JPWO2009122955A1 - Rubber composition for mold release recovery - Google Patents

Abstract

In the compression-type mold release recovery rubber-based composition that gives mold release properties to the mold surface after removing dirt on the mold surface generated in the molding process of the curable resin, ethylene- Using unvulcanized rubber in which the blending ratio of propylene rubber and butadiene rubber is set to 90/10 to 50/50 parts by weight, and blending a specific release agent, the unvulcanized rubber is 80% to 800% elongation after vulcanization and curing, 3 to 10 MPa in tensile strength, A60 to 95 rubber hardness (durometer hardness), 90% vulcanization time at a mold temperature of 175 ° C. (appropriate vulcanization point) An unvulcanized rubber having a value of tc (90) in the range of 50 to 100 seconds or 200 to 400 seconds is used.

Description

  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.

When molding a molded product such as an integrated circuit using a thermosetting resin molding material such as an epoxy resin molding material, the release agent contained in the thermosetting resin molding material oozes out at the interface between the molding and the mold. By doing so, a mold release action is exhibited with respect to the cull part, the cavity part, and the runner part. When such molding is performed continuously several hundred times or more, 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.
Therefore, in order to avoid these situations, it is necessary to carry out cleaning. After cleaning, the mold surface is cleaned, but the mold release agent is also removed. When restarting, there was a problem that the mold releasability was extremely deteriorated.
Therefore, after using the cleaning material, it was necessary to mold the mold release recovery resin composition, transfer the mold release agent in the mold release recovery resin composition to the mold surface, and recover the release properties. .

On the other hand, in place of the thermosetting melamine resin molding material, 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. Further, 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. 4,935,175, (See Kaihei 4-357007).
These mold cleaning resins can be broadly classified into two types: transfer type and compression type. The transfer type uses melamine-based resin molding materials, and the compression type uses melamine-based resin molding materials and rubber-based resins. A composition is used.
In recent years, with the integration, thinning, and surface mounting of integrated circuits and the like (abbreviated as IC / LSI), the shape and structure of molded products have been diversified. Fluidization and environmental measures are being planned.
For this reason, in the high fluidization type epoxy sealing material, resin clogging at the air vent part is likely to occur, and when these clogging occurs, the air does not escape and the resin does not flow, so the cavity part is not filled. Since it becomes defective, continuous molding becomes difficult. Therefore, in order to avoid these situations, it is necessary to carry out cleaning. However, with the transfer type cleaning material, it is difficult to remove the resin clogged in the air vent because the resin does not flow normally for the reasons described above. It was.

  Compression type cleaning materials are used to eliminate such clogging of the air vents, but when melamine 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 is complicated. On the other hand, when the rubber 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.

In addition, 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). When a rubber-based composition is used in a small number of molds for manufacturing a package, the number of packages is increased, so that a phenomenon that a molded product after curing sticks to the mold tends to occur. When removing this, there is a problem that chipping occurs in which the sheet-like molded product is broken and the rubber-based composition remains in the cavity. When chipping occurs in these molds, since the number of cavities is large, it takes a lot of time to remove the molded product at the chipping location, and the productivity is greatly reduced.
In order to solve the above-mentioned problems, it is excellent in workability (releasability) and moldability, the mold releasability after the mold release recovery process is maintained for a long time, and the number of continuous molding of the sealed molded product is large. There is a need for a rubber composition for recovery.

US Pat. No. 4,935,175 JP 04-357007 A

  As described above, although 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. .

  In addition, as described above, 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, as well as 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).
(1) In a resin composition that imparts releasability 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 Using a non-vulcanized 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 Containing at least one release agent selected from fatty acid amide release agents, the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, and a tensile strength of 3 to 3. Unvulcanized rubber with 10 MPa, rubber hardness (durometer hardness) of A60 to 95, 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. in the range of 50 to 100 seconds Compression characterized by Rubber composition for recovering mold release. (Hereinafter referred to as the first mold release recovery rubber composition)
(2) In a resin composition that gives mold releasability 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 Using a non-vulcanized 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 Containing at least one release agent selected from fatty acid amide release agents, the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, and a tensile strength of 3 to 3. Unvulcanized rubber with 10 MPa, rubber hardness (durometer hardness) A60-95, 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. in the range of 200-400 seconds Compression characterized by -Type mold release recovery rubber composition. (Hereinafter referred to as the second mold release recovery rubber composition)
(3) In a resin composition that gives mold releasability 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 Of unvulcanized rubber with a blending ratio of 90/10 to 50/50 parts by weight, and a metal soap-based release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and a fatty acid It contains at least one release agent selected from amide release agents, and the unvulcanized rubber has an elongation rate of 80 to 800% after vulcanization and curing, and a tensile strength of 3 to 10 MPa, It 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.

Hereinafter, first, the first mold release recovery rubber composition of the present invention will be described in detail.
The unvulcanized rubber used in the present invention is a mixture of ethylene-propylene rubber and butadiene rubber.
The ethylene-propylene rubber (hereinafter sometimes abbreviated as EPM) is intended to include both ordinary ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (hereinafter sometimes abbreviated as EPDM). is there.

As said EPM, the copolymerization ratio of ethylene and α-olefin (particularly propylene) is ethylene / α-olefin = 55/45 to 83/17 in molar ratio, and Mooney viscosity ML _{1 + 4} (100 ° C.) is 5 to 300. In particular, the copolymerization ratio is such that the molar ratio ethylene / α-olefin = 55/45 to 61/39 and the Mooney viscosity ML _{1 + 4} (100 ° C.) is 36 to 44.

The EPDM is a terpolymer composed of ethylene, α-olefin, and a cyclic or non-cyclic product having a nonconjugated double bond. More specifically, it is a terpolymer composed of ethylene, an α-olefin (particularly propylene), and a polyene monomer.
Examples of the polyene monomer include dicyclopentadiene, 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, 1,6-heptadiene, methyl-tetrahydroindene, 1,4-hexadiene and the like. 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 α-olefin. More preferably, ethylene is 30 to 60 mol%. And as EPDM which is the said terpolymer, it is preferable to use that whose Mooney viscosity ML1 _{+ 4} (100 degreeC) is 20-70.

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.

And the compounding ratio of the said ethylene-propylene rubber and butadiene rubber is 90 / 10-50 / 50 weight part by weight ratio, Preferably it is 80 / 20-60 / 40 weight part.
When the ethylene-propylene rubber is blended 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) of A60 to 95, preferably A70 to 90 after vulcanization and curing. 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. for 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.

In addition to the unvulcanized rubber, 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.
Examples of the metal soap release agent include calcium stearate, zinc stearate, zinc myristate and the like. Organic fatty acid ester release agents, synthetic waxes, fatty acid amide release agents include Rico wax OP (Montannic acid partially saponified ester manufactured by Clariant Japan Co., Ltd.), Roxyol G-78 (Cognis Japan Co., Ltd. polymer composite) 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- Examples include P (fatty acid amide manufactured by Kao Corporation), Alflow HT-50 (fatty acid amide manufactured by NOF Corporation), and the like.
The ratio of the metal soap release agent to other release agents (organic fatty acid ester release agent, synthetic wax, fatty acid amide release agent) 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 (organic fatty acid ester release agent, synthetic wax, fatty acid amide release agent) is 0. 0 parts by weight with respect to 100 parts by weight of the unvulcanized rubber. 5 to 30 parts by weight is preferred.
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 (reinforcing agent) 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 the cleaning agent 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. In addition, a cleaning aid such as a surfactant can be used.

  Examples of the vulcanizing agent 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. In general, 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. In addition, vulcanization aids such as acrylic acid monomers and sulfur can be used.

  Examples of the vulcanization accelerator include guanidines such as diphenylguanidine and triphenylguanidine, for example, 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.

  In addition to these blends, the first mold release recovery rubber composition of the present invention can use a pigment or a colorant, for example, in order to distinguish it from a cleaning material. For example, inorganic pigments such as titanium oxide, carbon black, zinc white, cadmium yellow, bengara, bitumen, iron black, ultramarine, lithopone, titanium yellow, cobalt blue, etc., for example, phthalocyanine, azo, diazo, hansa yellow, quinacridone Examples thereof include 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 with respect to 100 parts by weight of the unvulcanized rubber.

Next, the second mold release recovery rubber composition of the present invention will be described.
In the second mold release recovery rubber composition of the present invention, the unvulcanized rubber used as the base resin is 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.

  If the value of 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.

Next, the third mold release recovery rubber composition of the present invention will be described.
In the third mold release recovery rubber composition of the present invention, 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 mold 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. 10-50 weight part is preferable with respect to 100 weight part. 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-based compositions of the present invention is not particularly limited, and known methods can be employed. For example, 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. When the temperature of the mixed dough reaches 70 to 110 ° C., 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. If necessary, the rubber composition for mold release recovery of the present invention is molded into an appropriate shape such as a sheet. And

  Examples of the kneading means 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 vulcanization is promoted and stable performance cannot be obtained, it is preferably a sheet that can be easily cooled in a short time.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

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.

[Vulcanization speed]
Measure 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C using a method based on JIS K6300-2 “How to determine vulcanization characteristics using a vibratory vulcanization tester”. did.

[Release test]
Initializing the mold When testing the rubber composition for mold release recovery, it is necessary to make the mold surface state before the test steady, so a commercially available melamine resin mold cleaning material (Nippon Carbide) 5 shots are cleaned by transfer molding using Nicalet ECR-CL, manufactured by Kogyo Co., Ltd., and compression molding using a commercially available melamine resin mold cleaning material (Nicaret ECR-SW7320, manufactured by Nippon Carbide Industries, Ltd.). The two-shot cleaning was performed according to the above, and the mold was cleaned.
<Molding condition>
Mold: In Examples 1 to 8, QFP was used.
In Examples 9 to 12, PDIP-8L (8 pot-96 cavity) was used.
Mold temperature: 175 ° C / 175 ° C
Curing time: ECR-CL 300 seconds
SW7320 180-second mold release recovery test After completion of cleaning for mold initialization, the mold release recovery rubber-based composition was molded by compression molding into three shots with a curing time of 200 seconds. Then, it shape | molded using the commercially available biphenyl type epoxy resin molding material (Sumitomo Bakelite Co., Ltd. EME-7351T), and evaluated mold release property and continuous moldability.
<Molding condition>
Mold: QFP or PDIP-8L
Mold temperature: 175 ° C / 175 ° C
Curing time: 100 seconds

Example 1 (first rubber release composition for mold release recovery of the present invention)
1050 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 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. Next, 45 g of polyoxyalkylene decyl ether surfactant (3 parts by weight with respect to 100 parts by weight of EPDM and BR mixed dough), 15 g of stearic acid (1 part by weight), 630 g of white carbon (42 parts by weight of the same), Process oil [trade name PW-380; manufactured by Idemitsu Kosan Co., Ltd.] 45 g (3 parts by weight), calcium carbonate 75 g (5 parts by weight), titanium oxide 75 g (5 parts by weight), zinc oxide 75 g (5 parts by weight) Part), 60 g (4 parts by weight) of zinc stearate and 85 g (5.7 parts by weight of montanic acid partially saponified ester) manufactured by Ricowax OP (Clariant Japan Co., Ltd.) were added and kneaded for about 3 minutes. Finally, 48 g (3.2 parts by weight) of 1,1-bis (t-butylperoxy) cyclohexane was 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, and cooled to 25 ° C. or less to obtain a rubber composition A for sheet mold release recovery having a thickness of 6 mm. .
Table 1 shows the characteristic values of the obtained rubber composition A for mold release recovery and the results of the release recovery test. As can be seen from the test results, the sheet-like mold release recovery rubber-based composition A exhibited good moldability and mold release recovery.

Example 2 (first rubber release composition for mold release recovery of the present invention)
In Example 1, 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 compound 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)
In 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), Ricole 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)
In Example 1, 825 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] In place of 60 g of zinc stearate (4 parts by weight) instead of 60 g of calcium stearate (4 parts by weight), instead of 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.

Comparative Example 1
In 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)
1050 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 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. Next, 45 g of polyoxyalkylene decyl ether surfactant (3 parts by weight with respect to 100 parts by weight of EPDM and BR mixed dough), 15 g of stearic acid (1 part by weight), 600 g of white carbon (40 parts by weight), Process oil [trade name PW-380; manufactured by Idemitsu Kosan Co., Ltd.] 45 g (3 parts by weight), calcium carbonate 75 g (5 parts by weight), titanium oxide 75 g (5 parts by weight), zinc oxide 75 g (5 parts by weight) Part), 60 g (4 parts by weight) of zinc stearate and 85 g (5.7 parts by weight of montanic acid partially saponified ester) manufactured by Ricowax OP (Clariant Japan Co., Ltd.) were added and kneaded for about 3 minutes. Finally, 48 g (3.2 parts by weight) of dicumyl peroxide was added and the mixture was kneaded for about 1 minute. During this period, the temperature of the kneaded product was adjusted so as not to exceed 110 ° C. The obtained kneaded material was quickly passed through a pressure roll, processed into a sheet shape and cooled to 25 ° C. or less to obtain a rubber composition F for sheet mold release recovery having a thickness of 6 mm. .
Table 2 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition F. As can be seen from the test results, the sheet-based mold release recovery rubber composition F exhibited good moldability and release recovery.

Example 6 (second mold release recovery rubber composition of the present invention)
In Example 5, 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 compound 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)
In 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) In the same manner, except for using 85 g (5.7 parts by weight) of Recolub H-4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) A rubber-based composition H was obtained.
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)
In Example 5, instead of the BR dough Mooney viscosity _{ML 1 + 4 (100 ℃)} 42,1,4 cis-bond content of 95 wt% of one] 450 g, BR dough Mooney viscosity _{ML 1 + 4 (100 ℃)} 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. In the same manner, except that 85 g of fatty acid amide S (fatty acid amide manufactured by Kao Corporation) (5.7 parts by weight) was used instead of 85 g of OP (5.7 parts by weight), a 6 mm thick sheet It was obtained Jokin type release rubber composition I for a recovery.
Table 2 shows the characteristic values and release recovery test results of the rubber composition I for recovery of release from the sheet-shaped mold. As can be seen from the test results, the sheet-type mold release recovery rubber composition I exhibited good moldability and mold release recovery.

Comparative Example 2
In 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 When 600 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. Next, 45 g of polyoxyalkylene decyl ether surfactant (3 parts by weight with respect to 100 parts by weight of EPDM and BR mixed dough), 15 g of stearic acid (1 part by weight), 900 g of white carbon (60 parts by weight), 75 g of titanium oxide (5 parts by weight), 1.5 g of carbon black (0.1 parts by weight), 225 g of zinc stearate (15 parts by weight), Roxyol G-78 (polymer composite ester manufactured by Cognis Japan Co., Ltd.) 150 g (10 parts by weight) and 150 g (10 parts by weight) of Recolbe H-4 (modified hydrocarbon manufactured by Clariant Japan KK) were added and kneaded for about 3 minutes. Finally, 18 g (1.2 parts by weight) of dicumyl peroxide was added and the mixture was kneaded for about 1 minute. During this period, the temperature of the kneaded product was adjusted so as not to exceed 110 ° C. The obtained kneaded material was quickly passed through a pressure roll, processed into a sheet shape and cooled to 25 ° C. or less to obtain a rubber composition K for sheet mold release recovery having a thickness of 6 mm. .
Table 3 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition K. As can be seen from the test results, the sheet-type mold release recovery rubber composition K exhibited good moldability and mold release recovery.

Example 10 (third rubber release composition for mold release recovery of the present invention)
In Example 9, 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). In the same manner, except that the blending amount of Roxyol G-78 is changed from 150 g (10 parts by weight) to 225 g (15 parts by weight). 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)
In Example 9, 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). Part) to 105 g (7 parts by weight), instead of 150 g (10 parts by weight) of Recolub H-4, 45 g (3 parts by weight) of fatty acid amide S (fatty acid amide manufactured by Kao Corporation) Release of 6mm thick sheet mold in the same way except changing the blending amount of dicumyl peroxide from 18g (1.2 parts by weight) to 30g (2 parts by weight) To obtain a rubber-based composition for M for recovery.
Table 3 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition M. As can be seen from the test results, the sheet-based mold release recovery rubber-based composition M exhibited good moldability and mold release recovery.

Example 12 (Third mold release recovery rubber composition of the present invention)
In Example 9, instead of BR dough Mooney viscosity _{ML 1 + 4 (100 ℃)} 42,1,4 cis-bond content of 95 wt% of one] 600 g, BR dough Mooney viscosity _{ML 1 + 4 (100 ℃)} 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). ), Zinc stearate 105 g (7 parts by weight) and calcium stearate 195 g (13 parts by weight) were used, and the amount of Roxyol G-78 was changed from 150 g (10 parts by weight) to 300 g (20 parts by weight). ), Instead of 18 g (1.2 parts by weight) of dicumyl peroxide, 35 g (2.3 parts by weight) of dicumyl peroxide and 1,1-bi (T-butylperoxy) cyclohexane 13g except for using (0.9 parts by weight) in the same manner to obtain a sheet-shaped mold release recovery rubber based composition N with a thickness of 6 mm.
Table 3 shows the characteristic values and release recovery test results of the obtained sheet-shaped mold release recovery rubber-based composition N. As can be seen from the test results, the sheet-based mold release recovery rubber-based composition N showed good moldability and mold release recovery.

  By using the rubber composition for mold release recovery according to the present invention, excellent mold release recovery property can be obtained, which is due to the recent enhancement of functionality of epoxy sealing resin and enhancement of functionality of semiconductor elements. It is possible to prevent sticking that occurs in the cavity portion, the air vent portion, and the like. Moreover, since mold releasability is maintained over a long period of time, excellent continuous formability is exhibited, leading to improved productivity.

Claims (7)

  In the resin composition that gives mold releasability to the mold surface after removing the mold surface dirt generated in the molding process of the curable resin, the blending ratio of ethylene-propylene rubber and butadiene rubber as the base resin Uses an unvulcanized rubber set to 90 / 10-50 / 50 parts by weight, and uses a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and a fatty acid amide type Containing at least one release agent selected from among release agents, the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, a tensile strength of 3 to 10 MPa, and a rubber Hard rubber (durometer hardness) is A60 to 95, 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. is an unvulcanized rubber having a value in the range of 50 to 100 seconds. Compression type featuring Rubber composition for mold release recovery.   In the resin composition that gives mold releasability to the mold surface after removing the mold surface dirt generated in the molding process of the curable resin, the blending ratio of ethylene-propylene rubber and butadiene rubber as the base resin Uses an unvulcanized rubber set to 90 / 10-50 / 50 parts by weight, and uses a metal soap release agent, an organic fatty acid ester release agent, a synthetic wax release agent, and a fatty acid amide type Containing at least one release agent selected from among release agents, the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, a tensile strength of 3 to 10 MPa, and a rubber Hard rubber (durometer hardness) is A60 to 95, 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. is an unvulcanized rubber having a value in the range of 200 to 400 seconds. Compression tie featuring Rubber mold composition for mold release recovery.   In the resin composition that gives mold releasability to the mold surface after removing the mold surface dirt generated in the molding process of the curable resin, the blending ratio of ethylene-propylene rubber and butadiene rubber as the base resin However, it uses unvulcanized rubber set to 90 / 10-50 / 50 parts by weight, and uses metal soap release agent, organic fatty acid ester release agent, synthetic wax release agent and fatty acid amide release agent. It contains at least one release agent selected from molds, and the unvulcanized rubber has an elongation of 80 to 800% after vulcanization and curing, a tensile strength of 3 to 10 MPa, a rubber hardness ( Durometer hardness) is A60 to 95, 90% vulcanization time (appropriate vulcanization point) tc (90) at a mold temperature of 175 ° C. is unvulcanized rubber having a value in the range of 200 to 400 seconds. Compression type gold A rubber composition for mold release recovery.   The rubber composition for mold release recovery according to any one of claims 1 to 3, wherein the organic fatty acid ester release agent is a partially saponified ester of montanic acid or a polymer composite ester.   The rubber composition for mold release recovery according to any one of claims 1 to 3, wherein the synthetic wax is a modified hydrocarbon wax or a mineral oil synthetic wax.   Furthermore, at least 1 sort (s) of a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization acceleration aid, and a pigment is contained. The rubber composition for mold release recovery according to any one of the above.   A mold release recovery method using the rubber composition for mold release recovery according to any one of claims 1 to 6.