WO2014119485A1 - 金型清掃用樹脂組成物及び金型清掃方法 - Google Patents
金型清掃用樹脂組成物及び金型清掃方法 Download PDFInfo
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- WO2014119485A1 WO2014119485A1 PCT/JP2014/051543 JP2014051543W WO2014119485A1 WO 2014119485 A1 WO2014119485 A1 WO 2014119485A1 JP 2014051543 W JP2014051543 W JP 2014051543W WO 2014119485 A1 WO2014119485 A1 WO 2014119485A1
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- mold cleaning
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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
Definitions
- the present invention relates to a mold cleaning resin composition and a mold cleaning method.
- the mold cleaning composition contains at least one selected from the group consisting of synthetic rubber and synthetic resin, at least one selected from the group consisting of alkali metal salts and alkali metal hydroxides, and water.
- a mold cleaner composition see, for example, Japanese Patent Application Laid-Open No. 2011-21156
- a mold cleaning composition containing at least one selected from the group and an organic solvent has been proposed to improve cleaning performance. .
- the mold contamination improving rubber composition contains rubber and an alkali metal phosphate, it is possible to prevent deterioration of the mold cleaning workability due to the addition of silica and contamination of the mold due to the vulcanizing agent. (For example, see Japanese Patent Laid-Open No. 04-234444).
- a conventional mold cleaning resin composition containing an alkali metal salt or the like does not have sufficient storage stability and may not exhibit sufficient cleaning performance after a long period of time (for example, 6 months). there were.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a mold cleaning resin composition excellent in cleaning performance and storage stability and a mold cleaning method using the same.
- a synthetic rubber a compound selected from the group consisting of an alkali metal salt and an alkali metal hydroxide, silica, and a vulcanizing agent, and a moisture content of 0.20% by mass or more 3 It is a resin composition for mold cleaning which is .5% by mass or less.
- ⁇ 2> The mold cleaning resin composition according to ⁇ 1>, wherein the synthetic rubber includes ethylene-propylene rubber and butadiene rubber.
- the mass ratio of the content of the compound selected from the group consisting of the alkali metal salt and the alkali metal hydroxide to the water content is from 0.1 to 5.0. It is a resin composition for metal mold
- ⁇ 5> The mold cleaning resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein a mass ratio of the silica content to the water content is 3 or more and 30 or less. is there.
- ⁇ 6> The mold cleaning according to any one of ⁇ 1> to ⁇ 5>, wherein the silica has an equilibrium moisture content of 5% by mass to 9% by mass at a relative humidity of 60% and a temperature of 23 ° C. Resin composition.
- the content of the compound selected from the group consisting of the alkali metal salt and the alkali metal hydroxide is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the synthetic rubber.
- the content of the vulcanizing agent is any one of ⁇ 1> to ⁇ 7>, in which the content is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the synthetic rubber. It is a resin composition for metal mold cleaning.
- ⁇ 9> A step of applying the mold cleaning resin composition according to any one of ⁇ 1> to ⁇ 8> to the inner surface of the molding die, and the mold cleaning resin composition And a step of heating the formed molding die.
- a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
- the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
- the “inner surface of the molding die” means a region in contact with a workpiece to be molded by the molding die.
- the “molding mold” may be simply referred to as “mold”.
- the resin composition for mold cleaning of the present invention includes a synthetic rubber, at least one selected from the group consisting of an alkali metal salt and an alkali metal hydroxide (hereinafter, also referred to as “specific cleaning agent”), silica, A vulcanizing agent, and the moisture content is 0.20% by mass or more and 3.50% by mass or less in the total mass of the mold cleaning resin composition.
- specific cleaning agent an alkali metal salt and an alkali metal hydroxide
- silica silica
- a vulcanizing agent A vulcanizing agent
- the resin composition for mold cleaning of the present invention contains silica and a specific cleaning agent that is at least one selected from the group consisting of alkali metal salts and alkali metal hydroxides, and the moisture content is specified.
- the specific cleaning agent acts effectively and can exhibit excellent cleaning performance.
- the mold cleaning resin composition of the present invention exhibits excellent cleaning performance even after a long period (for example, 6 months) has elapsed since the mold cleaning resin composition was produced. Can do. This can be considered as follows, for example.
- the conventional mold cleaning resin composition containing an alkali metal salt, etc. reduces the amount of water contained in the mold cleaning resin composition during storage of the mold cleaning resin composition, and the initial set physical properties (Mooney Viscosity, tensile strength, elongation, vulcanization characteristics, etc.) are considered to change. It is considered that the mold cleaning resin composition having a reduced amount of moisture during storage does not stretch properly during mold cleaning, and thus causes poor filling of the mold and poor mold cleaning.
- the inventors of the present invention include silica in the mold cleaning resin composition, and further the moisture content is 0.20% by mass or more and 3.50% by mass or less, so that the moisture over time is increased. It has been found that a decrease in the amount can be suppressed. Thereby, it is thought that the resin composition for metal mold
- a resin composition for mold cleaning generally containing an alkali metal salt and moisture exhibits excellent mold cleaning ability.
- the vulcanizing agent contained in the mold cleaning resin composition tends to deteriorate (decompose) due to the influence of heat, light, oxygen in the air, etc.
- the mold cleaning composition after long-term storage In some cases, the vulcanization performance may be reduced.
- the mold cleaning resin composition is not sufficiently cured at the time of mold cleaning, and therefore, contaminants cannot be sufficiently removed from the mold surface.
- the inventors of the present invention believe that in a resin composition for mold cleaning during long-term storage, deterioration of the vulcanizing agent is promoted by moisture contained in the mold cleaning composition.
- the moisture content is 0.20 mass% to 3.50 mass% after silica is contained instead.
- the moisture in the mold cleaning resin composition may be water added during the production of the mold cleaning resin composition or may be moisture contained in the material constituting the mold cleaning resin composition.
- the moisture in the mold cleaning resin composition is preferably moisture contained in the material constituting the mold cleaning resin composition from the viewpoint of cleaning performance and storage stability.
- the moisture content in the mold cleaning resin composition is 0.20% by mass or more and 3.50% by mass or less, and 0.50% by mass or more and 3.00% by mass from the viewpoint of mold cleaning properties and storage stability.
- % Is preferably 0.80% by mass or more and 2.90% by mass or less, more preferably 1.25% by mass or more and 2.80% by mass or less, and 1.40% by mass.
- % To 1.80% by mass is particularly preferable.
- the moisture content in the mold cleaning resin composition can be measured by the Karl Fischer method. Specifically, it is measured by a moisture vaporization-coulometric titration method using a Karl Fischer moisture meter CA-100 and a moisture vaporizer VA-100 manufactured by Mitsubishi Chemical Corporation. In addition, the temperature for vaporization shall be 180 degreeC.
- the resin composition for mold cleaning contains at least one synthetic rubber as a rubber component.
- the synthetic rubber is not particularly limited, and can be appropriately selected from commonly used synthetic rubbers.
- Synthetic rubber is so-called unvulcanized rubber, for example, ethylene- ⁇ -olefin rubber such as butadiene rubber (BR), nitrile rubber (NBR), ethylene-propylene rubber (EPR), styrene-butadiene rubber (SBR), Examples include polyisoprene rubber (IR), butyl rubber (IIR), silicone rubber (Q), and fluororubber (FKM). These may be used alone or in combination of two or more. These unvulcanized rubbers are vulcanized in the mold to become vulcanized rubber.
- the synthetic rubber is preferably at least one selected from the group consisting of ethylene-propylene rubber and butadiene rubber from the viewpoint of low contamination during mold cleaning and low odor during vulcanization. More preferably, it is a mixture of at least one ethylene-propylene rubber and at least one butadiene rubber.
- ethylene-propylene rubber includes both ordinary ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (hereinafter sometimes abbreviated as “EPDM”). Meaning at least one selected from the group consisting of ethylene-propylene rubber and ethylene-propylene-diene rubber.
- EPM ordinary ethylene-propylene rubber
- EPDM ethylene-propylene-diene rubber
- Examples of the ⁇ -olefin include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.
- the ethylene / propylene ratio in the ethylene-propylene rubber can be calculated by measuring a 1 H-NMR (proton nuclear magnetic resonance) spectrum at a resonance frequency of 1 H: 500 MHz for the resin composition for mold cleaning. .
- the 1 H-NMR spectrum is measured in the same manner, thereby making it clearer.
- the ethylene / propylene ratio can also be calculated.
- the ethylene-propylene-diene rubber means a terpolymer comprising ethylene, an ⁇ -olefin containing at least propylene, and a diene monomer which is a cyclic or non-cyclic product having two non-conjugated double bonds.
- terpolymers composed of ethylene, an ⁇ -olefin such as propylene, and a diene monomer are examples of terpolymers composed of ethylene, an ⁇ -olefin such as propylene, and a diene monomer.
- diene monomer examples include ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,15-hexadecadiene, 1,17-octadecadien, 1,19-icosadien, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nonadiene, dicyclo Pentadiene, 1,5-cyclooctadiene, 1,7-cyclododecadiene, 1,5,9-cyclododecatriene, 1,4-cycloheptadiene, 1,4-cyclohexadiene, norbornadiene, methylene norbornene, 2- Methylpentadiene-1,4,1,5-hexadiene, 1,
- the content of the structural unit derived from the diene component in the ethylene-propylene-diene rubber is preferably 6.5% by mass to 9.5% by mass in the total mass of the ethylene-propylene-diene rubber, and 7.0% by mass. % To 9.0% by mass, more preferably 7.5% to 8.5% by mass.
- the iodine value of the ethylene-propylene-diene rubber is preferably 12-22, and more preferably 14-18.
- the copolymerization ratio of each monomer in the terpolymer ethylene-propylene-diene rubber is as follows: ethylene is 30 mol% to 80 mol%, diene monomer is 0.1 mol% to 3 mol%, and the remainder is ⁇ -olefin. In some cases, it is preferable that ethylene is 30 mol% to 70 mol%, diene monomer is 0.1 mol% to 3 mol%, and the remainder is ⁇ -olefin.
- ethylene-propylene-diene rubber one having a Mooney viscosity ML 1 + 4 (100 ° C.) of 5 to 70 is preferably used.
- the Mooney viscosity ML 1 + 4 (100 ° C.) of the ethylene-propylene rubber is not particularly limited. From the viewpoint of cleaning performance, the Mooney viscosity ML 1 + 4 (100 ° C.) of the ethylene-propylene rubber is preferably 5 to 40, and more preferably 5 to 30.
- the Mooney viscosity is measured in accordance with JIS K 6300-1, “Unvulcanized rubber—Physical characteristics—Part 1: Determination of viscosity and scorch time using Mooney viscometer”.
- the content of the ethylene-propylene rubber is preferably 10% by mass to 50% by mass, and preferably 20% by mass to 40% by mass in the total mass of the mold cleaning resin composition from the viewpoint of cleaning performance. It is more preferable.
- the mold cleaning resin composition may contain one kind of ethylene-propylene rubber, or may contain two or more kinds in combination.
- the resin composition for mold cleaning preferably contains at least one butadiene rubber.
- the butadiene rubber is not particularly limited, and can be appropriately selected from commonly used butadiene rubbers. Among them, from the viewpoint of cleaning performance, butadiene rubber is a butadiene rubber having a high cis structure in which the content of cis 1,4 bonds is 90% by mass or more and a Mooney viscosity ML 1 + 4 (100 ° C.) of 20 to 60. A butadiene rubber having a high cis structure in which the content of the cis 1,4 bond is 90% by mass or more and a Mooney viscosity ML 1 + 4 (100 ° C.) of 30 to 45 is more preferable.
- the said butadiene rubber may be used individually by 1 type, and may use 2 or more types together.
- the mold cleaning resin composition contains the ethylene-propylene rubber and the butadiene rubber, the hardness of the mold cleaning resin composition should be kept appropriate when removing dirt on the inner surface of the molding die.
- the resin composition for mold cleaning can be appropriately filled up to the details inside the mold. Moreover, since the strength of the mold cleaning resin composition can be maintained, the mold cleaning resin composition does not become brittle, and after removing the dirt, the mold cleaning resin composition is released from the mold. Work can be done easily.
- the mass ratio (A) / (B) of the content of the ethylene-propylene rubber (A) contained in the resin composition for mold cleaning to the content of the butadiene rubber (B) is 20/80 to 90/10. It is preferable that the ratio is 30/70 to 80/20. If the ethylene-propylene rubber is 90 parts by mass or less in 100 parts by mass of the total amount of ethylene-propylene rubber and butadiene rubber, good mold releasability is maintained and the cleaning operation time is not prolonged. If the butadiene rubber is 80 parts by mass or less, the mold releasability is good and the flexibility of the molded product after vulcanization is maintained. Therefore, if the blending ratio of the ethylene-propylene rubber and the butadiene rubber is within the above range, it is preferable from the viewpoint of cleaning performance.
- the ethylene in the mold cleaning resin composition - the mass ratio to the content of the butadiene rubber content of propylene rubbers, for mold cleaning resin composition, 1 H-NMR (the proton nuclear magnetic resonance) spectra 1
- the resonance frequency of H can be calculated by measuring at 500 MHz.
- the synthetic rubber preferably has an elongation of 40% to 800%, more preferably 100% to 300% after vulcanization and curing. If the elongation percentage after vulcanization and curing of the synthetic rubber is 40% or more, the moldability after vulcanization is maintained, which is preferable from the viewpoint of cleaning performance.
- the synthetic rubber preferably has a tensile strength after vulcanization and curing of 3 MPa to 10 MPa, and more preferably 5 MPa to 8 MPa. If the tensile strength of the synthetic rubber after vulcanization and curing is 3 MPa or more, the occurrence of chipping is reduced, which is preferable from the viewpoint of cleaning performance.
- the synthetic rubber preferably has a rubber hardness (durometer hardness) after vulcanization curing of A60 to 95, and more preferably A70 to 90. If the rubber hardness after vulcanization and curing of the synthetic rubber is within this range, the occurrence frequency of chipping and voids is low, which is preferable from the viewpoint of cleaning performance.
- the resin composition for mold cleaning preferably contains ethylene-propylene rubber and butadiene rubber, which are synthetic rubbers, as rubber components, but besides these, other rubber materials such as natural rubber, urethane rubber, nitrile rubber, and silicone rubber are used.
- a rubber component may be contained.
- the content of the synthetic rubber is preferably 20% by mass to 90% by mass, and preferably 30% by mass to 80% by mass, based on mass, in all components contained in the mold cleaning resin composition. More preferably, it is more preferably 40% by mass to 70% by mass.
- the resin composition for mold cleaning contains a specific cleaning agent that is at least one compound selected from the group consisting of alkali metal salts and alkali metal hydroxides.
- a specific cleaning agent that is at least one compound selected from the group consisting of alkali metal salts and alkali metal hydroxides.
- the alkali metal in the alkali metal salt or alkali metal oxide that is the specific cleaning agent include lithium, sodium, potassium, rubidium, and cesium.
- the alkali metal is preferably at least one selected from the group consisting of lithium, sodium, and potassium from the viewpoint of cleaning performance, and is preferably at least one selected from the group consisting of sodium and potassium. More preferred.
- Alkali metal salts include silicate, borate, phosphate, metaphosphate, hypophosphate, phosphorous acid (phosphonic acid) salt, hypophosphorous acid (phosphinic acid) salt, pyrophosphate, Inorganic acid salts such as trimetaphosphate, tetrametaphosphate, pyrophosphorous acid, carbonate, sulfate, nitrate, hydrochloride; acrylate, adipate, ascorbate, aspartate, aminobenzoate , Alginate, benzoate, oleate, formate, citrate, glycolate, gluconate, glutamate, cinnamate, succinate, acetate, salicylate, oxalate, tartaric acid Organic salts such as salts, toluenesulfonate, nicotinate, lactate, urate, halogen-substituted acetate, phthalate, benzenesulfonate, malonate, butyrate,
- the alkali metal salt may be partially converted to an alkali metal salt.
- the alkali metal salt is, for example, a trivalent phosphate, a first salt having one alkali metal and two hydrogens, a second salt having two alkali metals and one hydrogen, or three alkali metals. Any of the third salts having Further, the alkali metal salt may be any of an acidic salt, an alkaline salt, or a neutral salt. Among these, from the viewpoint of suppressing the corrosiveness to the mold, the alkali metal salt is preferably an alkaline salt or a neutral salt. As the alkali metal salt, a hydrate may be used.
- alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. Hydrates may be used as the alkali metal hydroxide.
- the specific cleaning agent it is preferable to use at least one selected from the group consisting of trisodium phosphate, tripotassium phosphate, sodium hydroxide, and potassium hydroxide.
- An alkali metal salt and an alkali metal hydroxide may be used individually by 1 type, and may use 2 or more types together.
- the content of the specific cleaning agent in the mold cleaning resin composition is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the synthetic rubber from the viewpoint of cleaning performance and storage stability. Preferably, it is 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass.
- the mass ratio of the content of the specific cleaning agent to the water content is from 0.1 to 5.0 in terms of cleaning performance and storage stability. Preferably, it is 0.3 or more and 3.0 or less, and more preferably 0.5 or more and 1.5 or less.
- the mold cleaning resin composition may contain other cleaning agent in addition to the specific cleaning agent.
- another cleaning agent it can select suitably from the cleaning agent used for the resin composition for metal mold
- other cleaning agents include anionic surfactants, nonionic surfactants, metal soaps, and the like.
- the content of the other cleaning agents is preferably 5 parts by mass or less with respect to 100 parts by mass of the synthetic rubber, and 3 parts by mass or less. More preferably.
- the lower limit of the content of other cleaning agents is not particularly limited, but is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the synthetic rubber.
- the resin composition for mold cleaning contains silica.
- Silica functions as a filler, for example. There is no restriction
- the silica may be wet silica or dry silica.
- the water content of silica is preferably 6% by mass or more and 20% by mass or less, and more preferably 7% by mass or more and 10% by mass or less from the viewpoint of cleaning performance and storage stability.
- the water content of silica can be measured by a water vaporization-coulometric titration method using a Karl Fischer moisture meter, and the details are the same as the method for measuring the water content of the resin composition for mold cleaning.
- Silica preferably has an equilibrium moisture content of 5% by mass or more and 9% by mass or less at a relative humidity of 60% and 23 ° C. from the viewpoint of cleaning performance and storage stability. It is more preferably 8.5% by mass or less, and further preferably 6% by mass or more and 8% by mass or less.
- the bulk density of silica is preferably 30 g / l or more and 300 g / l or less, and more preferably 100 g / l or more and 300 g / l or less, from the viewpoint of manufacturing workability of the mold cleaning resin composition.
- the bulk density of silica is measured according to JIS K5105-18.
- silica examples include nip seal AQ, nip seal LP, nip seal NA, nip seal VN3 (manufactured by Tosoh Silica Co., Ltd.), and the like.
- the content of silica in the mold cleaning resin composition is preferably 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the synthetic rubber. It is more preferably 15 parts by mass or more and 50 parts by mass or less, and further preferably 20 parts by mass or more and 45 parts by mass or less.
- the mass ratio of the silica content to the water content is preferably 3.0 or more and 30 or less from the viewpoint of cleaning performance and storage stability. It is more preferably 0.0 or more and 20 or less, and further preferably 5.0 or more and 15 or less.
- the resin composition for mold cleaning may contain a filler other than silica in addition to silica.
- the resin composition for mold cleaning contains a filler other than silica in addition to silica, so that a sufficient pressure is applied to the resin composition for mold cleaning during pressurization during mold cleaning. .
- the mold cleaning resin composition spreads to every corner of the mold, and the inner surface of the mold does not wear out without wearing the mold. Dirt can be removed more efficiently.
- the mold cleaning resin composition preferably contains a filler other than silica in addition to silica.
- the filler other than silica may be either an organic filler or an inorganic filler, from the viewpoint of more efficiently removing dirt on the inner surface of the molding die without wearing the die, Inorganic fillers are more preferred.
- the inorganic filler examples include alumina, calcium carbonate, aluminum hydroxide, and titanium oxide.
- the filler has an appropriate hardness capable of removing dirt on the inner surface of the molding die without wearing the die, and from the viewpoint of applying sufficient pressure during pressurization during die cleaning, titanium oxide and At least one selected from the group consisting of calcium carbonate is preferred.
- the filler other than silica may be used alone or in combination of two or more.
- the content is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the synthetic rubber. More preferably, it is at least 8 parts by weight.
- the mold cleaning resin composition contains at least one vulcanizing agent.
- the vulcanizing agent is not particularly limited as long as it can crosslink synthetic rubber, and does not need to contain sulfur molecules in the compound.
- vulcanization is a concept including both crosslinking of synthetic rubber by adding sulfur and crosslinking of synthetic rubber using peroxide.
- the vulcanizing agent examples include sulfur, sulfur monochloride, selenium, tellurium, zinc oxide, magnesium oxide, lead monoxide, sulfur-containing organic compounds, dithiocarbamates, oximes, tetrachloro-p-benzoquinone, dinitroso compounds, modified compounds.
- a phenol resin, a polyamine, a peroxide, etc. are mentioned.
- a peroxide is preferable.
- an organic peroxide or an inorganic peroxide may be sufficient, and an organic peroxide is more preferable.
- the resin composition for mold cleaning contains an organic peroxide as a vulcanizing agent, there is no corrosive action of the mold during cleaning, which tends to occur when a vulcanizing agent containing sulfur is used, and the mold is released in a short time.
- the crosslinking of the unvulcanized rubber necessary for the process can proceed, and the crosslinking proceeds appropriately. Therefore, the cleaning resin composition after cleaning can be easily removed from the mold.
- the organic peroxide only needs to have at least one divalent peroxide structure (—O—O—) and at least one hydrocarbon group.
- the peroxide preferably has a one minute half-life temperature of 100 ° C. to 190 ° C. If the one-minute half-life temperature of the peroxide is higher than 190 ° C, the molding time becomes excessive when the mold is cleaned. Also, if the one-minute half-life temperature of the peroxide is higher than 190 ° C, if the mold temperature cannot be raised during mold cleaning, the mold cleaning resin composition does not sufficiently vulcanize and becomes brittle. There is a tendency for the workability of the system to decrease.
- the one minute half-life temperature of the peroxide is more preferably 140 ° C. to 190 ° C., and further preferably 145 ° C. to 180 ° C.
- the one-minute half-life temperature of peroxide is the temperature at which the peroxide concentration decreases to half of the initial value in one minute.
- the half-life (t 1/2 ) at each temperature is obtained for each different temperature, and the obtained lnt 1/2 and 1 / T are plotted.
- the temperature at which the half-life (t 1/2 ) is 1 minute, that is, the 1-minute half-life temperature can be obtained from the plotted graph.
- organic peroxide examples include 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexane, t-butylperoxyneodecanoate, bis (3,5,5-trimethylhexanoyl) peroxide, 2,5-dimethyl-2,5-bis ( 2-ethylhexylperoxy) hexane, bis (4-methylbenzoyl) peroxide, benzoyl peroxide, t-butylperoxybutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl Nomocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, n-butyl-4,4-
- the vulcanizing agent may be used alone or in combination with two or more kinds according to the design of the mold cleaning resin composition, and the vulcanization rate may be adjusted.
- the content of the vulcanizing agent in the mold cleaning resin composition is 1 part by mass to 20 parts by mass when the synthetic rubber contained in the mold cleaning resin composition is 100 parts by mass. Preferably, it is 3 to 10 parts by mass, more preferably 4 to 8 parts by mass.
- the content of the vulcanizing agent in the resin composition for mold cleaning is 20 parts by mass or less, the mold cleaning resin composition after the cleaning is prevented from becoming brittle. The removal operation of the mold cleaning resin composition can be facilitated.
- the content of the vulcanizing agent in the mold cleaning resin composition is 1 part by mass or more, vulcanization is sufficiently advanced, and the mold cleaning resin composition is prevented from sticking to the mold during cleaning. Therefore, the cleaning workability can be further improved.
- the mold cleaning resin composition of the present invention may also contain a vulcanization aid.
- the vulcanization aid include acrylic acid monomer, sulfur, and zinc oxide.
- a peroxide is used as the vulcanizing agent, at least one selected from the group consisting of sulfur and zinc oxide can be used as a vulcanizing aid.
- the resin composition for mold cleaning of the present invention can also contain a vulcanization accelerator.
- the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, and thiazole vulcanization accelerators.
- the guanidine vulcanization accelerator include diphenyl guanidine and triphenyl guanidine.
- the aldehyde-amine vulcanization accelerator examples include formaldehyde-paratoluidine condensate and acetaldehyde-aniline condensate.
- the thiazole vulcanization accelerator examples include 2-mercaptobenzothiazole and dibenzothiazyl disulfide.
- the mold cleaning resin composition of the present invention can also contain a vulcanization accelerator.
- the vulcanization acceleration aid include magnesia, resurge, lime and the like. The kind and amount of the vulcanization aid, the vulcanization accelerator, and the vulcanization acceleration aid can be appropriately selected according to the design of the resin composition for mold cleaning.
- the mold cleaning resin composition of the present invention may contain other components such as an organic solvent, a lubricant, a mold release agent, and other additives as necessary.
- the mold cleaning resin composition may contain at least one organic solvent.
- an organic solvent There is no restriction
- Specific examples of the organic solvent include alcohol solvents such as polyhydric alcohols and polyhydric alcohol monoalkyl ethers; amide solvents; ketone solvents; ether solvents and the like.
- alcohol solvents are preferable, and polyhydric alcohols, polyhydric alcohol monoalkyl ethers, and the like are more preferable.
- the organic solvent is preferably a liquid when the mold is washed, more preferably has a low volatility when the mold is heated, and further preferably has a boiling point of 180 ° C. or higher.
- Specific examples of the solvent having a boiling point of 180 ° C. or higher include ethylene glycol monobutyl ether (boiling point: 188 ° C.), propylene glycol (boiling point: 187 ° C.), dipropylene glycol methyl ether (boiling point: 190 ° C.), diethylene glycol. And monomethyl ether (194 ° C.).
- the content is preferably 5 parts by mass or less and more preferably 4 parts by mass or less with respect to 100 parts by mass of the synthetic rubber. Preferably, it is 3 parts by mass or less.
- the lower limit of the content of the organic solvent is not particularly limited, but is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the synthetic rubber.
- an organic solvent may be used individually by 1 type, and may use 2 or more types together.
- the mold cleaning resin composition may contain at least one lubricant.
- the lubricant include metal soap lubricants, fatty acid ester lubricants, fatty acid lubricants, amide lubricants, hydrocarbon lubricants, anionic surfactants and the like.
- the metal soap lubricant include zinc stearate, zinc myristate, aluminum stearate, calcium stearate and the like.
- the fatty acid ester lubricant include butyl stearate, butyl laurate, stearyl stearate and the like.
- fatty acid lubricants include stearic acid, behenic acid, and montanic acid.
- amide-based lubricant include ethylene bisstearamide, erucic acid amide, oleic acid amide, stearic acid amide, and behenic acid amide.
- hydrocarbon lubricant include liquid paraffin, paraffin wax, and synthetic polyethylene wax.
- the lubricant is preferably at least one selected from the group consisting of stearic acid, behenic acid, and montanic acid, and more preferably stearic acid, from the viewpoint of improving the dispersion of the compounding agent during kneading during processing.
- the lubricant may be used alone or in combination of two or more.
- the content thereof is 0.1% by mass to 20% by mass in the total components contained in the mold cleaning resin composition. It is preferably 0.3% by mass to 15% by mass.
- the content of the lubricant is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the synthetic rubber. preferable.
- the mold cleaning resin composition may contain at least one mold release agent.
- the mold cleaning resin composition contains a release agent, the mold release effect after molding becomes excellent, and the workability during cleaning is improved.
- the release agent include metal soap release agents, fatty acid ester release agents, synthetic waxes, and fatty acid amide release agents.
- the metal soap release agent include calcium stearate, zinc stearate, and zinc myristate.
- fatty acid ester release agents Commercially available fatty acid ester release agents, synthetic waxes, and fatty acid amide release agents include Lycowax OP (manufactured by Clariant Japan, montanic acid partially saponified ester), Roxyol G-78 (Emerio Oleochemicals Japan Ltd.) Company, polymer composite ester), Recolve H-4 (manufactured by Clariant Japan, modified hydrocarbon), Roxyol VPN881 (manufactured by Emery Oleochemicals Japan, mineral oil-based synthetic wax), fatty acid amide S (manufactured by Kao Corporation) Fatty acid amide), Kao wax EB-P (produced by Kao Corporation, fatty acid amide), Alflow HT-50 (produced by NOF Corporation, fatty acid amide), and the like.
- the type and amount of the release agent can be appropriately selected according to the design of the mold cleaning resin composition.
- a mold release agent may be used individually by 1 type, and may use 2 or more types
- additives include known additives such as a plasticizer, a tackifier, a foaming agent, a coupling agent, and a scorch inhibitor. These are appropriately selected according to the purpose and the like.
- Preparation method It does not specifically limit as a preparation method of the resin composition for metal mold
- a method for preparing the mold cleaning resin composition of the present invention for example, various components are kneaded using a pressure kneader with a jacket, a Banbury mixer, a roll mixer, etc., and a mold cleaning resin composition is obtained as a kneaded product.
- the preparation method which obtains a thing is mentioned.
- the obtained kneaded material can be formed into a sheet-like shape by passing through a pressure roll.
- the shape of the mold cleaning resin composition can be appropriately selected depending on the mold to be used.
- the thickness of the sheet is not particularly limited, and may be in the range of 3 mm to 10 mm, for example.
- the resin composition for mold cleaning of the present invention can be used for cleaning a molding mold.
- the type of the molding die is not particularly limited. Examples of the molding die include an optical member sealing die, a semiconductor material sealing die, and a rubber molding die. Specific examples of the molding die include a sealing die for a light emitting diode (LED), a sealing die for a semiconductor package, a rubber packing molding die, a thermosetting resin component molding die, and the like. . From the viewpoint of the molding temperature and curing time of the mold, the molding mold is preferably an LED sealing mold, a semiconductor package sealing mold, or the like.
- cleaning target resin is not particularly limited.
- the resin include an epoxy resin, a melamine resin, and a urea resin.
- the mold cleaning method when the resin composition for mold cleaning is used is roughly classified into a transfer type and a compression type.
- the resin composition for mold cleaning of the present invention can be applied to both transfer type and compression type mold cleaning methods.
- the resin composition for mold cleaning of the present invention is more preferably applied to a compression-type mold cleaning method from the viewpoint of improving workability and shortening the cleaning work time.
- the mold cleaning resin composition may be used by heating the mold provided with the mold cleaning resin composition to a temperature corresponding to the molding temperature of the resin to be cleaned.
- the molding temperature is appropriately selected according to the type of the resin to be cleaned. For example, when the cleaning target resin is an epoxy resin, the mold may be heated to about 170 ° C.
- the mold cleaning method of the present invention includes a step of applying the above-described mold cleaning resin composition of the present invention to the inner surface of a molding die (hereinafter also referred to as “applying step”), and mold cleaning. And a step of heating the mold provided with the resin composition (hereinafter also referred to as “heating step”).
- the mold cleaning method of the present invention may have other steps as necessary. According to the mold cleaning resin composition of the present invention, the cleaning performance is sufficiently maintained even when a long period of time (for example, 6 months) has elapsed since the manufacture of the mold cleaning resin composition. Dirt on the mold can be removed. Details of the molding die and the type of resin molded by the molding die are as described above.
- the applying step in the present invention is a step of applying the mold cleaning resin composition to the inner surface of the molding die. Details of the configuration, preferred mode, and the like of the mold cleaning resin composition used in this step are as described above.
- the method for applying the mold cleaning resin composition to the inner surface of the molding die is not particularly limited, and a known method can be employed.
- the imparting method include known methods such as a compression molding method (compression molding method), a transfer molding method, and the like.
- the resin composition for mold cleaning is applied to the inner surface of the molding die, it can be applied so as to cover a part or the entire surface of the cavity portion of the molding die.
- a metal cleaning resin composition so as to cover the entire surface of the cavity portion of the molding die.
- the heating step is a step of heating the mold cleaning resin composition applied to the inner surface of the molding die.
- the heating method and heating conditions are not particularly limited, and are known methods depending on the type of the resin to be cleaned and the composition of the mold cleaning resin composition of the present invention. And conditions can be selected as appropriate.
- the temperature is the same as the temperature when molding the resin to be cleaned with a mold, and is the same as the method when molding the resin to be cleaned with a mold. It is preferable to heat the mold cleaning resin composition by this method. Thereby, it is not necessary to heat or cool the mold for cleaning the mold, and the mold can be formed immediately after the mold cleaning.
- the temperature in the heating step is preferably 160 ° C. to 190 ° C., more preferably 170 ° C. to 180 ° C.
- the heating time is not particularly limited as long as the resin composition for mold cleaning is sufficiently vulcanized and spreads over the entire inner surface of the mold.
- the heating time is preferably 150 seconds to 500 seconds, and more preferably 180 seconds to 360 seconds.
- the applying step and the heating step may be repeated a plurality of times.
- the number of repetitions of the applying step and the heating step (hereinafter also referred to as “shot number”) is preferably 2 to 7 times, and more preferably 2 to 5 times.
- shot number is preferably 2 to 7 times, and more preferably 2 to 5 times.
- the mold cleaning method of the present invention may be provided with other steps as necessary.
- Examples of other processes include a preheating process and a pre-pressurizing process.
- Example 1 -Production of Resin Composition for Mold Cleaning
- Mooney viscosity ML 1 + 4 (100 ° C.) 24 diene content 8.1 parts
- iodine value 22 40 parts
- butadiene rubber (trade name BR01, manufactured by JSR Corporation, Mooney vis
- 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name Perhexa 25B-40, manufactured by NOF Corporation, 1 minute half-life temperature 179.8 ° C.) as a vulcanizing agent 6 parts were added and kneaded for about 1 minute. During this period, the temperature of the kneaded product was adjusted so as not to exceed 100 ° C. The obtained kneaded material was quickly passed through a pressure roll, processed into a sheet shape, cooled to 25 ° C. or lower, and formed into a sheet shape having a thickness of 7 mm to obtain the resin composition for mold cleaning of Example 1. It was.
- ⁇ Storage stability evaluation> The mold cleaning resin composition obtained above was allowed to stand for 6 months in an environment at 23 ° C., and then the cleaning performance was evaluated in the same manner as the test performed in the cleaning performance evaluation.
- the resin composition for mold cleaning was sealed and stored in an aluminum vapor-deposited polyethylene bag with a chuck in order to prevent a decrease in moisture content and deterioration due to light irradiation.
- the vulcanizability at the time of washing was evaluated by observing the degree of sticking of the mold cleaning resin composition to the mold.
- the evaluation criteria are as follows: -Evaluation criteria- A: Sticking to the mold did not occur. B: Sticking to the mold occurred, but it was easily removed by hand. C: Sticking to the mold occurred, and when peeled off by hand, the resin composition was cracked and a part remained on the mold surface.
- Example 2 to 8 Comparative Examples 1 to 3>
- Example 2 to 8 and Comparative Examples 1 to 3 were performed in the same manner as in Example 1 except that the blending components were changed as shown in Table 1.
- a mold cleaning resin composition was obtained.
- Table 1 shows the evaluation results of the cleaning performance evaluation and the storage stability evaluation. In Table 1, “-” indicates that it is not blended. Details of each component are as follows.
- Butadiene rubber JSR BR01 manufactured by JSR Corporation, Mooney viscosity ML 1 + 4 (100 ° C.) 45, cis 1,4 bond content 95%
- Nitrile rubber JSR N239SV manufactured by JSR Corporation, Mooney viscosity ML 1 + 4 (100 ° C.) 30, content rate of acrylonitrile bond 34%
- Styrene-butadiene rubber JSR 1502 manufactured by JSR Corporation, Mooney viscosity ML 1 + 4 (100 ° C.) 52, styrene bond content 23.5%
- Nip seal AQ Silica, manufactured by Tosoh Silica Co., Ltd., water content 8%, equilibrium moisture content 7% (relative humidity 60%, 23 ° C.)
- Nip seal LP Silica, manufactured by Tosoh Silica Co., Ltd., water content 6%, equilibrium moisture content 7% (relative humidity 60%, 23 ° C.)
- Nip seal NA Silica, manufactured by Tosoh Silica Co., Ltd., water content 6%
- Leolosil DM-10 Silica, manufactured by Tokuyama Corporation, water content 0.1% CR-80: Titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.
- Lubricant F-3 Stearic acid, vulcanizing agent manufactured by Kawaken Fine Chemical Co., Ltd. Perhexa 25B-40: manufactured by NOF Corporation, 1 minute half-life temperature 179.8 ° C Perhexa V-40: manufactured by NOF Corporation, 1 minute half-life temperature 172.5 ° C Release agent LOXIOL G78: Polymer composite ester, manufactured by Emery Oleochemicals Japan Co., Ltd. Zn-St GF200: Zinc stearate, manufactured by NOF Corporation Licolub H4: Modified hydrocarbon, manufactured by Clariant Japan Co., Ltd.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Detergent Compositions (AREA)
Abstract
Description
また、金型汚染改良ゴム組成物が、ゴムとリン酸アルカリ金属塩とを含むことで、シリカ添加による金型の洗浄作業性の低下や加硫剤による金型の汚染を防ぐことができるとされている(例えば、特開平04-234444号公報参照)。
<1> 合成ゴムと、アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる化合物と、シリカと、加硫剤と、を含有し、水分の含有率が、0.20質量%以上3.5質量%以下である金型清掃用樹脂組成物である。
本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本明細書において、「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
本明細書において、「成形金型の内部表面」とは、成形金型により成形される被成形物と接する領域を意味する。なお、本明細書中では、「成形金型」を、単に「金型」と称する場合がある。
<金型清掃用樹脂組成物>
本発明の金型清掃用樹脂組成物は、合成ゴムと、アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる少なくとも1種(以下、「特定洗浄剤」ともいう)と、シリカと、加硫剤と、を含有し、水分の含有率が金型清掃用樹脂組成物の総質量中に0.20質量%以上3.50質量%以下である。
なお、金型清掃用樹脂組成物における水分含有率は、カールフィッシャー法で測定することができる。具体的には、三菱化学株式会社製のカールフィッシャー水分計CA-100及び水分気化装置VA-100を用いて、水分気化-電量滴定法により測定される。なお、気化するための温度は180℃とする。
金型清掃用樹脂組成物は、ゴム成分として合成ゴムの少なくとも1種を含む。合成ゴムは特に制限されず、通常用いられる合成ゴムから適宜選択することができる。合成ゴムは、いわゆる未加硫ゴムであり、例えば、ブタジエンゴム(BR)、ニトリルゴム(NBR)、エチレン-プロピレンゴム(EPR)等のエチレン-α-オレフィンゴム、スチレン-ブタジエンゴム(SBR)、ポリイソプレンゴム(IR)、ブチルゴム(IIR)、シリコーンゴム(Q)、フッ素ゴム(FKM)などが挙げられる。これらは1種単独又は2種以上併せて用いられる。これら未加硫ゴムは、金型内において加硫されて加硫ゴムとなる。
前記α-オレフィンとしては、プロピレンの他に、イソブチレン、1-ブテン、1-ペンテン、1-ヘキセン、3-メチル-1-ペンテン、4-メチル-1-ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン等が挙げられる。
エチレン-プロピレンゴム及びブタジエンゴムの総量100質量部中に、エチレン-プロピレンゴムが90質量部以下であれば、良好な金型離型性が維持され、クリーニング作業時間が長くなることもない。また、ブタジエンゴムが80質量部以下であれば、金型離型性が良好であり、かつ加硫後の成形物の柔軟性も維持される。そのため、前記エチレン-プロピレンゴムと前記ブタジエンゴムとの配合割合が上記範囲内にあれば、清掃性能の観点より好ましい。
前記合成ゴムは、加硫硬化した後の引張強度が3MPa~10MPaであるものが好ましく、5MPa~8MPaであるものがより好ましい。合成ゴムの加硫硬化した後の引張強度が3MPa以上であれば、チッピングの発生が低減されるため、清掃性能の観点より好ましい。
前記合成ゴムは、加硫硬化した後のゴム硬度(デュロメータ硬さ)がA60~95であることが好ましく、A70~90であることがより好ましい。合成ゴムの加硫硬化した後のゴム硬度がこの範囲内にあれば、チッピング及びボイドの発生頻度も低いため、清掃性能の観点より好ましい。
金型清掃用樹脂組成物は、アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる少なくとも1種の化合物である特定洗浄剤を含む。
特定洗浄剤であるアルカリ金属塩又はアルカリ金属酸化物におけるアルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等が挙げられる。これらの中でもアルカリ金属は、清掃性能の観点から、リチウム、ナトリウム、及びカリウムからなる群より選ばれる少なくとも1種であることが好ましく、ナトリウム及びカリウムからなる群より選ばれる少なくとも1種であることがより好ましい。
アルカリ金属塩及びアルカリ金属水酸化物は、1種単独で用いてもよいし、また2種以上を併用してもよい。
金型清掃用樹脂組成物は、シリカを含む。シリカは、例えば、充填剤として機能する。シリカとしては特に制限はなく、含水非晶質シリカ、無水非晶質シリカ、結晶性シリカ等を挙げることができ、市販のシリカから適宜選択することができる。また、シリカは、湿式シリカであっても、乾式シリカであってもよい。
シリカの含水量は、清掃性能と保存安定性との観点から、6質量%以上20質量%以下であることが好ましく、7質量%以上10質量%以下であることがより好ましい。なお、シリカの含水量は、カールフィッシャー水分計を用いて水分気化-電量滴定法で測定することができ、詳細は、金型清掃用樹脂組成物の水分含有率の測定方法と同様である。
前記シリカ以外の充填剤としては、有機充填剤及び無機充填剤のいずれであってもよく、金型を摩耗することなく成形金型の内部表面の汚れをより効率的に除去できる観点からは、無機充填剤がより好ましい。
前記充填剤としては、金型を摩耗することなく成形金型の内部表面の汚れを除去できる適切な硬度を有し、金型清掃時の加圧時に充分に圧力がかかる観点から、酸化チタン及び炭酸カルシウムからなる群より選ばれる少なくとも1種が好ましい。
金型清掃用樹脂組成物が、シリカ以外の充填剤を含む場合、前記シリカ以外の充填剤は、1種単独で用いてもよく、また2種以上を併用してもよい。
金型清掃用樹脂組成物は、加硫剤の少なくとも1種を含む。加硫剤としては、合成ゴムを架橋可能なものであればよく、硫黄分子を化合物中に含んでいなくともよい。
なお、本発明において加硫とは、硫黄を添加して合成ゴムを架橋すること及び過酸化物を用いて合成ゴムを架橋することの両方を包含する概念である。
前記過酸化物としては、1分間半減期温度が、100℃~190℃であるものが好ましい。過酸化物の1分間半減期温度が190℃より高いと、金型清掃時に成形時間が過剰となる。また、過酸化物の1分間半減期温度が190℃より高いと、金型清掃時に金型温度を上げられない場合、金型清掃用樹脂組成物が十分に加硫せず脆くなることで清掃の作業性が低下する傾向がある。過酸化物の1分間半減期温度が100℃未満であると、金型清掃用樹脂組成物の製造時、及び混練加工時に加硫が進行するため、金型清掃時に金型の形状に十分に追随できなくなる傾向がある。
また、前記過酸化物の1分間半減期温度は、140℃~190℃であることがより好ましく、145℃~180℃であることが更に好ましい。
具体的に、1分間半減期温度は、以下のようにして求めることができる。まず、前記過酸化物をある一定温度(T)で熱分解させた際、前記過酸化物の初期濃度をa、前記過酸化物の分解量をxとし、時間(t)とlna/(a-x)の関係をプロットすることで、得られた直線の傾き定数kを求める。次に、温度(T)における半減期は、その定義である式 kt1/2=ln2に、先に求めたkを代入することで求めることができる。さらに、同様の手順を繰り返すことで異なる温度毎にその温度での半減期(t1/2)をそれぞれ求め、得られたlnt1/2と1/Tとをプロットする。
このようにして得られた直線を外挿することで、このプロットした図から半減期(t1/2)が1分間である温度、すなわち1分間半減期温度を求めることができる。
本発明の金型清掃用樹脂組成物は、加硫促進剤を含有することもできる。
前記加硫促進剤としては、グアニジン系、アルデヒド-アミン系、アルデヒド-アンモニア系、チアゾール系等の加硫促進剤を挙げることができる。
前記グアニジン系加硫促進剤としては、ジフェニルグアニジン、トリフェニルグアニジン等が挙げられる。
前記アルデヒド-アミン系加硫促進剤としては、ホルムアルデヒド-パラトルイジン縮合物、アセトアルデヒド-アニリン縮合物等が挙げられる。
前記チアゾール系加硫促進剤としては、2-メルカプトベンゾチアゾール、ジベンゾチアジルジスルフィド等が挙げられる。
また、前記加硫促進剤の他に、本発明の金型清掃用樹脂組成物は、加硫促進助剤を含有することもできる。前記加硫促進助剤としては、マグネシア、リサージ、石灰等が挙げられる。
前記加硫助剤、前記加硫促進剤、及び前記加硫促進助剤の種類及び量は、金型清掃用樹脂組成物の設計に合わせて適宜選択することができる。
本発明の金型清掃用樹脂組成物は、必要に応じて、有機溶剤、滑剤、離型剤、その他添加剤等の他の成分を含有していてもよい。
金型清掃用樹脂組成物は、有機溶剤の少なくとも1種を含んでいてもよい。有機溶剤としては特に制限はなく、通常用いられる有機溶剤から適宜選択することができる。有機溶剤としては、具体的には、多価アルコール、多価アルコールモノアルキルエーテル等のアルコール溶剤;アミド溶剤;ケトン溶剤;エーテル溶剤などを挙げることができる。有機溶剤としては、アルコール溶剤が好ましく、多価アルコール、多価アルコールモノアルキルエーテル等がより好ましい。
また、有機溶剤は、1種単独で用いてもよく、また2種以上を併用してもよい。
金型清掃用樹脂組成物は、滑剤の少なくとも1種を含んでいてもよい。金型清掃用樹脂組成物が滑剤を含有することにより、製造時の混練において配合剤の分散性が向上する。
滑剤としては、金属石鹸系滑剤、脂肪酸エステル系滑剤、脂肪酸系滑剤、アミド系滑剤、炭化水素系滑剤、アニオン系界面活性剤等が挙げられる。
金属石鹸系滑剤としては、ステアリン酸亜鉛、ミリスチン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム等が挙げられる。
脂肪酸エステル系滑剤としては、ブチルステアレート、ブチルラウレート、ステアリルステアレート等が挙げられる。
脂肪酸系滑剤としては、ステアリン酸、ベヘン酸、モンタン酸等が挙げられる。
アミド系滑剤としては、エチレンビスステアロアミド、エルカ酸アミド、オレイン酸アミド、ステアリン酸アミド、ベヘニン酸アミド等が挙げられる。
炭化水素系滑剤としては、流動パラフィン、パラフィンワックス、合成ポリエチレンワックス等が挙げられる。
前記滑剤としては、加工時の混練において配合剤の分散を良好にする観点から、ステアリン酸、ベヘン酸、及びモンタン酸からなる群より選ばれる少なくとも1種が好ましく、ステアリン酸がより好ましい。
金型清掃用樹脂組成物において、滑剤は、1種単独で用いてもよく、2種以上を併用してもよい。
金型清掃用樹脂組成物が、滑剤を含む場合、その含有量は、金型清掃用樹脂組成物に含有される全成分中に、質量基準で、0.1質量%~20質量%であることが好ましく、0.3質量%~15質量%であることがより好ましい。また、滑剤の含有量は、合成ゴムの含有量100質量部に対して0.1質量部以上20質量部以下であることが好ましく、0.5質量部以上10質量部以下であることがより好ましい。
金型清掃用樹脂組成物は、離型剤の少なくとも1種を含有してもよい。金型清掃用樹脂組成物は、離型剤を含有することにより、成形後の金型離型効果が優れたものとなり、清掃時の作業性が向上する。
離型剤としては、金属石鹸系離型剤、脂肪酸エステル系離型剤、合成ワックス、脂肪酸アミド系離型剤等が挙げられる。
金属石鹸系離型剤としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ミリスチン酸亜鉛等が挙げられる。
市販の脂肪酸エステル系離型剤、合成ワックス、及び脂肪酸アミド系離型剤としては、リコワックスOP(クラリアントジャパン株式会社製、モンタン酸部分ケン化エステル)、ロキシオールG-78(エメリーオレオケミカルズジャパン株式会社製、高分子複合エステル)、リコルブH-4(クラリアントジャパン株式会社製、変性炭化水素)、ロキシオールVPN881(エメリーオレオケミカルズジャパン株式会社製、鉱油系合成ワックス)、脂肪酸アマイドS(花王株式会社製、脂肪酸アミド)、カオーワックスEB-P(花王株式会社製、脂肪酸アミド)、アルフローHT-50(日油株式会社製、脂肪酸アミド)等が挙げられる。
離型剤の種類及び量は、金型清掃用樹脂組成物の設計に合わせて適宜選択することができる。また、離型剤は、1種単独で用いてもよく、2種以上を併用してもよい。
その他添加剤としては、可塑剤、粘着付与剤、発泡剤、カップリング剤、スコーチ防止剤等の公知の添加剤を挙げることができる。これらは目的等に応じて適宜選択される。
本発明の金型清掃用樹脂組成物の調製方法としては、特に限定されるものではなく、公知の方法を採用することができる。
本発明の金型清掃用樹脂組成物の調製方法としては、例えば、ジャケット付き加圧型ニーダー、バンバリーミキサー、ロールミキサー等を用いて、各種成分を混練して、混練物として金型清掃用樹脂組成物を得る調製方法が挙げられる。得られた混練物は、加圧ロールに通してシート状等の形状に成形することができる。
金型清掃用樹脂組成物の形状は、使用する金型により、適宜選択することができる。
金型清掃用樹脂組成物をシート状に成形した場合、シートの厚みは特に制限されるものではなく、例えば、3mm~10mm等の範囲にすることができる。
本発明の金型清掃用樹脂組成物は、成形金型の清掃のために用いることができる。成形金型の種類としては、特に限定されるものではない。成形金型としては、例えば、光学部材封止用金型、半導体材料封止用金型、ゴム成形金型等が挙げられる。成形金型としては、具体的には、発光ダイオード(LED)用の封止金型、半導体パッケージ用の封止金型、ゴムパッキン成形金型、熱硬化性樹脂部品成形金型等が挙げられる。金型の成形温度と硬化時間との観点より、成形金型としては、LED用の封止金型、半導体パッケージ封止金型等が好ましい。
本発明の金型清掃方法は、既述の本発明の金型清掃用樹脂組成物を、成形金型の内部表面に付与する工程(以下、「付与工程」ともいう)と、金型清掃用樹脂組成物が付与された金型を加熱する工程(以下、「加熱工程」ともいう)とを有する。本発明の金型清掃方法は、必要に応じてその他の工程を有していてもよい。
本発明の金型清掃用樹脂組成物によれば、金型清掃用樹脂組成物の製造から長時間(例えば6ヶ月)経過した場合でも、清掃性能が充分に維持されているため、効率的に金型の汚れを除去することができる。
成形金型、及び成形金型により成形される樹脂の種類等の詳細については、既述した通りである。
本発明における付与工程は、金型清掃用樹脂組成物を成形金型の内部表面に付与する工程である。本工程で用いる金型清掃用樹脂組成物の構成、好ましい態様等の詳細については、既述した通りである。
金型清掃用樹脂組成物を成形金型の内部表面に付与する際には、成形金型のキャビティ部分の一部又は全部の表面を覆うように付与することができる。成形時には、樹脂が成形金型の内部表面全体に行き渡るため、金型清掃方法においては、成形金型のキャビティ部分の全部の表面を覆うように、金属清掃用樹脂組成物を付与することが好ましい。
加熱工程は、成形金型内部表面に付与した金型清掃用樹脂組成物を加熱する工程である。
加熱方法及び加熱条件(温度、時間、回数等)は、特に限定されるものではなく、前記清掃対象樹脂の種類、及び本発明の金型清掃用樹脂組成物の組成に応じて、公知の方法及び条件を適宜選択することができる。
加熱工程における温度としては、160℃~190℃であることが好ましく、170℃~180℃であることがより好ましい。
本発明の金型清掃方法は、必要に応じてその他の工程を設けてもよい。その他の工程としては、予熱工程、予備加圧工程等が挙げられる。
・金型清掃用樹脂組成物の作製
実施例1にかかる金型清掃用樹脂組成物を、以下の手順で作製した。
3000mlのジャケット付き加圧型ニーダー中に、エチレン-プロピレンゴム(商品名EPT 4021H、三井化学株式会社製、エチレン:プロピレンの組成比=55:45、ムーニー粘度ML1+4(100℃)24、ジエン含有率8.1%、ヨウ素価22)を40部と、ブタジエンゴム(商品名BR01、JSR株式会社製、ムーニー粘度ML1+4(100℃)45、比重0.9、シス1,4結合含有率95%)を60部と、を添加し、冷却しながら約3分間加圧混練した。
混練生地がパン生地状になり、混練生地の温度が約80℃となった。
次いで、アルカリ金属塩としてリン酸三カリウムを2部と、滑剤としてステアリン酸(商品名F-3、川研ファインケミカル株式会社製)を1部と、離型剤として高分子複合エステル(商品名LOXIOL G78、エメリーオレオケミカルズジャパン株式会社製)を1部、ステアリン酸亜鉛(商品名Zn-St GF200、日本油脂株式会社製)を1部、及び変性炭化水素(商品名Licolub H4、クラリアントジャパン株式会社製)を0.5部と、充填剤として含水非晶質シリカ(商品名ニップシールAQ、東ソー・シリカ株式会社製、含水量8%、平衡水分含有率7%(相対湿度60%、23℃))を30部と、酸化チタン(商品名CR-80、石原産業株式会社製)を5部と、を加えて約3分間混練した。
最後に、加硫剤として2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン(商品名パーヘキサ25B-40、日油株式会社製、1分間半減期温度179.8℃)6部を加えて引続き約1分間混練した。
この間の混練物温度は100℃を超えないように調節した。
得られた混練物は、速やかに加圧ロールに通し、シート状に加工すると共に25℃以下に冷却し、厚さ7mmのシート状にして、実施例1の金型清掃用樹脂組成物を得た。
市販のビフェニル系エポキシ樹脂成形材料(商品名EME-G700、住友ベークライト株式会社製)を用い、先端に超硬合金製のチップが付いたプランジャーを備えたQFP28×28(6ポット-12キャビティ)の金型で500ショットの成形を行い、成形金型の内部表面の汚れを形成した。
この内部表面に汚れを有する成形金型を用いて、上記で得られた金型清掃用樹脂組成物について繰り返しコンプレッション成形を行い、成形金型の内部表面の汚れが除去できるまでに要した成形回数(ショット数)により、清掃性能を評価した。なお、成形金型の内部表面の汚れの除去状態は目視により判定した。また、成形金型の内部表面の汚れが除去できるまでに要した金型清掃用樹脂組成物の繰り返し成形回数(クリーニング完了ショット数)が4回以下であるものが合格である。
上記で得られた金型清掃用樹脂組成物を、23℃の環境下で6ヶ月放置した後、上記清掃性能評価で行った試験と同様にして清掃性能を評価した。なお、金型清掃用樹脂組成物は、水分量の低下と光の照射による劣化とを防ぐため、チャック付きのアルミニウム蒸着処理ポリエチレン製袋に密閉し保存した。
また、洗浄時の加硫性を金型清掃用樹脂組成物の金型への貼り付きの程度を観察することで評価した。評価基準は以下の通りである
-評価基準-
A:金型への貼り付きが起こらなかった。
B:金型への貼り付きが起こるが、手で容易に剥がせた。
C:金型への貼り付きが起こり、手で剥がすと樹脂組成物が割れ、一部が金型表面に残った。
実施例1の金型清掃用樹脂組成物の作製において、配合成分を表1に記載したようにそれぞれ変更した以外は、実施例1と同様にして、実施例2~8及び比較例1~3の金型清掃用樹脂組成物を得た。清掃性能評価及び保存安定性評価の評価結果を表1に示す。なお、表1中、「-」は未配合であることを示す。また各成分の詳細は以下の通りである。
EPT 4021H:三井化学株式会社製、エチレン/プロピレン比=55.5/44.5、ムーニー粘度ML1+4(100℃)24、ジエン含有率8.1%、ヨウ素価22
ブタジエンゴム
JSR BR01:JSR株式会社製、ムーニー粘度ML1+4(100℃)45、シス1,4結合の含有率95%、
ニトリルゴム
JSR N239SV:JSR株式会社製、ムーニー粘度ML1+4(100℃)30、アクリロニトリル結合の含有率34%
スチレン-ブタジエンゴム
JSR 1502:JSR株式会社製、ムーニー粘度ML1+4(100℃)52、スチレン結合の含有率23.5%
ニップシールAQ:シリカ、東ソー・シリカ株式会社製、含水量8%、平衡水分含有率7%(相対湿度60%、23℃)
ニップシールLP:シリカ、東ソー・シリカ株式会社製、含水量6%、平衡水分含有率7%(相対湿度60%、23℃)
ニップシールNA:シリカ、東ソー・シリカ株式会社製、含水量6%
レオロシールDM-10:シリカ、株式会社トクヤマ製、含水量0.1%
CR-80:酸化チタン、石原産業株式会社社製
F-3:ステアリン酸、川研ファインケミカル株式会社製
加硫剤
パーヘキサ25B-40:日油株式会社製、1分間半減期温度179.8℃
パーヘキサV-40:日油株式会社製、1分間半減期温度172.5℃
離型剤
LOXIOL G78:高分子複合エステル、エメリーオレオケミカルズジャパン株式会社製
Zn-St GF200:ステアリン酸亜鉛、日油株式会社製
Licolub H4:変性炭化水素、クラリアントジャパン株式会社製
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的に、かつ、個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (9)
- 合成ゴムと、
アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる化合物と、
シリカと、
加硫剤と、
を含有し、水分の含有率が、0.20質量%以上3.50質量%以下である金型清掃用樹脂組成物。 - 前記合成ゴムは、エチレン-プロピレンゴム及びブタジエンゴムを含む請求項1に記載の金型清掃用樹脂組成物。
- 前記シリカの含有量が、前記合成ゴムの含有量100質量部に対して、10質量部以上60質量部以下である請求項1又は請求項2に記載の金型清掃用樹脂組成物。
- 前記水分の含有量に対する、前記アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる化合物の含有量の質量比が、0.1以上5.0以下である請求項1~請求項3のいずれか1項に記載の金型清掃用樹脂組成物。
- 前記水分の含有量に対する、前記シリカの含有量の質量比が、3以上30以下である請求項1~請求項4のいずれか1項に記載の金型清掃用樹脂組成物。
- 前記シリカは、相対湿度60%、温度23℃における平衡水分含有率が5質量%以上9質量%以下である請求項1~請求項5のいずれか1項に記載の金型清掃用樹脂組成物。
- 前記アルカリ金属塩及びアルカリ金属水酸化物からなる群より選ばれる化合物の含有量が、前記合成ゴムの含有量100質量部に対して、0.1質量部以上10質量部以下である請求項1~請求項6のいずれか1項に記載の金型清掃用樹脂組成物。
- 前記加硫剤の含有量が、前記合成ゴムの含有量100質量部に対して、1質量部以上20質量部以下である請求項1~請求項7のいずれか1項に記載の金型清掃用樹脂組成物。
- 請求項1~請求項8のいずれか1項に記載の金型清掃用樹脂組成物を、成形金型の内部表面に付与する工程と、
前記金型清掃用樹脂組成物が付与された成形金型を加熱する工程と、
を含む金型清掃方法。
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