KR20100085025A

KR20100085025A - Mold cleaning rubber compositon

Info

Publication number: KR20100085025A
Application number: KR1020107007524A
Authority: KR
Inventors: 히로아키 노무라; 키요히토 히로미츠; 오사무 스나고
Original assignee: 닛뽕 카바이도 고교 가부시키가이샤
Priority date: 2007-10-29
Filing date: 2008-10-21
Publication date: 2010-07-28
Also published as: HK1143565A1; KR101491757B1; CN101821075A; JPWO2009057479A1; TW200930757A; MY155143A; JP5391072B2; TWI428384B; CN101821075B; WO2009057479A1

Abstract

In the rubber composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of curable resin, As a base resin, the compounding ratio of ethylene propylene rubber and butadiene rubber is set to 90/10-50/50 weight part, As unvulcanized rubber, elongation rate after vulcanization of the above unvulcanized rubber is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) is A 60 to 95, 90% at mold temperature of 175 ° C. Vulcanization Time (Proper Vulcanization Point) An unvulcanized rubber having a range of 50 to 100 seconds or 200 to 400 seconds is used. Among small package manufacturing molds and small packages having deep cavities such as PDIP and SOIC, etc., when used for cleaning a small number of pins, especially a small package manufacturing mold, tc (90) is in the range of 200 to 400 seconds. It is preferable to contain a mold release agent together with the said unvulcanized rubber.

Description

Rubber-based composition for mold cleaning {MOLD CLEANING RUBBER COMPOSITON}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-based composition for mold cleaning, and in detail, in a resin composition for mold cleaning for removing dirt on the surface of a mold generated in the molding step of the curable resin, as a base resin, specific unvulcanized. It relates to a rubber-based composition for mold cleaning, characterized in that rubber is used.

Conventionally, during molding of an encapsulated product such as an integrated circuit made of a thermosetting resin such as an epoxy resin, if the molding is continued for a long time, the surface of the mold becomes dirty, and if the mold continues continuously, the surface of the encapsulated product becomes dirty. In many cases, the molding operation could not be continued, such as an encapsulated molding adhered to the mold. For this reason, it is necessary to clean the mold regularly, and a method of forming the mold cleaning resin by molding the resin for cleaning the mold at the ratio of several shots every several hundred shot moldings of the molding material has been proposed. No. 52-788 discloses a method for cleaning a mold by molding a resin composition for mold cleaning comprising an amino resin, an organic substrate and / or an inorganic substrate, and a mold release agent.

On the other hand, instead of the thermosetting melamine resin molding material, an oxidized deterioration layer such as a release agent present on the surface of the mold is decomposed by the cleaning component when vulcanized and vulcanized in a mold using an unvulcanized rubber compound containing a cleaning component. At the same time, a method of cleaning the mold surface by integrating with the vulcanized rubber and then removing the vulcanized rubber from the mold has been proposed. Moreover, the rubber type composition which set the butadiene rubber / ethylene-propylene rubber component as 90/10-50/50 weight part as unvulcanized rubber component is also proposed (for example, Unexamined-Japanese-Patent No. 63-227308, Unexamined-Japanese-Patent). See Patent Publication No. Hei 4-357007).

As a cleaning material of a metal mold | die, it can be largely divided into two types, a transfer type and a compression type, melamine type resin molding material is used for a transfer type, and melamine type resin molding material and rubber type cleaning material are used for a compression type.

In recent years, along with high integration, thinning, and surface mounting of integrated circuits (abbreviated as IC and LSI), diversification of the shape and structure of molded products has been progressed, and therefore, high fluidization and environmental compatibility of semiconductor encapsulation materials are achieved. It is becoming.

For this reason, in the epoxy resin material of the high fluidization type, resin clogging in the air vent portion is likely to occur, and when this clogging occurs, the air is not released and resin does not flow. Since unfilling occurs and becomes defective, continuous molding becomes difficult. Therefore, in order to avoid this situation, it is necessary to perform cleaning. In the transfer type cleaning material, it is difficult to remove the resin blocked by the air vent because the resin does not flow normally for the above-mentioned reasons.

Compression-type cleaning materials are used to eliminate the clogging of air vents. When melamine-based resin molding materials are used, the clogging of the air vents is eliminated, but the pressure around the mold is not sufficiently applied by the outflow of the resin. The outer periphery of the molded article tends to recede, and the work of removing the molded article after curing from the mold is complicated. On the other hand, when a rubber cleaning material is used, since the whole cleaning material hardens similarly and can be mold-released from a metal mold | die as a sheet-like molded object, workability improves. However, in terms of fluidity, the rubber-based cleaning material is not as good as the melamine-based resin molding material, so that the filling property into the cavity is poor and there is a problem that dirt such as cavity corners cannot be removed.

Also, for small package manufacturing molds with a deep cavity or small packages such as Plastic Dual Inline Package (hereinafter referred to as PDIP) or Small Outline Integrated Circuit (hereinafter referred to as SOIC), the number of pins, especially for small package manufacturing dies In the case where the rubber-based cleaning material is used, the phenomenon that the molded product after the curing sticks to the mold tends to occur because the number of cavities per mold of the package increases. When this was removed, there was a problem that the sheet-like molded product broke and chipping in which the rubber-based cleaning material remained in the cavity occurred. If chipping occurs in these molds, the number of cavities requires a great deal of time to remove the molding of the chipping portion.

In order to solve the above problems, the rubber system is excellent in workability (releasability) and formability and does not cause unfilling in the cavity corner portion, or because it has extensibility and high strength, so that no phenomenon such as chipping occurs during mold release. Cleaning materials are desired.

Japanese Patent Publication No. 52-788 Japanese Patent Laid-Open No. 63-227308 Japanese Patent Application Laid-Open No. 04-357007

The present invention provides a rubber-based cleaning material that has good workability (release property) as described above, but eliminates defects in conventional rubber-based cleaning materials that cause void formation or chipping, and does not cause voids or chipping. Let's make it a task.

In addition, the present invention solves the defects in the conventional rubber-based cleaning material, which has good workability (releasability) but voids or chipping, or no voids but poor workability (releasability), resulting in chipping. An object of the present invention is to provide a rubber-based cleaning material which does not cause voids or chipping even in a small package manufacturing die or a small package having a deep cavity such as an SOIC or a small package, especially in a small package manufacturing die.

This invention solves the said subject by providing the rubber type composition for metal mold | die cleaning of following (1), (2) and (3).

(1) The resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the molding process of curable resin WHEREIN: The compounding ratio of ethylene-propylene rubber and butadiene rubber as a base resin is 90/10-50/50 weight part. While using the unvulcanized rubber set, the elongation rate after the vulcanized rubber is cured and cured is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) is A 60 to 95, mold 90% vulcanization time (suitable vulcanization point) tc (90) at the temperature of 175 degreeC exists in the range of the value of 50-100 seconds (The following is called rubber composition for metal mold | die cleaning for a 1st metal mold | die cleaning hereafter.).

(2) The resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of curable resin WHEREIN: The compounding ratio of ethylene propylene rubber and butadiene rubber as a base resin is 90/10-50/50 weight part. While using the unvulcanized rubber set, the elongation rate after the vulcanized rubber is cured and cured is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) is A 60 to 95, and mold temperature is 175 ° C. 90% vulcanization time (suitable vulcanization point) tc (90) in the range of the value of 200 ~ 400 seconds rubber composition for cleaning the mold (hereinafter referred to as the rubber composition for the second mold cleaning).

(3) The resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of a curable resin WHEREIN: The compounding ratio of ethylene-propylene rubber and butadiene rubber as a base resin is 90/10-50/50 weight part. While using the unvulcanized rubber set, the elongation rate after the vulcanized rubber is cured and cured is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) is A 60 to 95, and mold temperature is 175 ° C. 90% vulcanization time (suitable vulcanization point) in tc (90) is an unvulcanized rubber in the range of 200 to 400 seconds, and at least one mold release rubber-based composition for cleaning the mold, characterized in that 3 is referred to as rubber-based composition for mold cleaning.

The rubber composition for cleaning the first, second and third molds of the present invention is excellent in formability and strength as well as workability (releasability), and furthermore, no void or chipping occurs.

The rubber composition for metal mold | die cleaning of the 1st, 2nd and 3rd of this invention is the unvulcanized rubber used as base resin, 80-800% of elongation after vulcanization hardening, 3-10 MPa of tensile strength, rubber hardness (durometer) Strength) is A 60-95, 90% vulcanization time (appropriate vulcanization point) in mold temperature 175 degreeC tc (90) becomes a range of the value of 50-100 second or 200-400 second, As a result, cleaning of the air vent part It is a rubber-based composition which can be easily carried out and is also excellent in moldability and strength while maintaining workability (peelability), which is a characteristic of the rubber-based cleaning material.

Moreover, the 3rd mold cleaning rubber composition of this invention contains at least 1 sort (s) of mold release agent, and is the metal mold | die for small package manufacture, especially small package manufacture with a small number of pins among small-capacity package and a small package with a deep cavity like PDIP, SOIC, etc. Rubber-based composition suitable for cleaning.

Below. First, the rubber-based composition for cleaning the first mold 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.

Ethylene propylene rubber (hereinafter sometimes abbreviated as EPM) is intended to include both normal ethylene propylene rubber (EPM) and ethylene-propylene-diene rubber (hereinafter sometimes referred to as EPDM). to be.

As the EPM, and the copolymerization ratio is the molar ratio of ethylene / α- olefin = 55 / 45-83 / 17 as of ethylene and α- olefin (especially propylene), a Mooney viscosity _{(Mooney viscosity) ML 1 +4 (} 100 ℃) 5 to a ~ 300 is preferred, especially preferably the copolymer ratio of the ethylene / α- olefin = 55/45 ~ 61/39 by molar ratio, a 36-44 Mooney viscosity ML ₁ ₊₄ (100 ℃).

The EPDM is a terpolymer composed of ethylene, α-olefin, and a cyclic or acyclic compound having a non-conjugated double bond. In detail, it is a terpolymer which consists of ethylene, (alpha) -olefin (especially propylene), and a polyene monomer.

Examples of the polyene monomers include dicyclopentadiene, 5-cyclooctadiene, 1,7-cyclododecadiene, 1,5,9-cyclododecatene, 1,4-cycloheptadiene and 1,4-cyclo Hexadiene, norbornadiene, methylenenorbornene, 2-methylpentadiene-1,4,1,5-hexadiene, 1,6-heptadiene, methyl-tetrahydroindene, 1,4-hexadiene Etc. can be mentioned. The copolymerization ratio of each monomer in such a terpolymer becomes like this. Preferably it is 30-80 mol% of ethylene, 0.1-2 mol% of a polyene monomer, and the remainder is an alpha olefin. More preferably, it is 30-60 mol% of ethylene. In addition, the emitter as a polymer of EPDM, it is preferable to use the Mooney viscosity ML ₁ ₊₄ of (100 ℃) is 20 to 70.

The butadiene rubber (hereinafter sometimes abbreviated as BR) has a high sheath structure with a content of cis 1,4 bond of 90% by weight or more, and a Mooney viscosity ML _{1 + 4} (100 ° C.) is 20 to 60 Especially, 30-45 is used suitably.

The blending ratio of the ethylene-propylene rubber and butadiene rubber is 90/10 to 50/50 parts by weight, preferably 80/20 to 60/40 parts by weight.

If the ethylene-propylene rubber is blended in an amount of more than 90 parts by weight, mold releasability worsens and the cleaning operation time becomes long, which is not preferable. Although mold release property improves when a butadiene rubber is mix | blended more than 50 weight part, it is unpreferable since the molding after vulcanization hardens and falls off, and chipping becomes easy to generate | occur | produce.

The unvulcanized rubber has an elongation after vulcanization of 80 to 800%, preferably 100 to 300%. If the elongation rate is 80% or less, the moldability is deteriorated, which is not preferable.

The unvulcanized rubber has a tensile strength of 3 to 10 MPa, preferably 5 to 8 MPa after vulcanization and curing. If the tensile strength is 3 MPa or less, chipping occurs, which is not preferable.

The said unvulcanized rubber is a rubber hardness (durometer hardness) after vulcanization hardening A 60-95, Preferably it is A 70-90. If the rubber hardness is out of this range, chipping or voiding is not preferable.

The unvulcanized rubber has a 90% vulcanization time (suitable vulcanization point) tc (90) at a mold temperature of 175 ° C of 50 to 100 seconds, preferably 70 to 100 seconds. If the value of tc (90) is within the above range, the vulcanization rate is not too fast and resin can be filled to every corner of the cavity, so that cleaning can be performed without problems such as sticking. . Moreover, since cleaning can be performed with an efficient hardening time compared with the conventional rubber type cleaning material, it becomes possible to reduce a total cleaning time.

The rubber composition of the present invention may contain a filler, a cleaning agent, a cleaning aid, a vulcanizing agent, a vulcanizing aid, a vulcanization accelerator, a vulcanization accelerator, and the like in addition to the unvulcanized rubber.

Examples of the filler (reinforcing agent) include silica, alumina, calcium carbonate, aluminum hydroxide, titanium oxide, and the like. The amount of the filler used is preferably 10 to 70 parts by weight, more preferably 30 to 60 parts by weight based on 100 parts by weight of the unvulcanized rubber.

As the cleaning agent, for example, amines such as monoethanolamine, diethanolamine, triethanolamine, N-methyl diethanolamine, N, N-di-n-butylethanolamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol ethers, such as triethylene glycol dimethyl ether, imidazole, and imidazoline are mentioned. The usage-amount of the said washing | cleaning agent becomes like this. Preferably it is 5-50 weight part, More preferably, it is 5-30 weight part with respect to 100 weight part of unvulcanized rubber. In addition, cleaning aids, such as 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, and the like. Diallyl peroxide organic peroxides such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, Peroxy such as 2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane And ketal organic peroxides. Generally, peroxy ketals have a long half-life compared with diallyl peroxides, and these may be used independently with the design of a composition, and they may adjust a vulcanization rate by using a long half and a short one together. The amount of the vulcanizing agent used is preferably 1 to 6 parts by weight, more preferably 2 to 4 parts by weight based on 100 parts by weight of the unvulcanized rubber. In addition, vulcanization aids, such as an acrylic acid monomer and sulfur, can be used.

As a vulcanizing accelerator, for example, guanidine-based compounds such as diphenylguanidine and triphenylguanidine, for example, aldehyde-amine or aldehyde-ammonia-based compounds such as formaldehyde-paratoluidine condensate and acetoaldehyde-aniline reactant, for example 2 And thiazoles such as mercaptobenzothiazole and dibenzothiazyl disulfide; and the like, and vulcanization accelerators such as magnesia, litharge, and lime can be used.

The rubber-based composition of the present invention can be used in addition to these formulations, for example, as necessary, for example, red oxide, sensitized, iron black, ultramarine blue, carbon black, lithopone, titanium yellow, cobalt blue, Inorganic or organic pigments such as Hanza yellow and quinacridone red; For example, metal soap type lubricants, such as zinc stearate, zinc myristic acid, aluminum stearate, and calcium stearate, for example, fatty acid ester type lubricants, such as butyl stearate, butyl laurate, and stearyl stearate, for example, ethylenebis Amide type lubricants such as ethylenebisstearamide, erucamide, oleic acid amide, stearic acid amide, and behenic acid amide can be used in combination.

Next, the rubber-based composition for cleaning the second mold of the present invention will be described.

In the second rubber composition for metal mold cleaning of the present invention, the unvulcanized rubber used as the base resin has a 90% vulcanization time (suitable vulcanization point) tc (90) at a mold temperature of 175 ° C, preferably 200 to 400 seconds. It is the same as the rubber-based composition for cleaning the first mold of the present invention except that it is an unvulcanized rubber of 250 to 350 seconds.

The adjustment of the value of tc (90) can be appropriately adjusted by the kind and amount of diene, the kind and amount of peroxide, the kind and amount of vulcanization accelerator, the kind 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 rate is not too fast, and the rubber composition gradually follows the mold shape when the mold is clamped, thereby voiding every corner of the cavity. The resin can be filled without the occurrence of. In addition, cleaning can be performed without causing problems such as sticking resulting from unfilled or voiding.

Next, the rubber composition for 3rd metal mold | die cleaning of this invention is demonstrated.

The rubber composition for 3rd metal mold | die cleaning of this invention contains the rubber composition for 2nd metal mold | die cleaning of this invention at least 1 type of mold release agent.

Examples of the mold release agent include metal soap-based mold release agents, fatty acid ester mold release agents, synthetic waxes, and fatty acid amide mold release agents.

As an example of a metal soap type mold release agent, calcium stearate, zinc stearate, zinc myristic acid, etc. can be illustrated, for example. Examples of fatty acid ester-based mold release agents, synthetic waxes, and fatty acid amide-based mold release agents include Licowax OP (Clariant Japan Co., Ltd., Montan acid partially saponified ester), and oxyol G-78 (Cognis ) Japan Co., Ltd., polymer composite ester), Recolub H-4 (Client Japan Co., Ltd., denatured hydrocarbon), Loxyol VPN881 (Cognis Japan Co., Ltd., mineral oil synthetic wax) ), Fatty acid amide S (Kao Kawasaki Co., Ltd., fatty acid amide), Kao wax EB-P (Kao Kawasaki Co., Ltd., fatty acid amide), Alflow HT-50 (NOF Co., fatty acid amide) It can be illustrated.

These mold release agents are 3-15 weight part with respect to 100 weight part of unvulcanized rubber, Preferably 5-10 weight part is mix | blended.

When the amount of the release agent is insufficient, even in a small package having a deep cavity such as PDIP or SOIC, in a mold for manufacturing a small package, especially a small package, the mold release property is relatively low because the number of cavities placed on the mold increases. . If the amount of the release agent is too large, mold release property is good, but the cleaning property is deteriorated, which is not preferable.

The preparation method of the rubber composition for the 1st and 2nd metal mold cleaning of this invention is not specifically limited, A well-known method can be employ | adopted. For example, EPM and BR dough are introduced into a pressurized kneader with a jacket to start mixing kneading, and mixing mixing is continued while observing the temperature of the dough properly until the mixing kneading of EPM and BR becomes a rice cake shape. . And when the temperature of the said mixture dough became 70-100 degreeC, it mixed for several minutes, adding white carbon, an amino alcohol type compound, a cyclic amide compound, a process oil, a nonionic surfactant, stearic acid, etc. Knead. Subsequently, organic peroxide, sulfur, etc. are added, it disperse | distributes quickly, and it takes out, and if needed, it shape | molds to a suitable shape, such as a sheet form, and is made into the rubber type composition for metal mold | die cleaning of this invention.

In the preparation method of the rubber-based composition for cleaning the third mold of the present invention, for example, in the method for preparing the rubber-based composition for cleaning the second mold of the present invention, the release agent is added to the mixture dough of EPM and BR together with other additives. You may add it.

As the kneading means, in addition to the pressurized kneader, for example, a Banbury mixer, a roll mixer, and the like can be given.

Although the form of the rubber composition for the 1st, 2nd, and 3rd metal mold | die cleaning of this invention is not specifically limited, If the mixed resin composition does not cool quickly, vulcanization is accelerated by preheating at the time of mixing kneading, and stable performance is improved. Since it is not obtained, it is preferable that it is a sheet form which can be easily cooled in a short time as a form of the rubber type composition for metal mold | die cleaning of this invention.

Although an Example etc. are given to the following and this invention is demonstrated in more detail, this invention is not limited at all by these Examples.

(Test Methods)

The test method of evaluation of the various physical properties described in the Example and the comparative example is as follows.

Elongation and Tensile Strength

It measures based on the tensile strength in JISK6251 and the measuring method of elongation at the time of cutting.

Unvulcanized samples are molded at a mold temperature of 175 ° C, molding pressure of 10 MPa (gauge pressure), and molding time of 5 minutes using a 37T automatic press. The molded test piece size was 80 x 160 x 2 mm in the form of a sheet, punched with a No. 3 dumbbell to make a test piece for measurement.

[Rubber hardness]

It measures by the method based on JISK6253 "The hardness test method of a vulcanized rubber and a thermoplastic rubber."

Three 80 x 160 x 2 mm test pieces obtained under the above test piece preparation conditions were stacked, and the durometer hardness was measured using a durometer of the type according to rubber hardness.

[Vulcanization rate]

90% vulcanization time (suitable vulcanization point) tc (90) was measured at the mold temperature of 175 degreeC using the method based on JISK6300-2 "The method of obtaining the vulcanization characteristic by a vibration type vulcanization tester."

[Cleaning test]

Molding dirt is realized by 500 shot molding using PDIP-14L (8 port-48 cavity) using commercially available biphenyl epoxy resin molding material (Sumitomo Bakelite Co., Ltd., EME-7351T). It was. Using this soiled mold, evaluation was performed by repeatedly molding the resin composition for mold cleaning until the mold surface was cleanly cleaned. In Examples 9-12, it evaluated by the metal mold | die of PDIP-8L (8 port-96 cavity).

(Example 1) (1st rubber composition for metal mold | die cleaning of this invention)

1050 g of EPDM dough [Money viscosity ML ₁ ₊₄ (100 ° C.) 23] and BR dough [Money viscosity ML ₁ ₊₄ (100 ° C.) 42, 1,4 sheath bond content in 3000 ml of jacketed pressurized kneader 95% by weight] After adding 450 g of the mixture and pressing and kneading for about 3 minutes while cooling, the mixture dough of EPDM and BR became a rice cake, and the temperature became about 80 ° C. Subsequently, 150 g of monoethanolamine (10 parts by weight based on 100 parts by weight of a mixture of EPDM and BR), 75 g of polyoxyalkylenedecyl ether-based surfactant (5 parts by weight of copper), 15 g of stearic acid (1 part by weight) , 750 g of white carbon (50 parts by weight), 75 g of calcium carbonate (5 parts by weight), 75 g of titanium oxide (5 parts by weight) and 75 g of zinc oxide (5 parts by weight) were added and mixed for about 3 minutes. Finally, 48 g of 1,1-bis (t-butylperoxy) cyclohexane (3 parts by weight of copper) was added, followed by mixing for about 1 minute. The mixing dough temperature between them was adjusted not to exceed 100 ℃. The rubber mixture composition A for sheet-like metal mold | die cleaning of thickness 6mm was obtained by passing the obtained mixture dough quickly through a press roll, processing it into a sheet form, and cooling to 25 degrees C or less.

Table 1 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition A. As can be seen from the test results, the rubber composition A for cleaning a sheet-like mold showed good cleaning properties.

(Example 2) (the first rubber composition for cleaning the mold of the present invention)

900 g and BR dough [Money viscosity ML ₁ ₊₄ (100 ° C.) 42, 1,4 sheath bond in the compounding quantity of base resin as EPDM dough [Money viscosity ML ₁ ₊₄ (100 degreeC) 23] Content of 95% by weight] A rubber-based composition B for cleaning a sheet-like mold having a thickness of 6 mm was obtained in the same manner except for changing to 600 g.

Table 1 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition B. As can be seen from the test results, the rubber composition B for cleaning the sheet-shaped mold showed good cleaning properties.

Example 3 (1st rubber composition for metal mold | die cleaning of this invention)

In Example 1, instead of 150 g of monoethanolamine (10 parts by weight based on 100 parts by weight of the mixture of EPDM and BR), 450 g of (±) -1-amino-2-propanol (100 parts by weight of the mixture of EPDM and BR Except having used 30 weight part with respect to parts, the rubber composition C for sheet-like metal mold | die cleaning of thickness 6mm was similarly obtained.

Table 1 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition C. As can be seen from the test results, the rubber composition C for sheet-like mold cleaning showed good cleaning property.

(Example 4) (the first rubber composition for cleaning the mold of the present invention)

In the first embodiment, the base resin EPDM dough [Mooney viscosity ML ₁ ₊₄ (100 ℃) 23 would] 825g dough and BR [Mooney viscosity _{ML 1 +4 (100 ℃) 35} , 1,4 cis bond content of 95 Weight percent] to 675 g, and the amount of the white carbon to 750 g (50 parts by weight based on 100 parts by weight of the mixture of EPDM and BR) to 450 g (30 parts by weight based on 100 parts by weight of the mixture of EPDM and BR A rubber composition D for cleaning a sheet-like mold having a thickness of 6 mm was obtained in the same manner except for changing to).

Table 1 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition D. As can be seen from the test results, the rubber composition D for cleaning the sheet-shaped mold showed good cleaning properties.

(Comparative Example 1)

For Example 1, the amount of the base resin EPDM dough [Mooney viscosity ML ₁ ₊₄ to the (100 ℃) 23] 600g dough and BR [Mooney viscosity _{ML 1 +4 (100 ℃) 42} , 1,4 cis-bond Content of 95% by weight] A rubber-based composition E for cleaning a sheet-like mold having a thickness of 6 mm was obtained in the same manner except for changing to 900 g.

Table 1 shows the characteristic values and the cleaning test results of the obtained sheet-like mold-based rubber composition E for cleaning. As can be seen from the test results, unfilling in the cavity part, chipping into a mold, and the like occurred, which required a lot of cleaning work time. In addition, the cleaning performance was also poor, requiring a large number of shots to complete the cleaning.

Evaluation criteria of formability

○: The incidence of uncharged is less than 3%

(Triangle | delta): The incidence of uncharged is more than 3% and less than 10%

X: The incidence of uncharged is 10% or more

Evaluation Criteria of Mold Release

○: less than 3% incidence of chipping

(Triangle | delta): The incidence of chipping is 3% or more and less than 10%.

X: The incidence of chipping is 10% or more

(Example 5) (2nd rubber composition for metal mold | die cleaning of this invention)

In Example 1, instead of 48 g of 1,1-bis (t-butylperoxy) cyclohexane (3.2 parts by weight based on 100 parts by weight of a mixture of EPDM and BR), 48 g of dicumyl peroxide (mixing of EPDM and BR) 3.2 weight part with respect to 100 weight part of dough, The rubber composition F for sheet-like metal mold | die cleaning of thickness 6mm was similarly obtained except having adjusted so that the mixture dough temperature may not exceed 110 degreeC.

Table 2 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition F. As can be seen from the test results, the rubber composition F for sheet-like mold cleaning showed good moldability and cleaning property.

(Example 6) (2nd rubber composition for metal mold | die cleaning of this invention)

In Example 5, the amount of the base resin EPDM dough [Mooney viscosity ML ₁ ₊₄ to the (100 ℃) 23] 900g dough and BR [Mooney viscosity _{ML 1 +4 (100 ℃) 42} , 1,4 cis-bond Content of 95% by weight] A rubber-based composition G for sheet-like mold cleaning having a thickness of 6 mm was obtained in the same manner except for changing to 600 g.

Table 2 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition G. As can be seen from the test results, the rubber composition G for sheet-like mold cleaning showed good moldability and cleaning property.

(Example 7) (2nd rubber composition for metal mold | die cleaning of this invention)

In Example 5, instead of 150 g of monoethanolamine (10 parts by weight based on 100 parts by weight of the mixture of EPDM and BR), 300 g of (±) -1-amino-2-propanol (100 parts by weight of the mixture of EPDM and BR 20 parts by weight), instead of 48 g of dicumyl peroxide (3 parts by weight of copper), 28 g of dicumyl peroxide (1.9 parts of copper) and n-butyl 4,4-bis (t-butylperoxy) valerate Except having used 20g (copper 1.3 weight part), the rubber composition H for sheet-like metal mold | die cleaning of thickness 6mm was similarly obtained.

Table 2 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition H. As can be seen from the test results, the rubber-based composition H for cleaning the sheet-shaped mold showed good moldability and cleaning property.

Example 8 (2nd rubber composition for metal mold | die cleaning of this invention)

In Example 5, BR dough [Mooney viscosity _{ML 1 +4 (100 ℃) 42} , to the cis-1,4 bond content of 95% by weight] BR dough instead of 450g [Mooney viscosity ML ₁ ₊₄ (100 ℃) 35 , 1,4 cis bond content of 95% by weight] 1,1-bis (t-butyl) instead of 48g of dicumyl peroxide (3 parts by weight based on 100 parts by weight of a mixture of EPDM and BR) A rubber-based composition I for cleaning sheet-like molds having a thickness of 6 mm was obtained in the same manner except for changing to 13 g of peroxy) cyclohexane (0.9 parts by weight) and 35 g of dicumyl peroxide (2.3 parts by weight).

Table 2 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition I. As can be seen from the test results, the rubber composition I for cleaning sheet-like molds showed good moldability and cleaning properties.

(Comparative Example 2)

In Example 5, the amount of the base resin EPDM dough [Mooney viscosity ML ₁ ₊₄ to the (100 ℃) 23] 600g dough and BR [Mooney viscosity _{ML 1 +4 (100 ℃) 42} , 1,4 cis-bond Content of 95% by weight] A rubber-based composition J for sheet-like mold cleaning having a thickness of 6 mm was obtained in the same manner except for changing to 900 g.

Table 2 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition J. As can be seen from the test results, unfilling in the cavity part, chipping to the mold, and the like occurred, which required a lot of cleaning work time. In addition, the cleaning property was also poor, requiring a large number of shots to complete the cleaning.

Void Evaluation Criteria

○: the incidence of voids is less than 3%

(Triangle | delta): The incidence rate of a void is more than 3% and less than 10%

X: The incidence of voids is 10% or more

(Example 9) (third mold cleaning rubber composition of the present invention)

1050 g of EPDM dough [Money viscosity ML ₁ ₊₄ (100 ° C.) 23] and BR dough [Money viscosity ML ₁ ₊₄ (100 ° C.) 42, 1,4 sheath bond content in 3000 ml of jacketed pressurized kneader 95% by weight] After adding 450 g of the mixture and pressing and kneading for about 3 minutes while cooling, the mixture dough of EPDM and BR became a rice cake, and the temperature became about 80 ° C. Subsequently, 150 g of monoethanolamine (10 parts by weight based on 100 parts by weight of a mixture of EPDM and BR), 75 g of polyoxyalkylenedecyl ether-based surfactant (5 parts by weight of copper), 15 g of stearic acid (1 part by weight of copper), and white carbon 650 g (43 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), oxyol G-78 (Cognis Japan Co., Ltd.) 75 g (5 parts by weight) of a product, a polymer composite ester) and 75 g (5 parts by weight of copper) of Recolup H-4 (manufactured by Clarity Japan Co., Ltd., modified hydrocarbon) were added and mixed for about 3 minutes. Finally, 48 g of dicumyl peroxide (3 parts by weight of copper) were added, followed by mixing for about 1 minute. The mixing dough temperature therebetween was adjusted not to exceed 110 ° C. The rubber mixture composition K for sheet-like metal mold | die cleaning of thickness 6mm was obtained by passing the obtained mixture dough quickly through a press roll, processing into a sheet form, and cooling to 25 degrees C or less.

Table 3 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition K. As can be seen from the test results, the rubber composition K for sheet-like mold cleaning showed good moldability and cleaning property.

(Example 10) (third mold cleaning rubber composition of the present invention)

In Example 9, BR dough [with a Mooney viscosity ML ₁ ₊₄ (100 ° C) 23] instead of EPDM dough [with Mooney viscosity ML ₁ ₊₄ (100 ° C) 8] 900 g, BR dough [ Mooney viscosity ML ₁ ₊₄ (100 ° C) 42, 1,4 cis bond content of 95% by weight] of the compounding amount of 600g, oxyol G-78 compounding amount of 30g (100 parts by weight of mixed dough of EPDM and BR) 2 parts by weight) and the amount of Recolup H-4 is changed to 15 g (1 part by weight), and the same procedure is used for cleaning a sheet-shaped mold having a thickness of 6 mm in the same manner except adding 15 g of zinc stearate (1 part by weight). The rubber composition L was obtained.

Table 3 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition L. As can be seen from the test results, the sheet-like mold cleaning rubber composition L showed good moldability and cleaning property.

(Example 11)

In Example 9, the compounding quantity of white carbon was changed into 700g (47 weight part with respect to 100 weight part of mixture dough of EPDM and BR), and the compounding quantity of oxyol G-78 was changed to 45g (3 weight part of copper), Instead of using 75 g (5 parts by weight) of H-4, 30 g (2 parts by weight) of fatty acid amide S (Kako Kasei Co., Ltd., fatty acid amide) was used, and 75 g (5 parts by weight) of newly added zinc stearate Was added and the thickness was the same except that 48 g of 2,5-dimethyl-2,5-di-t-butylperoxyhexane (3 parts by weight of copper) was used instead of 48 g of dicumyl peroxide (3 parts by weight of copper). The rubber composition M for 6 mm sheet-form metal mold | die cleaning was obtained.

Table 3 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition M. As can be seen from the test results, the sheet-like mold cleaning rubber-based composition M showed good moldability and cleaning properties.

(Example 12)

BR dough [Money viscosity ML ₁ ₊₄ (100 degreeC) 35, Instead of 600 g of BR doughs [Money viscosity ML ₁ ₊₄ (100 degreeC) 42, 1,4 sheath content rate 95weight%] 1,4 cis bond content of 95% by weight] to 600 g, and instead of 650 g of white carbon (43 parts by weight of copper), 700 g of copper (47 parts by weight of copper) and 30 g of zinc stearate (2 parts by weight of copper) Instead of 75 g (5 parts by weight), 30 g (4 parts by weight) of oxyol G-78 (2 parts by weight) instead of 60 g (4 parts by weight) and dicumyl peroxide 48 g (3 parts by weight), di (t-butylperoxy Except having used 48 g of) -m- diisopropyl benzene (3 weight part of copper), it carried out similarly and obtained rubber composition N for sheet-like metal mold | die cleaning of thickness 6mm.

Table 3 shows the characteristic values and the cleaning test results of the obtained sheet-like mold cleaning rubber composition N. As can be seen from the test results, the rubber composition N for sheet-like mold cleaning showed good moldability and cleaning property.

As described above, the unvulcanized rubber in which the blending ratio of ethylene-propylene rubber and butadiene rubber is set at 90/10 to 50/50 parts by weight, the elongation after vulcanization is 80 to 800%, the tensile strength is 3 to 10 MPa, rubber Mold using unvulcanized rubber whose hardness (durometer hardness) is A 60 to 95 and 90% vulcanization time (qualified vulcanization point) at a mold temperature of 175 ° C. Tc (90) shows a value of 50 to 100 seconds or 200 to 400 seconds. By using the cleaning rubber composition, the workability (peelability) is good, and there is no chipping or voids, and the dirt of the air vent or the mold parting area as well as the dirt of the cavity, runners and gates can be easily Could be removed.

Among the rubber-based composition for mold cleaning of the present invention, in particular, the third rubber-based composition for metal mold cleaning of the present invention contains a mold release agent, so that the number of pins is small, particularly in a mold for manufacturing a small package having a deep cavity such as PDIP or SOIC, or a small package. Suitable for cleaning molds for small package manufacturing.

Claims

In the resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of curable resin, As a base resin, the compounding ratio of ethylene propylene rubber and butadiene rubber is set to 90/10-50/50 weight part, While using the unvulcanized rubber having a vulcanized rubber, the elongation rate after the vulcanized rubber is cured and cured is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) is A 60 ~ 95, 90% vulcanization time (suitable vulcanization point) tc (90) at a mold temperature of 175 ° C is in the range of the value of 50 to 100 seconds, rubber-based composition for mold cleaning.

In the resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of curable resin, As a base resin, the compounding ratio of ethylene propylene rubber and butadiene rubber is set to 90/10-50/50 weight part, While using the unvulcanized rubber, the elongation rate after the vulcanized rubber vulcanized is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) A 60 ~ 95, mold temperature at 175 ℃ 90% vulcanization time (suitable vulcanization point) tc (90) is in the range of the value of 200 to 400 seconds rubber-based composition for cleaning the mold.

In the resin composition for metal mold | die cleaning for removing the dirt of the metal mold surface which arises in the shaping | molding process of curable resin, As a base resin, the compounding ratio of ethylene propylene rubber and butadiene rubber is set to 90/10-50/50 weight part, While using the unvulcanized rubber, the elongation rate after the vulcanized rubber vulcanized is 80 to 800%, tensile strength is 3 to 10 MPa, rubber hardness (durometer hardness) A 60 ~ 95, mold temperature at 175 ℃ 90% vulcanization time (suitable vulcanization point) Although the tc (90) is an unvulcanized rubber in the range of a value of 200 to 400 seconds, it contains at least one release agent, characterized in that the rubber-based composition for cleaning the mold.

The method of claim 3,
The mixing | blending ratio of the said base resin and the said mold release agent is 3-15 weight part of mold release agents with respect to 100 weight part of base resins, The rubber-type composition for metal mold | die cleaning characterized by the above-mentioned.

The method according to any one of claims 1 to 4,
The rubber-based composition for mold cleaning, wherein the blending ratio of the ethylene-propylene rubber and the butadiene rubber is set to 80/20 to 60/40 parts by weight.

The method according to any one of claims 1 to 5,
Rubber composition for metal mold | die cleaning characterized by the above-mentioned.

The method according to any one of claims 1 to 6,
The rubber composition for metal mold | die cleaning further containing at least 1 sort (s) of a filler, a washing | cleaning agent, a washing | cleaning adjuvant, a vulcanizing agent, a vulcanizing adjuvant, a vulcanization accelerator, and a vulcanization promoting adjuvant.

A metal mold | die cleaning method using the rubber type composition for metal mold | die cleaning of any one of Claims 1-7.