TW200930757A - Mold cleaning rubber compositon - Google Patents

Abstract

This invention provides a mold cleaning rubber composition for removing soiling on the surface of a mold produced in a curable resin molding process. An unvulcanized rubber is used as a base material resin. The unvulcanied rubber comprises an ethylene-propylene rubber and a butadiene rubber at a mixing ratio of 90/10 to 50/50 on the basis of parts by weight. After the vulcanization curing of the unvulcanized rubber, the elongation is 80 to 800%, the tensile strength is 3 to 10 MPa, and the rubber hardness (durometer hardness) is A60 to 95. The 90% vulcanization time (proper vulcanization point) tc (90) at a mold temperature of 175 DEG C is 50 to 100 sec or 200 to 400 sec. When the mold cleaning rubber composition is used for cleaning for molds for the production of small-size packages having a large cavity depth, for example, PDIP or SOIC, and molds for the production of small packages, particularly small packages with a small number of pins, preferably, the mold cleaning rubber composition contains a release agent in addition to the unvulcanized rubber having a tc (90) value of 200 to 400 sec.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-based composition for mold cleaning, and more particularly to a method for removing dirt on a mold surface generated in a forming step of a curable resin. The resin composition for mold cleaning is characterized in that: The base resin is a specific unvulcanized rubber. [Prior Art] When a molded article such as an integrated circuit is molded by a thermosetting resin such as an epoxy resin, the following is often the case: if the molding is continued for a long time, the inner surface of the mold may be contaminated. When the molding is continued in this state, the surface of the sealed molded article may be contaminated, or the sealed molded article may adhere to the mold, and the forming operation may not proceed. Therefore, it is necessary to perform regular cleaning of the mold, and a method of forming a mold for cleaning the resin for a mold cleaning process by a number of times to form a mold for a mold cleaning is proposed. For example, in Japanese Patent Special Publication No. JP-A-52-788 discloses a method of cleaning a mold by molding a resin composition for mold cleaning comprising an amine-based resin, an organic substrate, and/or an inorganic matrix #10. On the other hand, the following method is proposed: when using a cleaning component

When a Kb rubber material or a compound is used in place of the above-mentioned thermosetting melamine resin molding material to be vulcanized and vulcanized in a mold, the oxidative degradation layer such as a release agent existing on the surface of the mold is decomposed by a cleaning component and vulcanized rubber. Integration, and then the vulcanized rubber is removed from the mold to clean the surface of the mold. Further, as an unvulcanized rubber, 135644.doc 200930757, it is also proposed that a rubber component having a butadiene rubber/ethylene-propylene content of 90/10 to 50/50 parts by weight is set to open. 03_227308, n $ & This patent special report). "Japan's special (four) Kaiping Xian and No. gong as a cleaning material for molds, can be roughly divided into types, transfer type of medium detection Λ main /, contraction type 2 - melamine resin molding material, used in compression type The melamine-based resin is made into a material and a rubber-based cleaning material.

❹

(4) _f road, etc. (abbreviation 4IC, thinning, surface-encapsulated servants; ^ ° ° continuous advancement, therefore, the shape and structure of ❹ are diversified, although the industry seeks high fluidity of semiconductor sealing materials and Therefore, the highly fluidized epoxy sealing material tends to cause clogging of the vent hole portion, and if the right clogging occurs, the venting property is poor, and the resin does not flow, so it is due to the cavity portion. It is unfilled and becomes poor, which makes continuous forming difficult. Therefore, it is necessary to perform cleaning in order to avoid such conditions. However, when the U material is transferred, the resin cannot flow normally due to the above reasons, so it is difficult to remove the vent hole. In order to eliminate the clogging of the vent hole as described above, a compression type cleaning material is used, and when the melamine resin molding material is used right, the clogging of the vent hole is eliminated, but the resin is discharged near the outer periphery of the mold. However, the pressure cannot be sufficiently applied, so that the peripheral portion of the molded article tends to become brittle, and the work of removing the hardened molded article from the mold is troublesome. In the case where a rubber-based cleaning material is used in this case, the cleaning material is hardened as a whole to form a sheet-like formed product' which can be released from the mold t, so workability is improved. 135644.doc 200930757 However, in the flow In terms of properties, rubber-based cleaning materials are inferior to melamine-based resin molding materials, so there is a problem that the filling property in the cavity is poor, and the dirt such as cavity angles cannot be removed. Also, such as the Plastic Dual Inline Package In-line package, the following is a brief description of PDIP) or Small 〇mIine Integrated Circuit (small outline integrated circuit, hereinafter referred to as s〇IC), such as a mold cavity for small package manufacturing, or a small package with a small number of pins. In the case where a rubber-based cleaning material is used in a small package manufacturing mold, the number of packages is increased, so that the molded product after curing tends to adhere to the mold. When it is removed, the sheet-like formed product is broken. , the problem of debris remaining in the cavity of the rubber knee cleaning material. If debris is generated in the mold, since the number of cavities is large, the debris is removed. A large amount of time is required for the molded article. In order to solve the above problem, an workability (release property) and moldability are obtained, and an unfilled portion is not generated in the cavity corner portion or due to delay

A rubber knee-cleaning material that stretches in strength without causing debris or the like when the mold is released. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Provided is a rubber-based cleaning material which is excellent in workability (release property) as described above, but which eliminates the disadvantage of a rubber-based cleaning material which generates voids or chips without generating voids or debris. 135644.doc 200930757 The conventional cavity of 'the work' or the like is particularly small, and the object of the present invention is to provide a good cleaning property (release property) of the rubber (four) cleaning material, but not only eliminate voids or breakage It is a defect that does not cause voids, but the workability (release property) is poor, and the rubber-based cleaning material is generated, and the number of pins is small in a small package manufacturing mold such as PDIp*s〇ic or ice. There are also no voids or debris in the mold for manufacturing the package. The present invention solves the above problems by providing the rubber-based composition for mold cleaning of the following (1), (7) and (3). ❹

(1) A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber and diced The blending ratio of the olefin rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 8 〇 to 8 〇〇%, and the tensile strength is 3 to 10 MPa. The rubber hardness (hardness hardness) is a range of values of 50 to 100 seconds at a mold temperature of A6 〇 95 and 175 C at a mold temperature of 90% vulcanization time (appropriate cure point) tc (9 〇). (hereinafter referred to as "the rubber composition for the first mold cleaning") (2) A rubber-based composition for cleaning a mold for removing dirt on the surface of the mold generated in the step of forming the curable resin, The method is characterized in that: the base resin is an unvulcanized rubber set to a ratio of 90/10 to 50/50 parts by weight, and the vulcanized hardened extension of the unvulcanized rubber is used. The ratio was 80 to 800%, the tensile strength was 3 to 10 MPa, and the rubber hardness (hardness hardness) was A60 to 95, 175. (: 90% vulcanization time at the mold temperature (appropriate vulcanization point) tc (9 〇) is a range of values of 135644.doc 9-200930757 200 to 400 seconds. (hereinafter, referred to as a second rubber mold for mold cleaning) (3) A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber The blending ratio with the butadiene rubber is set to 90/10-50/50 parts by weight of the unvulcanized rubber, and the elongation ratio of the unvulcanized rubber after vulcanization hardening is in the range of 8 〇 to 8 〇〇%, and the tensile strength A range of values of 200 to 400 seconds for a mold hardness of 3 to 10 MPa and a rubber hardness (hardness hardness) of A60 to 95 and a mold temperature of 1 75 ° C at a mold temperature of 90% (suitable vulcanization point) tc (9 〇) In addition, the rubber composition for mold cleaning contains at least one type of release agent. (hereinafter, referred to as a third rubber composition for cleaning a mold) The first, second, and third mold cleaning rubbers of the present invention The composition is excellent not only in workability (release property) but also in formability and The rubber composition of the first, second, and third mold cleanings of the present invention is a rubber-based composition: an unvulcanized rubber which is used as a base resin, and is vulcanized and hardened. The subsequent elongation is in the range of 80 to 800%, the tensile strength is 3 to 1 〇Mpa, the rubber hardness (hardness hardness) is A6 〇 95, 175, and 90% of the vulcanization time at the mold temperature (appropriate curing point) When tc (9 〇) is in the range of 5 〇 to 1 〇〇 second or 2 〇〇 to 4 〇〇 seconds, the vent hole portion is easily cleaned, and the rubber-based cleaning material is characterized by workability ( The peeling property is maintained, and the moldability and the strength are also excellent. The third rubber composition for mold cleaning of the present invention is suitable for use as long as it contains at least one release agent of 135644.doc •10-200930757. A mold-like mold for manufacturing a cavity cavity type such as PDIP4S〇IC, or a rubber-based composition for cleaning a package for manufacturing a package having a small number of pins in a small package. [Embodiment] Hereinafter, the first aspect of the present invention will be described. Mould cleaning rubber system The composition is described in detail. The unvulcanized rubber used in the present invention is a mixture of an ethylene-propylene rubber and a butadiene rubber. The ethylene-propylene rubber (hereinafter sometimes abbreviated as EPM) includes a usual ethylene-propylene. The meaning of both rubber (EPM) and ethylene-propylene-diene rubber (hereinafter sometimes abbreviated as EPDM). As the above EPM, it is preferred that the copolymerization ratio of ethylene to olefin (especially propylene) is in the molar ratio. The ratio is ethylene/α_olefin = 55/45 to 83/17, and the Mona viscosity ML1+4 (100C) is 5 to 300. Particularly preferably, the above copolymerization ratio is ethylene/α in terms of molar ratio. _ olefin = 55/45~61/39, and the Manner viscosity ML1+4 (l 〇〇 ° C) is 36~44. Further, the EPDM is a terpolymer formed of ethylene, an α-dilute hydrocarbon, and a cyclic or acyclic substance having a non-covalent double bond. More specifically, it is a terpolymer formed of ethylene, an α-olefin (especially propylene), and a polyolefin monomer. Examples of the above polyene precursors include dicyclopentadiene; 5-cyclooctadiene, 1,7-cyclododecadiene; 1,5,9-cyclododecanetriene; and i. Cycloheptadiene; 1,4-cyclohexadiene; norbornadiene; methylene norbornene; 2-methylpentadiene-1,4,1,5-hexadiene; 1,6- Heptadiene; mercapto tetrahydroanthracene; 1 > 4 • 135644.doc -11 - 200930757 - alkene and the like. The copolymerization ratio of each monomer in the above terpolymer is preferably from 30 to 8 Gmol% of the binder, 2 mol% of the polyorganism, and the remainder is (tetra) hydrocarbon. More preferably, the ethylene is 3 〇 ~ (10) ear %. Further, as the above-mentioned terpolymer, that is, EPDM, a good county #Λ平和野疋 uses Mengna viscosity ^^丨+4(1〇〇t;) as 2 0~7 0. Further, as the butadiene rubber (hereinafter abbreviated as BR), a high cis structure having a content of a trans-ruthenium bond of 9 〇 by weight or more is preferably used, and the internal viscosity ML1+4 (10 (TC) is 20 to 60, especially 3 to 45. Further, the ratio of the above ethylene-propylene rubber to butadiene rubber is 90/10 to 50/50 parts by weight, preferably 8〇/2 by weight. 〇~6〇/4〇 parts by weight. If the ethylene-propylene rubber is blended to more than 9 parts by weight, the mold release property is deteriorated, and the cleaning operation time becomes long, which is not preferable. If the butadiene rubber is blended as When the amount is more than 50 parts by weight, the mold release property is improved, but the molded product after vulcanization becomes hard and brittle, so that chipping is liable to occur, which is unsatisfactory. The elongation of the unvulcanized rubber after vulcanization and hardening is 8 〇 to 8 〇. 〇%, preferably 100 to 300 ° /. If the elongation is 8 % or less, the moldability is deteriorated, which is not preferable. The tensile strength of the unvulcanized rubber after vulcanization and hardening is 3 to 1 Torr. MPa, preferably 5 to 8 MPa. If the tensile strength is less than 3 MPa, it is prone to chipping, which is not preferable. The rubber hardness (hardness tester hardness) after vulcanization and hardening of the rubber is A60 to 95, preferably A70 to 90. If the rubber hardness is out of this range, it is liable to generate chips or voids, which is not preferable. 135644.doc • 12- 200930757 The 9未% vulcanization time (appropriate vulcanization point) tc(90) at the mold temperature of 175t of the above unvulcanized rubber is 50~100 seconds, preferably 7〇~1〇〇 seconds. The value of the range is such that the vulcanization rate is not too fast, and the resin can be filled to the corner of the cavity, and the cleaning can be performed without causing adhesion or the like. Further, compared with the conventional rubber-based cleaning material, it can be cleaned in an efficient hardening time, thereby reducing the cleaning time. The rubber-based composition of the present invention contains, in addition to the above-mentioned unvulcanized rubber,

It may contain a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization accelerating aid, and the like. Examples of the filler (reinforcing agent) include: cerium oxide, oxidized iron, carbon hydride, and titanium oxide. The amount of the filler to be used is preferably 1 G to 7 parts by weight, more preferably 30 to 60 parts by weight, per 1 part 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; ethanol monoterpene ether, ethylene glycol dimethyl ether, Glycol ethers such as triethylene glycol dioxime are used in the class of rice glycols. The amount of the above-mentioned cleaning agent used is relatively heavy, and is preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, relative to the unvulcanized rubber. In addition to this, a cleaning aid such as a surfactant can be used. Examples of the vulcanizing agent include, for example, di-tert-butyl peroxide, di-second-yl-based peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-diyl peroxidation. )-dipropyl propyl peroxide organic peroxide such as hexane; for example, bis(t-butylperoxy) 33,5 trimethylcyclohexane, 'i bis (second butyl peroxy) ring Benzene, 2,2-bis(t-butylperoxy) 135644.doc •13- 200930757 octyl, 4,4-bis(t-butylperoxy) n-butyl valerate, 2,2_double Peroxy ketal organic peroxides such as (t-butyl peroxy) butane. In general, 5, compared with monoallyl peroxides, the peroxidation shrinkage class j has a longer half-life, which can be used alone depending on the design of the composition, and can also have a longer half-life and a shorter one. And used to adjust the vulcanization rate. The amount of the vulcanizing agent to be used is preferably from 丨 6 parts by weight, more preferably from 2 to 4 parts by weight, per 100 parts by weight of the unvulcanized rubber. In addition to this, a vulcanization aid such as an acrylic monomer or sulfur can be used. Examples of the vulcanization accelerator include an anthracene system such as diphenylguanidine or triphenylsulfonium, and an aldehyde-amine system or an aldehyde-ammonia system such as a formaldehyde-p-toluidine condensate or an acetaldehyde-thromamine reactant; for example, 2- A sulfazole-promoting aid such as magnesium oxide, lead oxide or lime can be used as a thiazole system such as mercaptobenzothiazole or dibenzothiazole disulfide. In addition to the formulations, the rubber-based composition of the present invention may be used in combination with, for example, red dan, iron blue, iron black, ultramarine blue, carbon black, zinc bismuth titanium yellow H (tetra) yellow, 丫 定 _ red, etc. Organic pigments; for example, metal soaps such as zinc stearate, zinc mash, stearic acid, stearic acid, etc.; for example, butyl sulphate, butyl laurate, stearic acid The fatty acid is intended to be a lubricant; for example, a guanamine-based lubricant such as ethylene bis-lipidamine, melamine amide, stearylamine or behenamide, etc. Next, the second mold of the present invention The rubber composition for cleaning is described in the second rubber mold composition for cleaning of the mold of the present month, except for the vulcanization time of the unvulcanized rubber system 175 c used as the substrate t 135644.doc 14 200930757 (suitable The vulcanization point tc (9 〇) is the same as the rubber-based composition for the second mold cleaning of the present invention, except that the unvulcanized rubber is preferably 200 to 4 sec., preferably 25 〇 to 35 sec. The value of the adjustment can be based on the type or amount of the diene, the type or amount of the peroxide, The type or amount of the accelerator, the type or amount of the co-crosslinking agent, etc. are appropriately adjusted. If the value of the unvulcanized rubber tc (9 〇) is in the range of 2 〇〇 to 4 〇〇 seconds, the vulcanization rate is not It will be too fast, and the rubber-based composition will slowly follow the shape of the mold when clamping, so that the resin can be filled into the corner of the cavity without voids. Moreover, adhesion due to unfilled or voids may not occur. In the third step, the rubber composition for mold cleaning according to the present invention is the second rubber mold composition for cleaning the mold of the present invention. The release agent is formed by at least one type of release agent. Examples of the release agent include a metal soap release agent, a fatty acid ester release agent, a synthetic wax, a fatty acid amide amine release agent, and the like. Examples of the soap-based release agent include, for example, calcium stearate, stearic acid, zinc myristate, etc. Examples of the fatty acid ester-based release agent, synthetic soil, and fatty acid amide-based release agent are as follows: Lic〇wax OP (Clariant JaPan Co., Ltd. manufactures 'sulphuric acid partially saponified ester), L〇xiol G_78 (manufactured by Cognis japan Co., Ltd., polymer compound vinegar), Licolub H-4 (manufactured by Clariant Japan Co., Ltd., modified hydrocarbon), 135644 .doc -15- 200930757

Loxiol VPN881 (Mineral Oil Synthetic Wax manufactured by Cognis Japan Co., Ltd.), Fatty Amide S (manufactured by Kao Co., Ltd., fatty acid decylamine), Kao Wax EB-P (manufactured by Kao Co., Ltd., fatty acid guanamine), Alflow HT-50 (manufactured by Nippon Oil & Fat Co., Ltd., fatty acid guanamine). The release agent is preferably formulated in an amount of from 3 to 15 parts by weight, preferably from 5 to 1 part by weight, based on 100 parts by weight of the unvulcanized rubber. If the amount of the release agent is insufficient, it is deep in the cavity like PDip or SOIC.

In a small-sized package, in a mold for manufacturing a package having a small number of pins, the number of cavities disposed on the mold is increased, so that the mold release property is relatively lowered. If the amount of the releasing agent is too large, the mold release property is good, but the cleanability is deteriorated, which is not preferable. The method for producing the rubber composition of the second and second mold cleanings of the present invention is not particularly limited, and a known method can be employed. For example, in a pressurized kneading machine with a jacket, the raw materials are put into time and mixed, and the temperature of the suitable raw materials is observed. The surface is continuously kneaded until the mixed raw materials of Cong and BR become a cake. Further, when the temperature of the mixed raw material reaches 70 to 100 C, white carbon, an amino alcohol-based compound, a cyclic amide-containing hydrazine, a processing oil, a nonionic surfactant, stearic acid, or the like is added, and kneading is performed. The number is a clock. Then, the right-hand machine is added with an organic peroxide, sulfur, and the like. After dispersing, a suitable rubber-like composition for mold cleaning of the present invention is prepared by taking out an appropriate shape such as a sheet or the like. In the third mold cleaning method of the present invention, the preparation of the wm gel composition is, for example, the above-mentioned second mold clearing of the present invention, and the preparation method of the rubber-based composition 135644.doc 200930757 The release agent may be added together with other additives in the raw materials of the mixture of ^1 and 811. As the kneading means, in addition to the above-mentioned pressurizing type kneader, for example, a Banbury mixer, a roll mill, or the like can be mentioned.

The form of the rubber composition for cleaning the first, second, and third molds of the present invention is not particularly limited. If the resin composition that has been kneaded is not rapidly cooled, the vulcanization is promoted by the preheating during kneading. In the form of the rubber composition for mold cleaning of the present invention, it is preferably in the form of a sheet which can be easily cooled in a short period of time. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and the like, and the present invention is not limited by the examples and the like. Test method The test methods for various physical property evaluations described in the examples and the comparative examples are as follows. _ [Elongation and tensile strength] Measured according to the measurement method of tensile strength and elongation at break in JIS K6251. <Production conditions of test piece> Using a 37T automatic press, the mold temperature and molding pressure were (7) An unvulcanized sample was formed under the conditions of MPa (measured pressure) and a mixture of materials for 5 minutes. The formed test piece had a sheet size of 8 〇χ 16 〇χ 2 mm, and was punched with a No. 3 dumbbell to prepare a test piece for measurement. [Rubber hardness] 135644.doc •17· 200930757 The measurement was carried out by the method according to JIS K6253 “Test method for hardness of vulcanized rubber and thermoplastic rubber”. Three sheets of 6 〇 x 2 mm test pieces were obtained by the above test piece production conditions. The hardness of the durometer was measured using a durometer of a rubber hardness type. [Vulcanization rate] Using a method according to JIS K63 00-2 "Method for determining the vulcanization characteristics of a vibration type vulcanization tester", the 9 〇 0 / 〇 vulcanization time (appropriate vulcanization point) is measured at a mold temperature of 175 ° C. Tc (9〇). [Cleaning test] A commercially available biphenyl-based epoxy resin molding material (manufactured by Sumitomo Bakelite Co., Ltd., EME-735 1T) was used in a mold of PDIP-14L (8-can-48 cavity) by 500. The formation of the second is to achieve contamination of the mold. The mold for cleaning the mold was subjected to repeated use until the surface of the mold was cleaned by using the contaminated mold. In Examples 9 to 12, evaluation was carried out using a mold of PDIP-8L (8 cans - 96 cavity). Example 1 (The ninth mold cleaning rubber composition of the present invention) In a 3000 ml jacketed press type kneader, 1 〇 5 〇 之 卩〇 ^ ^ ^ ^ 孟 孟 孟 孟 孟 孟 孟 孟^1^+4(1〇〇.(:) is 23], and 45()§ 811 raw material [Menna viscosity ML1+4(l〇〇°c) is 42 and 1,4 cis bond contains The rate is 95% by weight], and the mixture is pressurized and kneaded for about 3 minutes while cooling, and then the mixture of 〇 与 and BR becomes a cake, and the temperature reaches about 8 〇. Then, 150 g is added (relative to 1 〇). 〇 parts by weight of the mixed raw materials of ePDM and BR are 1 part by weight of monoethanolamine, 75 g (relative to 1 part by weight) of £1> £)1^ and 311 135644.doc 18 200930757 5 parts by weight of the polyalkylene oxide oxime ether surfactant, 1, 5 g (relative to (10) parts by weight of the mixed raw material of EpD_(10), stearic acid, 750 g (relative to 100) 50 parts by weight of white carbon, 75 g (5 parts by weight relative to 丨 (8) parts by weight of a mixed raw material of EPDM and BR) of calcium carbonate '75 § (relative to parts by weight) Mix of EPDM and BR Material and 5 parts by weight) of titanium oxide and 75 g (1〇〇 parts by weight with respect to the d 1)] ^ zinc oxide mixed feed of BR and 5 parts by weight), the kneaded for about 3 minutes. Finally, 48 g (32 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) of l'l-bis(t-butylperoxy)cyclohexane was added, and the mixture was kneaded for about several minutes. The temperature of the kneaded material during this period is adjusted to not more than 1 〇 (rc. The obtained kneaded material is quickly passed through a pressure roller, processed into a sheet shape, and cooled to 25 t > c, thereby obtaining a sheet having a thickness of ό mm. The rubber-based composition a for cleaning the mold was shown in Table 1. The characteristic values of the rubber-based composition A for cleaning the sheet-like mold and the cleaning test results are shown in Table 1. According to the test results, it was found that the sheet mold was cleaned. The rubber composition A showed good cleanability. Example 2 (The rubber composition for mold cleaning of the present invention) In the first embodiment, the amount of the base resin was changed to 900 g of the EPDM raw material. Mengna viscosity ML1+4 (l〇〇°C) is 23] and 600 g of BR material [Menna viscosity ML1+4 (l〇(TC) is 42 and 1,4 cis bond content is 95 weight In the same manner, the rubber-based composition B for sheet mold cleaning having a thickness of 6 mm was obtained in the same manner. The characteristic value and cleanability of the rubber-based composition B for cleaning the sheet-like mold obtained were obtained. The test results are not determined according to the test results in Table 1, D, 135644.doc •19· 20093075 The rubber composition B for the 7-mold mold cleaning showed good cleanability. Example 3 (The first rubber composition for mold cleaning of the present invention) In Example 1, 450 g (relative to 100 parts by weight) was used. A mixture of EpDM and BR is 3 parts by weight of (±) 丨 胺 胺 胺 _2 _ _ _ , 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 相对 相对 相对 相对 相对 相对 丨 丨 丨 丨 丨 丨 丨In the same manner, a rubber composition C for sheet mold cleaning having a thickness of 6 mm was obtained in the same manner as in the case of the monoethanolamine in the same manner. The characteristic value of the obtained rubber-based composition C for sheet mold cleaning and The results of the cleaning test are shown in Table 1. According to the test results, the rubber composition C for sheet mold cleaning showed good cleanability. Example 4 (The rubber composition for cleaning the third mold of the present invention) In Example 1, 'the base resin was changed to 825 g< EPDM raw material [Menner viscosity ML+4 (100X:) was 23] and 675 g of BR raw material [Menner viscosity ML1+4 (i〇〇°) c) is 35 and the 1,4 cis bond content is 95% by weight. In addition, the white carbon is adjusted by 750 g ( 50 parts by weight based on 1 part by weight of the mixture of EPDM and 8 feet of the raw material is changed to 450 g (30 parts by weight based on 1 part by weight of the mixed raw material of EPDM and BR). The sheet-like mold cleaning rubber composition D having a thickness of 6 mm was obtained in the same manner. The characteristic values and the cleaning test results of the obtained rubber-based composition D for sheet mold cleaning are shown in Table 1. According to the test results, it was found that the rubber composition D for sheet mold cleaning showed good cleanability. Comparative Example 1 In Example 1, the amount of the base resin was changed to 6 〇〇g of 135644.doc • 20-200930757 EPDM raw material [Menner viscosity MLi+4 (100 ° C) was 23] and 900 g<BR raw material [Monner viscosity ML1+4 (100 ° C) is 42 and 1,4 cis bond content is 95% by weight], except that a sheet having a thickness of 6 mm is obtained in the same manner. Rubber-based composition E for mold cleaning. The characteristic values of the obtained rubber-based composition E for sheet mold cleaning were shown in Table 1 and the results of the cleaning test. According to the test results, it is necessary to have a large amount of cleaning work time, such as unfilled or cut to the mold in the cavity portion. Moreover, the cleanliness is also poor, and there must be more than 100 times of forming before cleaning. [Table 1] Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Composition A Composition B Composition C Composition D Composition E EPDM ratio 70 60 70 55 30 BR ratio 30 40 30 45 70 Extension Rate (°/〇) 270 150 253 98 59 Tensile strength (MPa) 5.2 4.1 4.9 4.3 4.1 Rubber hardness 90 91 90 91 92 tc(90) (seconds) 60 56 67 54 58 Formability 〇〇〇〇Δ Mold off Moulding 〇〇〇〇X Cleaning times 4 4 4 4 8 Evaluation of formability 1 1 〇: The rate of unfilling is less than 3% △: The rate of unfilling is 3% or more and less than 1〇% X : The unfilled production rate is 10% or more. The evaluation criteria of the mold release property 〇: the generation rate of the chips is less than 3% △: The generation rate of the chips is 3% or more and less than ι〇〇/0 X : JL of the chips The growth rate is 10% or more. Example 5 (the second rubber composition for mold cleaning of the present invention)

In Example 1, 48 g (3.2 parts by weight of a mixed raw material of 100 parts by weight of EPDM and BR 135644.doc -21 - 200930757) of dicumyl peroxide was used instead of 48 g (relative to 48 g). 1 part by weight of the mixed raw material of EPDM and BR is 32 parts by weight of 1'!-bis(t-butylperoxy)cyclohexane, and the temperature of the kneaded material is adjusted to not exceed 11 (rc ' In the same manner, the rubber-based composition for sheet-like mold cleaning having a thickness of 6 mm was obtained in the same manner, and the characteristic values of the rubber-based composition F for sheet-like mold cleaning obtained were shown in the table. 2. According to the test results, it was found that the sheet & mold cleaning gel composition F exhibited good formability and cleansing property. Example 6 (The second mold cleaning rubber composition of the present invention) In Example 5, the amount of the base resin was changed to a layer of EPDM raw material [Menner viscosity ML丨wore) of 23] and _ § when the raw material [Menner viscosity MLl+4 (100〇c) was 42 And the 14 cis bond content rate is 95% by weight]' In addition, a film having a thickness of 6 claws is obtained in the same manner. The mold cleaning rubber composition G. The characteristic values of the rubber composition G for sheet mold cleaning obtained and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the rubber composition G for sheet mold cleaning exhibited good formability and cleanability. Example 7 (Second mold cleaning rubber composition of the present invention) In Example 5, 300 g (2 parts by weight based on 100 parts by weight of the mixed material of the sand and the BR) was used. (±) 1-amino-2-propanol instead of 150 g (w weight damage relative to 100 parts by weight of iEpDM and 811 mixed material), and 28 g (relative to 1 〇〇 weight) 135644.doc •22· 200930757 The mixed raw material of EPDM and BR is i 9 parts by weight of diiso-biphenyl peroxide and 2 gg (relative to the mixture of EpDM and the weight of the material) 1.3 parts by weight of 4,4·bis(t-butylperoxy)-n-butyl valerate instead of 48 g (32 parts by weight relative to 00 parts by weight of the mixed raw material) In the same manner as above, a sheet-like mold cleaning rubber composition H having a thickness of 6 mm was obtained in the same manner. The characteristic values of the obtained gel-form composition for cleaning the sheet-like mold H and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the rubber-based composition H for sheet mold cleaning exhibited good formability and cleanability. Example 8 (Second mold cleaning rubber composition of the present invention) In Example 5, 450 g of BR raw material [Menna viscosity MLi + 4 (1〇〇t) was 42 and 1,4 cis The bond content is 95% by weight] changed to 45 〇 之 8 & raw material [Menner viscosity ML1+4 (l〇〇°c) is 35 and 1,4 cis bond content is % by weight], Further, 48 g (3.2 parts by weight based on 100 parts by weight of the mixed raw material of EpDM and BR) of dicumyl peroxide was changed to 13 g (relative to 1 part by weight of the mixed raw material of EPDM and BR) And 9 parts by weight of U-bis(t-butylperoxy)cyclohexane and 35 g (2.3 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) A sheet-like mold cleaning rubber composition I having a thickness of 6 mm was obtained in the same manner except for cumene. The characteristic values of the obtained rubber-based composition I for sheet mold cleaning and the results of the cleaning test are shown in Table 2. According to the test results, it was found that the sheet-like mold/green rubber composition I exhibited good formability and cleanness of 135644.doc -23-200930757. Comparative Example 2 In Example 5, the amount of the base resin was changed to 600 g of EPDM raw material [Menner viscosity MLi+4 (100 ° C) was 23] and 900 g of BR raw material [Menner viscosity ML1 A rubber mold composition for sheet mold cleaning J having a thickness of 6 mm was obtained in the same manner, except that the ratio of +4 (100 ° C ) was 42 and the 1,4- cis bond content was 95% by weight. . The characteristic values of the obtained rubber-based composition J for sheet mold cleaning were shown in Table 2 as a result of © and the cleaning test results. According to the test results, it is found that there is a large amount of cleaning work time in the cavity portion which is not filled or cut into the mold. Moreover, the cleanliness is also poor, and there must be more forming times before cleaning. [Table 2] Item Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Composition F Composition G Composition Η Composition I Composition J epdm ratio 70 60 70 70 40 BR ratio 30 40 30 30 60 4 Extensibility (%) 150 120 184 188 54 Tensile strength (MPa) 5.8 5.2 4.3 4.1 4.4 Rubber hardness 83 87 75 80 92 tc (90) (seconds) 329 297 278 267 58 Formability 〇〇〇〇 Δ Mold release Sex r 〇〇〇〇X Void 〇〇〇〇X Number of cleanings completed Γ 4 4 4 4 8 〇: The generation rate of voids is less than 3% △: The generation rate of voids is 3% or more and less than ι〇〇/0 X : The void generation rate was 10% or more. Example 9 (the third mold cleaning rubber composition of the present invention) was added to a 3000 ml jacketed press type kneader to add 1050 g of 135644.doc •24· 200930757 EPDM raw material [Menner viscosity ML1+4(i〇〇°c) is 23], and 45〇g of BR raw material [Menner viscosity ML1+4 (100 °C) is 42 and 1,4 cis bond When the content is 95% by weight, the mixture is pressurized and kneaded for about 3 minutes while cooling, and the mixed raw material of EPDM and BR becomes a cake-like shape and the temperature thereof reaches about 8 Torr. Hey. Then, 150 g (10 parts by weight relative to 1 part by weight of the mixed raw material of EPDM and BR) of monoethanolamine, 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) is added. Polyalkylene oxide oxime ether interface activity

And 15 g (1 part by weight relative to 100 parts by weight of the mixed raw material of EPdm and BR) of stearic acid, 650 g (43 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) White carbon, 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR), about 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) Titanium oxide, 75 g (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR), 75 g (5 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) Lixiol G-78 (polymer complex ester manufactured by Cognis Japan Co., Ltd.) and 75 g (5 parts by weight relative to 100 parts by weight of a mixed raw material of EPDM and BR) Licolub H-4 (Clariant Japan) The modified hydrocarbon produced by the company, mixed for about 3 minutes. Finally, 48 g (3.2 parts by weight based on 100 parts by weight of the mixed raw material of EPDM and BR) of dicumyl peroxide was added, and kneading was continued for about 1 minute. The temperature of the kneaded material during this period was adjusted to not exceed 110 °C. The kneaded material obtained was quickly passed through a pressure roll, processed into a sheet shape, and cooled to 25 ° C or lower, whereby a rubber composition K for sheet-like mold cleaning having a thickness of 6 mm was obtained. 135644.doc • 25-200930757 The characteristic values of the obtained rubber-based composition for sheet mold cleaning κ and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the rubber composition κ for cleaning a sheet mold exhibited good formability and cleanability. Example 10 (The third rubber mold composition for mold cleaning of the present invention) In Example 9, 900 g of EPDM raw material [Monner viscosity ML1+4 (100 °C) was used as a substitute for EPDM raw material) [Menner viscosity ML1+4 (100 °C) is 23], and the BR material [Menna viscosity MLi+4 (1〇〇Ο)

C) is 42 and the cis bond content is 95% by weight. The amount of the formulation is changed to 600 g, and the amount of the Loxiol G-78 is changed to 30 g (relative to 1 part by weight of EPDM and 2 parts by weight of the mixed raw material of BR, and the amount of Lie〇lub H-4 is changed to 丨5 g (1 part by weight relative to the mixed raw material of EpDM and br), new Adding 5 g of zinc stearate (parts by weight of the mixed raw material of EPDM and BR to the weight of the niobium), in addition to the same way, a 6 mm thick sheet-shaped mold cleaning rubber is obtained in the same manner. Composition L. The characteristic values of the rubber composition L for sheet mold cleaning obtained and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the sheet = cleansing rubber (IV) composition L exhibited good formability and clearing Example 11 in Example 9 'mixing the amount of white carbon to the weight of the coffee_BR mixture g ( Change the ratio to 100 (4) to 45... to 7 parts by weight" Change "1" to 45 g (3 parts by weight compared to the mixed raw material of 5.7644.doc • 26 - 200930757) Instead of using 75 S (with respect to 100 parts by weight of EPDM), g (2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of Fatty Amide S (manufactured by Kao Co., Ltd.) 5 parts by weight of the mixed raw material of BR, Licolub H-4, and then 75 g (5 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM 'and BR) of zinc stearate, and 48 is used. g (3.2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, instead of 48 〇g ( 3.2 parts by weight of dicumyl peroxide relative to 100 parts by weight of the mixed raw material of EPDM and BR, except In the manner of obtaining a rubber composition for cleaning a sheet-like mold having a thickness of 6 mm, the characteristic values of the obtained rubber-based composition for cleaning a sheet-like mold and the results of the cleaning test are shown in Table 3. It was found that the rubber composition for sheet mold cleaning showed good formability and cleanability. Example 12 In Example 10, 600 g of BR material [Menner viscosity ML1+4 (100 ° C) was 42 and 1,4 cis bond content is 95% by weight] changed to 600 g. BR material [Menner viscosity ML1+4 (100 ° C) is 35 and 1,4 cis bond content rate is 95 weight %), in addition, changing the white carbon of 65 0 g (43 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) to 700 g (compared to 1 part by weight of the mixture of EPDM and BR) 7 parts by weight of white carbon of the raw material, 30 g (2 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of zinc stearate was changed to 5 g (relative to 100 parts by weight of EPDM) And 5 parts by weight of zinc silicate's mixed with 135644.doc -27· 200930757 BR, 30 g (relative to 100 parts by weight of EPDM and BR) 2 parts by weight of the mixed raw material of Loxiol G-78 was changed to 60 g (4 parts by weight relative to 100 parts by weight of the mixed raw material of EPDM and BR) of Loxiol G-78, and 48 g (relative to 100) was used. In parts by weight of the mixed raw material of EPDM and BR, 3.2 parts by weight of the second (third • butyl peroxy)-m-isopropylbenzene, instead of 48 g (relative to 1 part by weight, EPDM and BR) A sheet-like mold 清洁 cleaning rubber-based composition N having a thickness of 6 mm was obtained in the same manner except that the raw material was mixed with 3.2 parts by weight of dicumyl peroxide. The characteristic values of the rubber composition N for sheet mold cleaning and the results of the cleaning test are shown in Table 3. According to the test results, it was found that the rubber composition N for sheet mold cleaning exhibited good formability and cleanability. [Table 3] Item Example 9 Example 10 Example 11 Example 12 Composition K Composition L Composition Μ Composition Ν EPDM ratio 70 60 70 60 BR ratio 30 40 30 90 Elongation (%) 138 128 157 140 Tensile strength (MPa) 7.0 6.2 8,3 7.2 Rubber hardness 87 84 80 84 tc(90) (seconds) 306 328 319 328 Formability 〇 - ~〇~ 〇〇 mold release 〇〇〇〇 cleaning completion 4 4 4 4 The above-mentioned usability industry utilizes a rubber-based composition for mold cleaning using an unvulcanized rubber, which is 135644.doc •28· 200930757 of an unvulcanized rubber-based ethylene-propylene rubber and butadiene rubber. The ratio is set to 90/10~50/50 to re-introduction. A. Injury, and the elongation after vulcanization and hardening is shown as 80~8〇〇%' tensile strength is shown as 3~i〇Mpa , rubber hardness (hardness tester hardness) is shown as A6 〇 ~ 95, 175 〇 c at the mold temperature 90% vulcanization time (appropriate cure point) tc (9 〇) is displayed as 5 〇 ~ 1 〇〇 seconds or = 200 ~ 400 seconds; this workability (peelability) is good, and no debris or voids are generated, not only Easy to remove the mold cavity or runner, gates of dirt 'and can be easily removed dirt vent or partition of the mold. In the rubber-based composition for cleaning a mold of the present invention, the third rubber composition for cleaning a mold of the present invention is preferably used for a mold for manufacturing a small-sized package such as PDIP or SOIC. Or the cleaning of a particularly small package manufacturing mold with a small number of pins in a small package. 135644.doc 29-

Claims (1)

200930757 X. Patent Application Range: 1. A rubber-based composition for mold cleaning, which is used for removing dirt on a surface of a mold generated in a forming step of a curable resin, characterized in that a substrate resin is used. The blending ratio of the dilute-propylene-baked rubber to the butyl rubber is set to 90/H) to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 8〇~8〇〇. %, tensile strength is 3~10 MPa, rubber hardness (hardness hardness) is A6〇~ and 90% vulcanization time at the mold temperature of 175 C (suitable vulcanization point) tc(90) is 50~1〇 The range of values for leap seconds. 2. A rubber-based composition for cleaning a mold, which is used for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, wherein the base resin is made of ethylene-propylene rubber and butadiene. The ratio of the rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the elongation of the unvulcanized rubber after vulcanization and hardening is 80 to 800%, and the tensile strength is 3 to 10 MPa. The rubber hardness (hardness hardness) is A60 to 95, and the 90% vulcanization time (suitable for vulcanization point) tc (90) at a mold temperature of 1751 is in the range of 200 to 400 seconds. 3. A rubber-based composition for cleaning a mold for removing dirt on a surface of a mold which is formed in a step of forming a curable resin, characterized in that the base resin is made of ethylene-propylene rubber and diced The blending ratio of the olefin rubber is set to 90/10 to 50/50 parts by weight of the unvulcanized rubber, and the unvulcanized rubber has an elongation after vulcanization and hardening of 8 〇 to 800%, a tensile strength of 3 to 10 MPa, and rubber. Hardness (hardness hardness) is A60 to 95, and 90% vulcanization time at a mold temperature of 175 ° C (appropriate cure point) tc (90) 135644.doc 200930757 · is a range of values of 200 to 400 seconds, and The rubber composition for mold cleaning contains at least one release agent. 4. The rubber-based composition for mold cleaning according to claim 3, wherein the ratio of the base resin to the release agent is from 3 to 15 parts by weight based on 1 part by weight of the base resin. . The rubber-based composition for mold cleaning according to any one of claims 1 to 4, wherein the ratio of the ethylene-propylene rubber to the butadiene rubber is set to 80/20 to 60/40 by weight. Share. The rubber-based composition for mold cleaning according to any one of Items 1 to 4, which is a compression type. The rubber-based composition for mold cleaning according to any one of the items 1 to 4, further comprising a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, and a vulcanization accelerator At least one species. A mold cleaning method using the rubber-based composition for mold cleaning according to any one of claims 1 to 4. 135 135644.doc 200930757 VII. Designated representative 囷: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: VIII. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (none) 135644.doc