WO2009122955A1 - 金型離型回復用ゴム系組成物 - Google Patents
金型離型回復用ゴム系組成物 Download PDFInfo
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- WO2009122955A1 WO2009122955A1 PCT/JP2009/055772 JP2009055772W WO2009122955A1 WO 2009122955 A1 WO2009122955 A1 WO 2009122955A1 JP 2009055772 W JP2009055772 W JP 2009055772W WO 2009122955 A1 WO2009122955 A1 WO 2009122955A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- 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
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- 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
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to a rubber composition for recovering mold release, and more specifically, for recovering mold release properties on a mold surface after removing dirt on the mold surface generated in a molding process of a curable resin.
- the present invention relates to a mold release recovery rubber composition characterized by using a specific unvulcanized rubber and a specific release agent as a base resin in the mold release recovery rubber composition.
- the release agent contained in the thermosetting resin molding material oozes out at the interface between the molding and the mold. By doing so, it exerts a mold release action on the cull part, cavity part, and runner part.
- a release agent or a low molecular weight material of the resin contained in the molding material is oxidized and deteriorated by repeated molding at a high temperature, and gradually accumulates on the mold. Therefore, the mold releasability of the molded product is remarkably deteriorated, appearance defects such as rough skin are generated on the surface of the molded product, and defects are caused in the printing process after molding.
- an unvulcanized rubber compound containing a cleaning component is used, which is present on the mold surface when vulcanized in a mold to form a vulcanized rubber.
- a method has been proposed in which an oxidatively deteriorated layer such as a release agent is decomposed by a cleaning component and integrated with a vulcanized rubber, and then the mold surface is cleaned by removing the vulcanized rubber from the mold.
- a rubber-based composition in which a butadiene rubber / ethylene-propylene rubber component is set to 90/10 to 50/50 parts by weight as an unvulcanized rubber component has been proposed (for example, US Pat. No.
- Compression type cleaning materials are used to eliminate such clogging of air vents, but when melamine-based resin molding materials are used, clogging of the air vent part is eliminated, but the vicinity of the mold periphery is caused by the outflow of resin. Since the pressure is not sufficiently applied, the outer peripheral portion of the molded product tends to become brittle, and the work of removing the cured molded product from the mold has been complicated. On the other hand, when the rubber-based composition is used, the entire composition is uniformly cured and can be released from the mold as a single sheet-like molded product, so that workability is improved. However, since the rubber-based composition is worse than the melamine-based resin molding material in terms of fluidity, there is a problem that the filling property into the cavity is poor and the dirt such as the cavity corner cannot be removed.
- the number of pins is small even in small package manufacturing molds such as Plastic Dual Inline Package (hereinafter abbreviated as PDIP) and Small Outline Integrated Circuit (hereinafter abbreviated as SOIC).
- PDIP Plastic Dual Inline Package
- SOIC Small Outline Integrated Circuit
- the present invention has good workability (releasability), it eliminates the drawbacks of the conventional mold release recovery rubber composition that generates voids and chipping, and causes voids and chipping. It is an object of the present invention to provide a mold release recovery rubber-based composition that has no mold release and has a long mold release property after recovery of the release property, and has a large number of continuous moldings of sealed molded products. .
- the present invention has good workability (releasability), but eliminates the drawbacks of the conventional mold release recovery rubber composition in which voids and chipping occur, and also provides PDIP, SOIC, etc. Even in small package manufacturing molds such as those with deep cavities and small package manufacturing molds with a small number of pins, voids and chipping do not occur and releasability is restored. It is an object of the present invention to provide a mold release recovery rubber-based composition that has long mold releasability for a long time and has a large number of continuous moldings of sealed molded products.
- This invention solves the said subject by providing the compression type metal mold release recovery rubber composition of the following (1), (2) and (3).
- a resin composition that gives mold releasability to the mold surface after removing dirt on the mold surface generated in the molding process of the curable resin as a base resin, ethylene-propylene rubber and butadiene rubber are used.
- ethylene-propylene rubber and butadiene rubber are used as a base resin.
- ethylene-propylene rubber and butadiene rubber are used as ethylene-propylene rubber and butadiene rubber.
- an unvulcanized rubber having a blending ratio of 90/10 to 50/50 parts by weight
- a metal soap release agent an organic fatty acid ester release agent, a synthetic wax release agent, and And at least one release agent selected from fatty acid amide release agents.
- the unvulcanized rubber has an elongation rate of 80 to 800% after vulcanization and curing, and a tensile strength of 3 to 3%.
- Compression characterized by Rubber composition for recovering mold release. (Hereinafter referred to as the first mold release recovery rubber composition) (2)
- a resin composition that gives mold release properties to the mold surface after removing dirt on the mold surface generated in the molding step of the curable resin as a base resin, ethylene-propylene rubber and butadiene rubber are used.
- an unvulcanized rubber having a blending ratio of 90/10 to 50/50 parts by weight, and a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and And at least one release agent selected from fatty acid amide release agents.
- the unvulcanized rubber has an elongation rate of 80 to 800% after vulcanization and curing, and a tensile strength of 3 to 3%.
- the second mold release recovery rubber composition (Hereinafter referred to as the second mold release recovery rubber composition) (3)
- a resin composition that imparts mold release properties to the mold surface after removing the mold surface stains generated in the molding process of the curable resin as a base resin, ethylene-propylene rubber and butadiene rubber are used.
- the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, a tensile strength of 3 to 10 MPa,
- This is an unvulcanized rubber having a rubber hardness (durometer hardness) of A60 to 95 and a 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. within a range of 200 to 400 seconds.
- Compressor characterized by A rubber-based composition for recovering mold mold release. (Hereinafter referred to as the third mold release recovery rubber composition)
- the first, second and third mold release recovery rubber compositions of the present invention are excellent not only in workability (mold release property) but also in moldability and strength, and consequently no occurrence of voids and chipping.
- the mold releasability after the releasability is maintained for a long time, and the number of continuous moldings of the sealed molded product is large.
- the rubber composition for recovering mold release of the second and third molds of the present invention has a small number of pins among small molds for manufacturing a package having a deep cavity such as PDIP and SOIC, and small packages. In particular, it is particularly suitable for recovering mold release of a small package manufacturing die.
- the unvulcanized rubber used in the present invention is a mixture of ethylene-propylene rubber and butadiene rubber.
- EPM Ethylene-propylene rubber
- EPDM ethylene-propylene-diene rubber
- the EPDM is a terpolymer comprising ethylene, an ⁇ -olefin, and a cyclic or non-cyclic product having a nonconjugated double bond. More specifically, it is a terpolymer composed of ethylene, an ⁇ -olefin (particularly propylene), and a polyene monomer.
- the polyene monomer include dicyclopentadiene, 5-cyclooctadiene, 1,7-cyclododecadiene, 1,5,9-cyclododecatriene, 1,4-cycloheptadiene, 1,4-cyclohexadiene, norbornadiene.
- the copolymerization ratio of each monomer in such a terpolymer is preferably 30 to 80 mol% for ethylene, 0.1 to 2 mol% for the polyene monomer, and the remainder being ⁇ -olefin. More preferably, ethylene is 30 to 60 mol%.
- EPDM it is preferable to use one having a Mooney viscosity ML 1 + 4 (100 ° C.) of 20 to 70.
- the butadiene rubber (hereinafter sometimes abbreviated as BR) has a high cis structure in which the content of cis 1,4 bonds is 90% by weight or more and has a Mooney viscosity ML 1 + 4 (100 ° C.) of 20-60. In particular, those of 30 to 45 are preferably used.
- the blending ratio of the ethylene-propylene rubber and the butadiene rubber is 90/10 to 50/50 parts by weight, preferably 80/20 to 60/40 parts by weight. If the ethylene-propylene rubber is added in an amount exceeding 90 parts by weight, the mold releasability deteriorates, which is not preferable. If the butadiene rubber exceeds 50 parts by weight, the mold releasability is improved, but the molded product after vulcanization is hard and brittle, and chipping is likely to occur, which is not preferable.
- the unvulcanized rubber has an elongation percentage after vulcanization and curing of 80 to 800%, preferably 100 to 300%. An elongation of 80% or less is not preferable because moldability deteriorates.
- the unvulcanized rubber has a tensile strength after vulcanization and curing of 3 to 10 MPa, preferably 5 to 8 MPa. If the tensile strength is 3 MPa or less, chipping occurs, which is not preferable.
- the unvulcanized rubber has a rubber hardness (durometer hardness) after vulcanization and curing (Durometer hardness) of A60 to 95, preferably A70 to 90. If the rubber hardness deviates from this range, chipping and voids are generated, which is not preferable.
- the unvulcanized rubber has a 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. of 50 to 100 seconds, preferably 70 to 100 seconds. If the value of tc (90) is within this range, the vulcanization speed will not be too fast, and the resin can be filled to every corner of the cavity, so that the mold release can be recovered without causing problems such as sticking. Can be implemented.
- the first mold release recovery rubber composition of the present invention comprises a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax and a fatty acid amide release agent. And at least one mold release agent selected from among the molds.
- the metal soap release agent include calcium stearate, zinc stearate, zinc myristate and the like.
- Organic fatty acid ester release agents, synthetic waxes, and fatty acid amide release agents include Rico wax OP (Montannic acid partially saponified ester manufactured by Clariant Japan Co., Ltd.), Roxyol G-78 (Polymer composite manufactured by Cognis Japan Co., Ltd.) Ester), Recolve H-4 (modified hydrocarbon wax manufactured by Clariant Japan Co., Ltd.), Roxyol VPN881 (mineral oil synthetic wax manufactured by Cognis Japan Co., Ltd.), fatty acid amide S (fatty acid amide manufactured by Kao Corporation), Kao wax EB- P (fatty acid amide manufactured by Kao Corporation), Alflow HT-50 (fatty acid amide manufactured by NOF Corporation) and the like can be exemplified.
- Rico wax OP Montannic acid partially saponified ester manufactured by Clariant Japan Co., Ltd.
- Roxyol G-78 Polymer composite manufactured by Cognis Japan Co., Ltd.) Ester
- Recolve H-4 modified hydrocarbon wax manufactured
- the ratio of the metal soap release agent to other release agents is preferably 90:10 to 30:70. If the ratio of the other release agent is excessive, the continuous moldability is deteriorated, which is not preferable.
- the total amount of addition of the metal soap release agent and other release agents is 0. 0 parts by weight with respect to 100 parts by weight of the unvulcanized rubber. 5 to 30 parts by weight are preferred.
- the mold release agent If the amount of the mold release agent is insufficient, the mold releasability decreases, and if the amount of the mold release agent is too large, the mold releasability is good, but the mold release recovery rubber composition is melted. This is not preferable because the fluidity of the film significantly decreases and the moldability deteriorates, and the number of dummy shots after the mold release recovery step increases.
- the first mold release recovery rubber composition of the present invention comprises a filler, a cleaning agent, a cleaning aid, a vulcanizing agent and a vulcanizing aid in addition to the unvulcanized rubber and the releasing agent. Further, a vulcanization accelerator, a vulcanization acceleration aid and the like can be contained.
- Examples of the filler include silica, alumina, calcium carbonate, aluminum hydroxide, and titanium oxide.
- the amount of the filler used is preferably 10 to 70 parts by weight, more preferably 30 to 60 parts by weight with respect to 100 parts by weight of the unvulcanized rubber.
- Examples of cleaning agents include amines such as monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-di-n-butylethanolamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc. Glycol ethers, imidazoles and imidazolines.
- the amount of the cleaning agent used is preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the unvulcanized rubber.
- a cleaning aid such as a surfactant can be used.
- vulcanizing agent examples include di-t- butyl peroxide, di-t- amyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- di- (t-butylperoxy)-hexane.
- Diallyl peroxide organic peroxides such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, Peroxyketals such as 2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane Oxides.
- peroxyketals have a longer half-life compared to diallyl peroxides, but these may be used alone in combination with the design of the composition, and those with a longer half-life and shorter You may adjust a vulcanization speed together.
- the amount of the vulcanizing agent used is preferably 1 to 6 parts by weight, more preferably 2 to 4 parts by weight with respect to 100 parts by weight of the unvulcanized rubber.
- vulcanization aids such as acrylic acid monomers and sulfur can be used.
- vulcanization accelerator examples include guanidines such as diphenylguanidine and triphenylguanidine, aldehyde-amines such as formaldehyde-paratoluidine condensate, acetaldehyde-aniline reactant, and aldehyde-ammonia, such as 2- Examples thereof include thiazoles such as mercaptobenzothiazole and dibenzothiazyl disulfide, and vulcanization accelerating aids such as magnesia, risurge and lime can be used.
- the first mold release recovery rubber-based composition of the present invention can use pigments and colorants, for example, in order to distinguish them from cleaning materials.
- pigments and colorants for example, inorganic pigments such as titanium oxide, carbon black, zinc white, cadmium yellow, bengara, bitumen, iron black, ultramarine blue, lithopone, titanium yellow, cobalt blue, etc.
- organic pigments such as red, fluorescent pigments such as benzoxazole, naphthotriazole, and coumarin, and colorants such as anthraquinone, indico, and azo dyes.
- the amount of the pigment or colorant used is preferably about 0.01 to 1 part by weight per 100 parts by weight of the unvulcanized rubber.
- the unvulcanized rubber used as the base resin is a 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. ) Is the same as the first mold release recovery rubber composition of the present invention except that it is an unvulcanized rubber for 200 to 400 seconds, preferably 250 to 350 seconds.
- the tc (90) value can be adjusted as appropriate according to the type and amount of diene, the type and amount of peroxide, the type and amount of vulcanization accelerator, the type and amount of co-crosslinking agent, and the like.
- tc (90) of the unvulcanized rubber is in the range of 200 to 400 seconds, the vulcanization speed will not be too fast and the resin can be filled to every corner of the cavity, so sticking, etc. It is possible to carry out mold release recovery without causing any problems.
- the release agent is a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and a fatty acid amide release agent. Except for the point that it is at least one release agent selected from among the above, it is the same as the second mold release recovery rubber composition of the present invention.
- the addition amount of at least one release agent selected from metal soap release agents, organic fatty acid ester release agents, synthetic wax release agents, and fatty acid amide release agents is unvulcanized rubber. 10 to 50 parts by weight is preferable with respect to 100 parts by weight. If the amount of the release agent is insufficient, even in a small package having a deep cavity such as PDIP or SOIC, the mold release property of a particularly small package manufacturing mold having a small number of pins is lowered. If the amount of the agent is too large, mold releasability is good, but fluidity when the mold release recovery rubber-based composition is melted remarkably deteriorates and moldability deteriorates. This is not preferable because the number of subsequent dummy shots increases.
- the method for preparing the first, second and third mold release recovery rubber compositions of the present invention is not particularly limited, and a known method can be employed.
- EPM and BR dough are put into a pressure kneader with a jacket and kneading is started, and kneading is continued while observing the temperature of the dough appropriately until the mixed dough of EPM and BR becomes mochi.
- a release agent, white carbon, amino alcohol compound, cyclic amide compound, process oil, nonionic surfactant, stearic acid, etc. are added. Knead for several minutes. Next, an organic peroxide and sulfur are added and dispersed quickly, and then taken out.
- the rubber composition for mold release recovery of the present invention is molded into an appropriate shape such as a sheet.
- an appropriate shape such as a sheet.
- kneading means examples include a Banbury mixer, a roll mixer, and the like, in addition to the pressure type kneader.
- the form of the first, second, and third mold release recovery rubber-based compositions of the present invention is not particularly limited, but the kneaded resin composition is preheated during kneading unless it is quickly cooled. Since the vulcanization is promoted and stable performance cannot be obtained, the sheet is preferably in the form of a sheet that can be easily cooled in a short time.
- Test Method Test methods for evaluating various physical properties described in Examples and Comparative Examples are as follows.
- [Elongation and tensile strength] It measures according to the measuring method of tensile strength and elongation at break in JIS K6251.
- ⁇ Test specimen preparation conditions> Using a 37T automatic press, an unvulcanized sample is molded at a mold temperature of 175 ° C., a molding pressure of 10 MPa (gauge pressure), and a molding time of 5 minutes. The size of the molded specimen was 80 ⁇ 160 ⁇ 2 mm, and this was punched out with a No. 3 dumbbell to obtain a test specimen for measurement.
- Rubber hardness It is measured by a method in accordance with JIS K6253 “Method for testing hardness of vulcanized rubber and thermoplastic rubber”. Three 80 ⁇ 160 ⁇ 2 mm test pieces obtained under the test piece preparation conditions described above were stacked, and the durometer hardness was measured using a durometer of a type corresponding to the rubber hardness.
- Mold temperature 175 ° C / 175 ° C Curing time: ECR-CL 300 seconds SW7320 180 seconds mold release recovery test After completion of mold initialization cleaning, the mold release recovery rubber composition was molded by compression molding into 3 shots with a curing time of 200 seconds. . Thereafter, molding was performed using a commercially available biphenyl-based epoxy resin molding material (EME-7351T manufactured by Sumitomo Bakelite Co., Ltd.), and the releasability and continuous moldability were evaluated.
- Example 1 (first rubber release composition for mold release recovery of the present invention) In a 3000 ml jacketed pressure kneader, EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C. 23)] 1050 g and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight When 450 g was added and pressure-kneaded for about 3 minutes while cooling, the EPDM and BR mixed dough became sticky and its temperature was about 80 ° C.
- Example 2 (first rubber release composition for mold release recovery of the present invention)
- the blending amount of the base resin was set to 900 g of EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 23] and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight] was changed to 600 g, and the amount of process oil [trade name PW-380; made by Idemitsu Kosan Co., Ltd.] was changed from 45 g (3 parts by weight) to 75 g (5 parts by weight).
- a thickness of 6 mm was used in the same manner except that 85 g (5.7 parts by weight) of Roxyol G-78 (polymer composite ester manufactured by Cognis Japan Co., Ltd.) was used instead of 85 g (5.7 parts by weight) of wax OP.
- the rubber composition B for sheet mold release recovery was obtained.
- Table 1 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition B. As can be seen from the test results, the sheet-like mold release recovery rubber-based composition B showed good moldability and release recovery.
- Example 3 (first rubber release composition for mold release recovery of the present invention)
- Example 1 instead of 60 g of zinc stearate (4 parts by weight), 60 g of calcium stearate (4 parts by weight) was used, and instead of 85 g of lycowax OP (5.7 parts by weight), Ricolb H- A rubber composition C for sheet mold release recovery with a thickness of 6 mm was obtained in the same manner except that 85 g (5.7 parts by weight) of 4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) was used.
- Table 1 shows the characteristic values and the release recovery test results of the obtained rubber composition C for recovery from release from a sheet-shaped mold. As can be seen from the test results, the sheet-based mold release recovery rubber-based composition C exhibited good moldability and mold release recovery.
- Example 4 (first rubber release composition for mold release recovery of the present invention)
- EPDM fabric of Mooney viscosity ML 1 + 4 (100 ° C.) 23] and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight]
- 60 g of zinc stearate (4 parts by weight) instead of 60 g of calcium stearate (4 parts by weight)
- 85 g of lycowax OP (5.7 parts by weight of the same)
- a rubber composition D for sheet mold release recovery with a thickness of 6 mm was obtained in the same manner except that 85 g (5.7 parts by weight) of fatty acid amide S (fatty acid amide manufactured by Kao Corporation) was used.
- Table 1 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition D. As can be seen from the test results, the sheet-based mold release recovery rubber-based composition D exhibited good moldability and mold release recovery.
- Example 1 the blending amount of the base resin was 600 g of EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 23] and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight] Except for changing to 900 g, a rubber composition E for sheet mold release recovery having a thickness of 6 mm was obtained in the same manner. Table 1 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition E. As can be seen from the test results, the rubber composition E for recovery from release from the sheet-shaped mold had voids and poor continuous moldability.
- Example 5 (second rubber composition for mold release recovery of the present invention) In a 3000 ml jacketed pressure kneader, EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C. 23)] 1050 g and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight When 450 g was added and pressure-kneaded for about 3 minutes while cooling, the EPDM and BR mixed dough became sticky and its temperature was about 80 ° C.
- Example 6 (second mold release recovery rubber composition of the present invention)
- the blending amount of the base resin was EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 23] 900 g and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight] was changed to 600 g, and the amount of process oil [trade name PW-380; made by Idemitsu Kosan Co., Ltd.] was changed from 45 g (3 parts by weight) to 75 g (5 parts by weight).
- a thickness of 6 mm was used in the same manner except that 85 g (5.7 parts by weight) of Roxyol G-78 (polymer composite ester manufactured by Cognis Japan Co., Ltd.) was used instead of 85 g (5.7 parts by weight) of wax OP.
- the rubber composition G for sheet mold release recovery was obtained.
- Table 2 shows the characteristic values and release recovery test results of the obtained rubber composition G for recovery from release from the sheet-shaped mold. As can be seen from the test results, the sheet-based mold release recovery rubber composition G exhibited good moldability and release recovery.
- Example 7 (second mold release recovery rubber composition of the present invention)
- Example 5 instead of 48 g of dicumyl peroxide (3.2 parts by weight), 28 g (1.9 parts by weight) of dicumyl peroxide and n-butyl 4,4-bis (t-butylperoxy) ) 20 g (1.3 parts by weight) of valerate, 60 g of calcium stearate (4 parts by weight) instead of 60 g of zinc stearate (4 parts by weight), 85 g of lycowax OP (5.7 parts by weight)
- Recolub H-4 modified hydrocarbon manufactured by Clariant Japan Co., Ltd.
- Table 2 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition H. As can be seen from the test results, the sheet-based mold release recovery rubber composition H showed good moldability and release recovery.
- Example 8 (second mold release recovery rubber composition of the present invention)
- Example 5 instead of the BR dough Mooney viscosity ML 1 + 4 (100 °C) 42,1,4 cis-bond content of 95 wt% of one] 450 g, BR dough Mooney viscosity ML 1 + 4 (100 °C) 35,1 , 4-cis bond content 95% by weight], 450 g of dicumyl peroxide 48 g (3.2 parts by weight) instead of 13 g 1,1-bis (t-butylperoxy) cyclohexane (same 0 9 parts by weight) and 35 g of dicumyl peroxide (2.3 parts by weight), and instead of 60 g of zinc stearate (4 parts by weight), 60 g of calcium stearate (4 parts by weight) was used.
- Example 5 the blending amount of the base resin was set to 450 g of EPDM fabric [of Mooney viscosity ML 1 + 4 (100 ° C.) 23] and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight] Except for changing to 1050 g, a rubber composition J for sheet mold release recovery having a thickness of 6 mm was obtained in the same manner. Table 2 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition J. As can be seen from the test results, in the rubber-based composition J for recovering mold release from the sheet, voids were generated and the continuous moldability was poor.
- Example 9 (Third Mold Release Recovery Rubber Composition of the Present Invention) 900 g of EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C. 23)] in a 3000 ml jacketed pressure kneader and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight
- EPDM fabric Mooney viscosity ML 1 + 4 (100 ° C. 23)
- BR fabric Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight
- Example 10 (third rubber release composition for mold release recovery of the present invention)
- the amount of white carbon was changed from 900 g (60 parts by weight) to 1050 g (70 parts by weight), and instead of 225 g of zinc stearate (15 parts by weight), 225 g of calcium stearate (15 parts of the same).
- the compounding amount of Roxyol G-78 was changed from 150 g (10 parts by weight) to 225 g (15 parts by weight)
- for release recovery from a sheet-like mold having a thickness of 6 mm A rubber-based composition L was obtained.
- Table 3 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition L. As can be seen from the test results, the sheet-based mold release recovery rubber-based composition L showed good moldability and release recovery.
- Example 11 (third rubber composition for mold release recovery of the present invention)
- the blending amount of the base resin was changed to EPDM fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 23] 1050 g and BR fabric [Mooney viscosity ML 1 + 4 (100 ° C.) 42, 1,4 cis bond content 95% by weight] was changed to 450 g, and instead of 225 g of zinc stearate (15 parts by weight), 150 g of calcium stearate (10 parts by weight) was used, and the amount of Roxyol G-78 was 150 g (10 parts by weight).
- Example 12 (Third mold release recovery rubber composition of the present invention)
- Example 9 instead of BR dough Mooney viscosity ML 1 + 4 (100 °C) 42,1,4 cis-bond content of 95 wt% of one] 600 g, BR dough Mooney viscosity ML 1 + 4 (100 °C) 35,1 , 4-cis bond content 95% by weight] using 450 g, the white carbon content was changed from 900 g (60 parts by weight) to 1050 g (70 parts by weight), and 225 g of zinc stearate (15 parts by weight).
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Abstract
Description
そこで、これらの状況を回避するためにクリーニングの実施が必要となるが、クリーニングした後は、金型表面がきれいになる反面、金型表面の離型剤も取り去られるため、クリーニング直後に封止成形を再開すると、極端に金型離型性が悪くなるという問題があった。
そのためクリーニング材の使用後に、金型離型回復樹脂組成物を成形し、金型表面に金型離型回復樹脂組成物中の離型剤を移行させ、離型性を回復させる必要があった。
これら金型清掃用樹脂としては、トランスファタイプとコンプレッションタイプの2つのタイプに大別でき、トランスファタイプには、メラミン系樹脂成形材料が使用され、コンプレッションタイプには、メラミン系樹脂成形材料並びにゴム系組成物が使用されている。
近年、集積回路等(IC・LSIと略記する)の高集積化、薄型化、表面実装化に伴い、成形品の形状、構造の多様化が進んでおり、このため、半導体封止材料の高流動化や環境対応化が計られている。
このため、高流動化タイプのエポキシ封止材では、エアベント部分での樹脂詰まりが発生しやすく、これらの詰まりが発生するとエア抜けが悪く樹脂が流れなくなるために、キャビティ部に未充填が発生し不良となることから連続成形が困難になる。そこで、これらの状況を回避するためにクリーニングの実施が必要となるが、トランスファタイプのクリーニング材では、前述の理由で樹脂が正常に流れないために、エアベントに詰まった樹脂を除去することは難しかった。
上記問題点を解決するため、作業性(離型性)、成形性に優れ、離型回復工程後の金型離型性が長時間持続し、封止成形品の連続成形回数が多い離型回復用ゴム系組成物が求められている。
(1)硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤と、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤とを含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が50~100秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。(以下、第1の金型離型回復用ゴム系組成物という)
(2)硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤と、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤とを含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が200~400秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。(以下、第2の金型離型回復用ゴム系組成物という)
(3)硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤を含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が200~400秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。(以下、第3の金型離型回復用ゴム系組成物という)
本発明において使用する未加硫ゴムは、エチレン-プロピレンゴムとブタジエンゴムとを混合併用するものである。
エチレン-プロピレンゴム(以下、EPMと略記することがある)とは、通常のエチレン-プロピレンゴム(EPM)とエチレン-プロピレン-ジエンゴム(以下、EPDMと略記することがある)の双方を含む趣旨である。
上記ポリエンモノマーとしては、ジシクロペンタジエン、5-シクロオクタジエン、1,7-シクロドデカジエン、1,5,9-シクロドデカトリエン、1,4-シクロヘプタジエン、1,4-シクロヘキサジエン、ノルボルナジエン、メチレンノルボルネン、2-メチルペンタジエン-1,4、1,5-ヘキサジエン、1,6-ヘプタジエン、メチル-テトラヒドロインデン、1,4-ヘキサジエン等があげられる。このようなターポリマー中の各モノマーの共重合割合は、好ましくはエチレンが30~80モル%、ポリエンモノマーが0.1~2モル%で残りがα-オレフィンである。より好ましくはエチレンが30~60モル%である。そして、上記ターポリマーであるEPDMとしては、ムーニー粘度ML1+4 (100℃)が20~70のものを用いるのが好ましい。
エチレン-プロピレンゴムが90重量部を超えて配合されると、金型離型性が悪くなるので好ましくない。ブタジエンゴムが50重量部を超えて配合されると、金型離型性は良くなるが、加硫後の成形物が硬くて脆くなることによりチッピングが発生しやすくなるので好ましくない。
上記未加硫ゴムは、加硫硬化した後の引張強度が3~10MPa、好ましくは5~8MPaのものである。引張強度が3MPa以下になると、チッピングが発生するので好ましくない。
上記未加硫ゴムは、加硫硬化した後のゴム硬度(デュロメータ硬さ)がA60~95、好ましくはA70~90のものである。ゴム硬度がこの範囲を逸脱すると、チッピングやボイドが発生するので好ましくない。
上記未加硫ゴムは、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が50~100秒、好ましくは70~100秒のものである。tc (90)の値が該範囲内であれば、加硫速度が速すぎることがなく、キャビティの隅々まで樹脂を充填させることが出来るため、スティッキング等の不具合を発生することなく離型回復を実施することが出来る。
金属石鹸系離型剤の例としては、例えば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を例示できる。有機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(コグニス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 変性炭化水素系ワックス)、ロキシオールVPN881(コグニス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(日本油脂株式会社製 脂肪酸アミド)等を例示できる。
金属石鹸系離型剤と、その他の離型剤(有機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)との割合は、90:10~30:70が好ましい。その他の離型剤の割合が過剰になると、連続成形性が悪くなるので好ましくない。
金属石鹸系離型剤及びその他の離型剤(有機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)の総添加量は、未加硫ゴム100重量部に対して、0.5~30重量部が好ましい。
離型剤の量が不足すると、金型離型性が低下し、離型剤の量が多すぎると金型離型性は良いが、金型離型回復用ゴム系組成物が溶融した際の流動性が著しく低下して成形性が悪くなる他、離型回復工程後のダミーショット回数が増加するため好ましくない。
洗浄剤としては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、N-メチルジエタノールアミン、N,N-ジ-n- ブチルエタノールアミン等のアミン類、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル等のグリコールエーテル類、イミダゾール類及びイミダゾリン類があげられる。上記洗浄剤の使用量は、未加硫ゴム100重量部に対して、好ましくは5~50重量部、より好ましくは5~30重量部である。この他にも界面活性剤等の洗浄助剤を用いることができる。
本発明の第2の金型離型回復用ゴム系組成物は、基材樹脂として使用する未加硫ゴムが、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が200~400秒、好ましくは250~350秒の未加硫ゴムである点を除き、本発明の第1の金型離型回復用ゴム系組成物と同じである。
上記tc (90)の値の調整は、ジエンの種類や量、過酸化物の種類や量、加硫促進剤の種類や量、共架橋剤の種類や量等により適宜調整することが出来る。
本発明の第3の金型離型回復用ゴム系組成物は、離型剤が、金属石鹸系離型剤、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤である点を除き、本発明の第2の金型離型回復用ゴム系組成物と同じである。
実施例及び比較例にて記載の各種物性評価の試験方法は以下の通りである。
〔伸び及び引張強度〕
JIS K6251における引張強さ及び切断時伸びの測定方法に準拠して測定する。
〈試験片の作製条件〉
37T自動プレス機を用い、金型温度175℃、成形圧10MPa(ゲージ圧)、成形時間5分にて未加硫試料を成形する。成形した試験片サイズは80×160×2mmのシート状で、これを3号ダンベルにて打ち抜いて測定用の試験片とした。
JIS K6253『加硫ゴム及び熱可塑性ゴムの硬さ試験方法』に準拠した方法で測定する。
前述の試験片作製条件にて得られた80×160×2mm試験片を3枚重ねにし、ゴム硬度に応じたタイプのデュロメータを用いてデュロメータ硬さを測定した。
JIS K6300-2『振動式加硫試験機による加硫特性の求め方』に準拠した方法を用い、金型温度175℃にて90%加硫時間(適正加硫点)tc (90)を測定した。
金型の初期化
金型離型回復用用ゴム系組成物の試験を行うに際し、試験前の金型表面状態を定常にする必要があるため、市販のメラミン樹脂系金型クリーニング材(日本カーバイド工業株式会社製 ニカレットECR-CL)を用いてトランスファ成形により5ショットのクリーニングを実施し、さらに市販のメラミン樹脂系金型クリーニング材(日本カーバイド工業株式会社製 ニカレットECR-SW7320)を用いてコンプレッション成形により2ショットのクリーニングを実施して金型洗浄を行った。
〈成形条件〉
金型:実施例1~8ではQFPを用いた。
実施例9~12ではPDIP-8L(8ポット-96キャビティ)を用いた。
金型温度:175℃/175℃
硬化時間:ECR-CL 300秒
SW7320 180秒
離型回復試験
金型初期化のための清掃終了後、金型離型回復用用ゴム系組成物をコンプレッション成形により硬化時間200秒で3ショット成形した。その後、市販のビフェニル系エポキシ樹脂成形材料(住友ベークライト株式会社製 EME-7351T)を用いて成形を実施し、離型性及び連続成形性を評価した。
〈成形条件〉
金型:QFP又はPDIP-8L
金型温度:175℃/175℃
硬化時間:100秒
3000mlのジャケット付き加圧型ニーダー中にEPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]を1050gとBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]450gを添加し、冷却しながら約3分間加圧混練すると、EPDMとBRの混合生地はモチ状になり、その温度は約80℃となった。次いで、ポリオキシアルキレンデシルエーテル系界面活性剤45g(EPDMとBRの混合生地100重量部に対して3重量部)、ステアリン酸15g(同1重量部)、ホワイトカーボン630g(同42重量部)、プロセスオイル [商品名PW-380;出光興産株式会社製] 45g(同3重量部)、炭酸カルシウム75g(同5重量部)、酸化チタン75g(同5重量部)、酸化亜鉛75g(同5重量部)、ステアリン酸亜鉛60g(同4重量部)及びリコワックス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)85g(同5.7重量部)を加えて約3分間混練した。最後に1,1-ビス(t-ブチルパーオキシ)シクロヘキサン48g(同3.2重量部)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。得られた混練物を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℃以下に冷却することにより、厚さ6mmのシート状金型離型回復用用ゴム系組成物Aを得た。
得られたシート状金型離型回復用用ゴム系組成物Aの特性値及び離型回復試験結果を表1に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Aは良好な成形性及び離型回復性を示した。
実施例1において、基材樹脂の配合量を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]900g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]600gに変更し、プロセスオイル [商品名PW-380;出光興産株式会社製] の配合量を45g(同3重量部)から75g(同5重量部)に変更し、リコワックスOP 85g(同5.7重量部)の替わりに、ロキシオールG-78(コグニスジャパン株式会社製 高分子複合エステル)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Bを得た。
得られたシート状金型離型回復用用ゴム系組成物Bの特性値及び離型回復試験結果を表1に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Bは良好な成形性及び離型回復性を示した。
実施例1において、ステアリン酸亜鉛60g(同4重量部)の替わりに、ステアリン酸カルシウム60g(同4重量部)を用い、リコワックスOP 85g(同5.7重量部)の替わりに、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)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Cを得た。
得られたシート状金型離型回復用用ゴム系組成物Cの特性値及び離型回復試験結果を表1に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Cは良好な成形性及び離型回復性を示した。
実施例1において、基材樹脂を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]825g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]675gに変更し、ステアリン酸亜鉛60g(同4重量部)の替わりに、ステアリン酸カルシウム60g(同4重量部)を用い、リコワックスOP 85g(同5.7重量部)の替わりに、脂肪酸アマイドS(花王株式会社製 脂肪酸アミド)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Dを得た。
得られたシート状金型離型回復用用ゴム系組成物Dの特性値及び離型回復試験結果を表1に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Dは良好な成形性及び離型回復性を示した。
実施例1において、基材樹脂の配合量を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]600g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]900gに変更する以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Eを得た。
得られたシート状金型離型回復用用ゴム系組成物Eの特性値及び離型回復試験結果を表1に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Eは、ボイドが発生し、連続成形性も不良であった。
3000mlのジャケット付き加圧型ニーダー中にEPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]を1050gとBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]450gを添加し、冷却しながら約3分間加圧混練すると、EPDMとBRの混合生地はモチ状になり、その温度は約80℃となった。次いで、ポリオキシアルキレンデシルエーテル系界面活性剤45g(EPDMとBRの混合生地100重量部に対して3重量部)、ステアリン酸15g(同1重量部)、ホワイトカーボン600g(同40重量部)、プロセスオイル [商品名PW-380;出光興産株式会社製] 45g(同3重量部)、炭酸カルシウム75g(同5重量部)、酸化チタン75g(同5重量部)、酸化亜鉛75g(同5重量部)、ステアリン酸亜鉛60g(同4重量部)及びリコワックス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)85g(同5.7重量部)を加えて約3分間混練した。最後にジクミルパーオキサイド48g(同3.2重量部)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110℃を超えないように調節した。得られた混練物を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℃以下に冷却することにより、厚さ6mmのシート状金型離型回復用用ゴム系組成物Fを得た。
得られたシート状金型離型回復用用ゴム系組成物Fの特性値及び離型回復試験結果を表2に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Fは良好な成形性及び離型回復性を示した。
実施例5において、基材樹脂の配合量を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]900g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]600gに変更し、プロセスオイル [商品名PW-380;出光興産株式会社製] の配合量を45g(同3重量部)から75g(同5重量部)に変更し、リコワックスOP 85g(同5.7重量部)の替わりに、ロキシオールG-78(コグニスジャパン株式会社製 高分子複合エステル)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Gを得た。
得られたシート状金型離型回復用用ゴム系組成物Gの特性値及び離型回復試験結果を表2に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Gは良好な成形性及び離型回復性を示した。
実施例5において、ジクミルパーオキサイド48g(同3.2重量部)の替わりに、ジクミルパーオキサイド28g(同1.9重量部)及びn-ブチル4,4-ビス(t-ブチルパーオキシ)バレレート20g(同1.3重量部)を用い、ステアリン酸亜鉛60g(同4重量部)の替わりに、ステアリン酸カルシウム60g(同4重量部)を用い、リコワックスOP 85g(同5.7重量部)の替わりに、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)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Hを得た。
得られたシート状金型離型回復用用ゴム系組成物Hの特性値及び離型回復試験結果を表2に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Hは良好な成形性及び離型回復性を示した。
実施例5において、BR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]450gの替わりに、BR生地[ムーニー粘度ML1+4(100℃) 35、1,4シス結合含有率95重量%のもの]450gを用い、ジクミルパーオキサイド48g(同3.2重量部)の替わりに、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン13g(同0.9重量部)及びジクミルパーオキサイド35g(同2.3重量部)を用い、ステアリン酸亜鉛60g(同4重量部)の替わりに、ステアリン酸カルシウム60g(同4重量部)を用い、リコワックスOP 85g(同5.7重量部)の替わりに、脂肪酸アマイドS(花王株式会社製 脂肪酸アミド)85g(同5.7重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Iを得た。
得られたシート状金型離型回復用用ゴム系組成物Iの特性値及び離型回復試験結果を表2に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Iは良好な成形性及び離型回復性を示した。
実施例5において、基材樹脂の配合量を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]450g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]1050gに変更する以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Jを得た。
得られたシート状金型離型回復用用ゴム系組成物Jの特性値及び離型回復試験結果を表2に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Jは、ボイドが発生し、連続成形性も不良であった。
3000mlのジャケット付き加圧型ニーダー中にEPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]を900gとBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]600gを添加し、冷却しながら約3分間加圧混練すると、EPDMとBRの混合生地はモチ状になり、その温度は約80℃となった。次いで、ポリオキシアルキレンデシルエーテル系界面活性剤45g(EPDMとBRの混合生地100重量部に対して3重量部)、ステアリン酸15g(同1重量部)、ホワイトカーボン900g(同60重量部)、酸化チタン75g(同5重量部)、カーボンブラック1.5g(同0.1重量部)、ステアリン酸亜鉛225g(同15重量部)、ロキシオールG-78(コグニスジャパン株式会社製 高分子複合エステル)150g(同10重量部)及びリコルブH-4(クラリアントジャパン株式会社製 変性炭化水素)150g(同10重量部)を加えて約3分間混練した。最後にジクミルパーオキサイド18g(同1.2重量部)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110℃を超えないように調節した。得られた混練物を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℃以下に冷却することにより、厚さ6mmのシート状金型離型回復用用ゴム系組成物Kを得た。
得られたシート状金型離型回復用用ゴム系組成物Kの特性値及び離型回復試験結果を表3に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Kは良好な成形性及び離型回復性を示した。
実施例9において、ホワイトカーボンの配合量を900g(同60重量部)から1050g(同70重量部)に変更し、ステアリン酸亜鉛225g(同15重量部)の替わりに、ステアリン酸カルシウム225g(同15重量部)を用い、ロキシオールG-78の配合量を150g(同10重量部)から225g(同15重量部)に変更する以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Lを得た。
得られたシート状金型離型回復用用ゴム系組成物Lの特性値及び離型回復試験結果を表3に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Lは良好な成形性及び離型回復性を示した。
実施例9において、基材樹脂の配合量を、EPDM生地[ムーニー粘度ML1+4(100℃) 23のもの]1050g及びBR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]450gに変更し、ステアリン酸亜鉛225g(同15重量部)の替わりに、ステアリン酸カルシウム150g(同10重量部)を用い、ロキシオールG-78の配合量を150g(同10重量部)から105g(同7重量部)に変更し、リコルブH-4 150g(同10重量部)の替わりに、脂肪酸アマイドS(花王株式会社製 脂肪酸アミド)45g(同3重量部)を用い、ジクミルパーオキサイドの配合量を18g(同1.2重量部)から30g(同2重量部)に変更する以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Mを得た。
得られたシート状金型離型回復用用ゴム系組成物Mの特性値及び離型回復試験結果を表3に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Mは良好な成形性及び離型回復性を示した。
実施例9において、BR生地[ムーニー粘度ML1+4(100℃) 42、1,4シス結合含有率95重量%のもの]600gの替わりに、BR生地[ムーニー粘度ML1+4(100℃) 35、1,4シス結合含有率95重量%のもの]450gを用い、ホワイトカーボンの配合量を900g(同60重量部)から1050g(同70重量部)に変更し、ステアリン酸亜鉛225g(同15重量部)の替わりに、ステアリン酸亜鉛105g(同7重量部)及びステアリン酸カルシウム195g(同13重量部)を用い、ロキシオールG-78の配合量を150g(同10重量部)から300g(同20重量部)に変更し、ジクミルパーオキサイド18g(同1.2重量部)の替わりに、ジクミルパーオキサイド35g(同2.3重量部)及び1,1-ビス(t-ブチルパーオキシ)シクロヘキサン13g(同0.9重量部)を用いる以外は同様にして、厚さ6mmのシート状金型離型回復用用ゴム系組成物Nを得た。
得られたシート状金型離型回復用用ゴム系組成物Nの特性値及び離型回復試験結果を表3に示す。試験結果から判るように、シート状金型離型回復用用ゴム系組成物Nは良好な成形性及び離型回復性を示した。
Claims (7)
- 硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤と、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤とを含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が50~100秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。
- 硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤と、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤とを含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が200~400秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。
- 硬化性樹脂の成形工程で発生する金型表面の汚れを取り除いた後に、金型表面に離型性を付与する樹脂組成物において、基材樹脂として、エチレン-プロピレンゴムとブタジエンゴムとの配合割合が、90/10~50/50重量部に設定されている未加硫ゴムを使用し、且つ金属石鹸系離型剤、有機脂肪酸エステル系離型剤、合成ワックス離型剤及び脂肪酸アミド系離型剤の中から選ばれた少なくとも1種の離型剤を含有し、上記未加硫ゴムが、加硫硬化した後の伸び率が80~800%、引張強度が3~10MPa、ゴム硬度(デュロメータ硬さ)がA60~95、金型温度175℃における90%加硫時間(適正加硫点)tc (90)が200~400秒の値の範囲にある未加硫ゴムであることを特徴とするコンプレッションタイプ金型離型回復用ゴム系組成物。
- 上記有機脂肪酸エステル系離型剤が、モンタン酸部分ケン化エステル又は高分子複合エステルである、請求の範囲第1~3項の何れかに記載の金型離型回復用ゴム系組成物。
- 上記合成ワックスが、変性炭化水素系ワックス又は鉱油系合成ワックスである、請求の範囲第1~3項の何れかに記載の金型離型回復用ゴム系組成物。
- 更に、充填剤、洗浄剤、洗浄助剤、加硫剤、加硫助剤、加硫促進剤、加硫促進助剤、顔料の少なくとも1種を含有する、請求の範囲第1~3項の何れかに記載の金型離型回復用ゴム系組成物。
- 請求の範囲第1~6項の何れかに記載の金型離型回復用ゴム系組成物を用いた金型離型回復方法。
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WO2014042199A1 (ja) * | 2012-09-14 | 2014-03-20 | 日本カーバイド工業株式会社 | 金型離型回復用樹脂組成物及び金型離型回復方法 |
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CN103171065A (zh) * | 2013-03-14 | 2013-06-26 | 西北工业大学 | 一种模具用的脱模胶及其制备方法 |
WO2016167415A1 (ko) * | 2015-04-17 | 2016-10-20 | 주식회사 나라켐 | 충진성이 우수한 고무 조성물 |
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JP2013035965A (ja) * | 2011-08-09 | 2013-02-21 | Fujikura Ltd | 絶縁組成物及び成形品 |
WO2014042199A1 (ja) * | 2012-09-14 | 2014-03-20 | 日本カーバイド工業株式会社 | 金型離型回復用樹脂組成物及び金型離型回復方法 |
JPWO2014042199A1 (ja) * | 2012-09-14 | 2016-08-18 | 日本カーバイド工業株式会社 | 金型離型回復用樹脂組成物及び金型離型回復方法 |
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JP5726517B2 (ja) | 2015-06-03 |
TW201000289A (en) | 2010-01-01 |
JPWO2009122955A1 (ja) | 2011-07-28 |
TWI449615B (zh) | 2014-08-21 |
KR20100138878A (ko) | 2010-12-31 |
CN101945746A (zh) | 2011-01-12 |
SG194416A1 (en) | 2013-11-29 |
CN101945746B (zh) | 2013-09-18 |
KR101591894B1 (ko) | 2016-02-18 |
MY161594A (en) | 2017-04-28 |
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