeed mixing approximately 3 minutes.
Mixing blank becomes the rice cake shape, and the temperature of mixing blank is approximately 80 ℃.
Then, add the 1-methylpiperazine as clean-out system (total 100 mass parts with respect to ethylene-propylene rubber(EPR) and divinyl rubber are 10 mass parts), the 13g of 130g the stearic acid as lubricant, (commodity are called Nipsil LP to the moisture amorphous silica as inorganic filling material of 637g, east Cao silicon-dioxide company) and the titanium oxide (commodity are called CR-80, Ishihara Sangyo Kaisha, Ltd.) of 65g also mixing approximately 3 minutes.
At last, add 104g as 1 of vulcanizing agent, 1-two (uncle's hexyl peroxy) hexanaphthene (commodity are called Perhexa HC, Japan Oil Co, half life temperature was 149.2 ℃ in 1 minute) also continued mixing approximately 1 minute.
Mixing thing temperature is during this period regulated so that it is no more than 100 ℃.
Resulting mixing thing is processed into sheet by backer roll immediately, and is cooled to below 25 ℃, and forming thickness is the sheet of 7mm, obtains the resin composition for cleaning mold of embodiment 1.
The evaluation method of spatter property test
The dirt on the inner surface of shaping dies is by using LED to realize with sealed mold, the shaping the silicone resin (commodity are called LPS-3419) as commercially available Shin-Etsu Chemial Co., Ltd's manufacturing of one of binary liquid shape silicone resin shaped material being carried out injecting for 400 times under 120 ℃ die temperature.
Cleaning operation by with this mould resin composition for cleaning mold being repeated to be shaped until can will shaping dies carry out till the soil release on inner surface.
300 seconds of the lower heating of condition (die temperature is 120 ℃) that the condition of the resin composition for cleaning mold of embodiment 1 when silicone resin being shaped with sealed mold with use LED is identical.
The evaluation of spatter property is undertaken by the removability of the dirt of the end of the needed frequency injection in cleaning mold chamber and visual judgement mold cavity.
For the evaluation of spatter property, frequency injection more at least spatter property is better.
About cleaning to the evaluation of the needed frequency injection of gate portions and end of mold cavity, in the situation that finish frequency injection be below 10 times by the record frequency injection estimate, in addition, be judged to be " * " with immediately carrying out cleaning the situation that to remove dirt for 10 times.
Following the carrying out of evaluation of the removability of the dirt by visual end to mold cavity: very good person is evaluated as " A ", good person is evaluated as " B ", existing problems person is evaluated as " C ".
The results are shown in the table 1.
＜embodiment 2～18, comparative example 1 〉
In the making of the resin composition for cleaning mold of embodiment 1, clean-out system and vulcanizing agent are changed to the clean-out system of putting down in writing in the table 1, in addition, operate similarly to Example 1, obtain the resin composition for cleaning mold of embodiment 2～embodiment 7 and embodiment 9～embodiment 18.The evaluation result of spatter property test is shown in table 1 and the table 2.The unit of the numerical value in the composition of table 1 and table 2 is g, and "-" expression does not cooperate.
In addition, resin composition for cleaning mold for embodiment 8, in the evaluation method of the spatter property of embodiment 1 test, replace silicone resin and estimate spatter property to Resins, epoxy (Resins, epoxy that Nitto Denko Corp makes, commodity are called NT-600H).In addition, be accompanied by cleaning object resin and change to Resins, epoxy from silicone resin, the die temperature in the evaluation method of spatter property test is changed to 150 ℃ from 120 ℃.In addition, operate similarly to Example 1 and obtain resin composition for cleaning mold, and carry out the evaluation of spatter property test.The results are shown in the table 1.
In the resin composition for cleaning mold of embodiment 1, clean-out system is changed to the clean-out system of record in the table 2, in addition, operate similarly to Example 1, obtain the resin composition for cleaning mold of comparative example 1.The evaluation result of spatter property test is shown in Table 2.
Table 1
*) curring time being set as 90 minutes estimates.
*) Resins, epoxy is estimated.
Table 2
Result by table 1 shows, the resin composition for cleaning mold of the present application has good spatter property.In addition, the frequency injection of finishing of embodiment 1～3,6 resin composition for cleaning mold is 5 times～6 times, and the dirt of the end of mold cavity also can fully clean, and shows that it has good especially spatter property.
In addition, for the resin composition for cleaning mold of embodiment 5, produced the clouding of thinking by due to the clean-out system on the inner surface of shaping dies, finishing frequency injection is 5 times.The each curring time of the resin composition for cleaning mold of embodiment 7 needs 90 minutes, but has the good spatter property equal with embodiment 1.In addition, shown by the result of embodiment 8, no matter the application's resin composition for cleaning mold cleans the object resin, and why kind all demonstrates good spatter property.In addition, for the resin composition for cleaning mold of embodiment 11, the curing of the resin composition for cleaning mold during cleaning is insufficient, the operability when needing to consider the rear removal of cleaning resin composition for cleaning mold, but its clean-up performance is high as can be known.On the other hand, 10 cleaning molds are also insufficient even the resin composition for cleaning mold of comparative example 1 repeats to be shaped, and show that its clean-up performance to silicone resin is poor.
Claims (5)
1. resin composition for cleaning mold, it contains:
Ethylene-propylene rubber(EPR) and divinyl rubber,
Be selected from by urea and derivative, monocyclic monoterpene, to have carbonatoms be that ethyl acetate, the carbonatoms of 4～6 alkyl is at least a clean-out system in the group that forms of 4～6 alcohol and the compound shown in the following formula (1), and
Vulcanizing agent,
In the formula (1), X represents Sauerstoffatom or NR ', and R and R ' represent that independently of one another hydrogen atom, carbonatoms are that 1～4 alkyl or carbonatoms are 2～4 hydroxyalkyl.
2. resin composition for cleaning mold according to claim 1, wherein, described clean-out system is for being selected from by 2-morpholine ethanol, urea, 1, at least a in the group that 3-dimethyl urea, limonene, Isoamyl Acetate FCC, pentyl acetate, 1-amylalcohol, morpholine, 4-methylmorpholine, 4-ethyl morpholine and 1-methylpiperazine form.
3. according to claim 1 or resin composition for cleaning mold claimed in claim 2, wherein, described vulcanizing agent is superoxide, and 1 minute half life temperature of this superoxide is 100 ℃～190 ℃.
4. resin composition for cleaning mold according to claim 3, wherein, described superoxide is for being selected from by 1,1-two (uncle's hexyl peroxy) hexanaphthene, 1,1-two (uncle's hexyl peroxy)-3,3,5-trimethyl-cyclohexane and 2, at least a in the group that the 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane forms.
5. cleaning mold method, it comprises:
With each described resin composition for cleaning mold in claim 1～claim 4 be applied to the inner lip-deep operation of shaping dies and
The operation that the mould that is applied with described resin composition for cleaning mold is heated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-057615 | 2012-03-14 | ||
| JP2012057615 | 2012-03-14 |
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| CN103304901A true CN103304901A (en) | 2013-09-18 |
| CN103304901B CN103304901B (en) | 2017-03-01 |
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| CN201310077864.9A Expired - Fee Related CN103304901B (en) | 2012-03-14 | 2013-03-12 | Resin composition for cleaning mold and cleaning mold method |
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| Country | Link |
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| JP (1) | JP6002065B2 (en) |
| KR (1) | KR20130105437A (en) |
| CN (1) | CN103304901B (en) |
| TW (1) | TWI565576B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047694A (en) * | 2017-12-27 | 2018-05-18 | 东莞市浦元电子有限公司 | Semiconductor packaging mold cleaning material and preparation method thereof |
| CN111712542A (en) * | 2018-05-29 | 2020-09-25 | Nok株式会社 | Rubber composition containing ethylene-propylene-nonconjugated polyene copolymer |
| CN112847970A (en) * | 2020-12-24 | 2021-05-28 | 天津德高化成新材料股份有限公司 | Foaming mold cleaning adhesive tape without carcinogenic, mutagenic or reproductive toxic components |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014119485A1 (en) * | 2013-01-31 | 2014-08-07 | 日本カーバイド工業株式会社 | Resin composition for mold cleaning, and mold cleaning method |
| JP6274948B2 (en) * | 2014-04-04 | 2018-02-07 | 日本カーバイド工業株式会社 | Mold cleaning resin composition and mold cleaning method using the same |
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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 |
| JP2005254786A (en) * | 2004-03-13 | 2005-09-22 | Toshiyuki Watabe | Molding die detergent and cleaning method |
| CN101821075A (en) * | 2007-10-29 | 2010-09-01 | 日本碳化物工业株式会社 | Mold cleaning rubber compositon |
| KR20110009873A (en) * | 2009-07-23 | 2011-01-31 | (주)에이씨티 | Rubber compound for clearing of semiconductor mold |
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| CN1275753C (en) * | 2000-12-13 | 2006-09-20 | 旭化成株式会社 | Detergent |
| JP2002210748A (en) * | 2001-01-18 | 2002-07-30 | West Japan Plastic Products Industrial Association | Detergent for plastic molding machine |
| JP2005344210A (en) * | 2004-05-06 | 2005-12-15 | Somakkusu Kk | Mold cleaning solution, mold cleaning method and mold cleaning apparatus |
| 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 |
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2013
- 2013-03-12 CN CN201310077864.9A patent/CN103304901B/en not_active Expired - Fee Related
- 2013-03-12 KR KR1020130025979A patent/KR20130105437A/en not_active Application Discontinuation
- 2013-03-13 JP JP2013050483A patent/JP6002065B2/en not_active Expired - Fee Related
- 2013-03-14 TW TW102109027A patent/TWI565576B/en not_active IP Right Cessation
Patent Citations (5)
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| JPH0220538A (en) * | 1988-07-08 | 1990-01-24 | Denki Kagaku Kogyo Kk | Rubber composition for cleaning mold |
| 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 |
| JP2005254786A (en) * | 2004-03-13 | 2005-09-22 | Toshiyuki Watabe | Molding die detergent and cleaning method |
| CN101821075A (en) * | 2007-10-29 | 2010-09-01 | 日本碳化物工业株式会社 | Mold cleaning rubber compositon |
| KR20110009873A (en) * | 2009-07-23 | 2011-01-31 | (주)에이씨티 | Rubber compound for clearing of semiconductor mold |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047694A (en) * | 2017-12-27 | 2018-05-18 | 东莞市浦元电子有限公司 | Semiconductor packaging mold cleaning material and preparation method thereof |
| CN111712542A (en) * | 2018-05-29 | 2020-09-25 | Nok株式会社 | Rubber composition containing ethylene-propylene-nonconjugated polyene copolymer |
| CN111712542B (en) * | 2018-05-29 | 2023-02-28 | Nok株式会社 | Rubber composition containing ethylene-propylene-nonconjugated polyene copolymer |
| CN112847970A (en) * | 2020-12-24 | 2021-05-28 | 天津德高化成新材料股份有限公司 | Foaming mold cleaning adhesive tape without carcinogenic, mutagenic or reproductive toxic components |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130105437A (en) | 2013-09-25 |
| JP2013216093A (en) | 2013-10-24 |
| TW201343355A (en) | 2013-11-01 |
| TWI565576B (en) | 2017-01-11 |
| JP6002065B2 (en) | 2016-10-05 |
| CN103304901B (en) | 2017-03-01 |
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