WO2014042199A1

WO2014042199A1 - Resin composition for mold release recovery and mold release recovery method

Info

Publication number: WO2014042199A1
Application number: PCT/JP2013/074568
Authority: WO
Inventors: 吉村　勝則; 野村　弘明
Original assignee: 日本カーバイド工業株式会社
Priority date: 2012-09-14
Filing date: 2013-09-11
Publication date: 2014-03-20
Also published as: JP6188697B2; JPWO2014042199A1; TW201420303A

Abstract

The present invention provides a resin composition that is for mold release recovery and that contains an ethylene-propylene rubber, a butadiene rubber, a vulcanizing agent, and a monovalent unsaturated fatty acid amide-based mold release agent.

Description

Mold release recovery resin composition and mold release recovery method

The present invention relates to a mold release recovery resin composition and a mold release recovery method.

Sealing molding materials containing a curable resin composition typified by an epoxy resin are widely used in sealing molding operations for integrated circuit elements and the like. However, if this sealing molding material is used for a long time for the sealing molding operation of integrated circuit elements or the like, there is a problem that the inner surface of the molding die is soiled due to the dirt derived from the sealing molding material.
If such dirt is left as it is, dirt adheres to the surface of a sealing molded product such as an integrated circuit element. Therefore, it is necessary to remove dirt on the inner surface of the molding die in the sealing molding process. Specifically, every time hundreds of shots of sealing molding are performed, a molding operation is performed at a rate of several shots using a mold cleaning resin composition instead of a sealing molding material. Dirt adhered to the surface inside the mold is removed.

Furthermore, after removing the dirt on the inner surface of the molding die using the resin composition for mold cleaning, the surface inside the molding die is obtained by performing molding operation using the resin composition for recovering mold release. Gives mold release properties. After the mold releasability is imparted in this manner, several hundred shots of sealing molding are continuously performed.

Such a mold release recovery resin composition has been conventionally proposed. For example, JP 2010-149358 A discloses a mold release sheet containing unvulcanized rubber and a release agent having a dropping point in the range of 120 to 150 ° C. In this mold release sheet, the release agent can be uniformly and easily applied to the mold surface after cleaning. In this mold release recovery resin composition, for example, an amide wax is used as a release agent.

International Publication No. 2009/122955 pamphlet is an unvulcanized rubber having a blending ratio (weight ratio) of ethylene-propylene rubber and butadiene rubber of 90/10 to 50/50. The mold release recovery resin composition in which the elongation, tensile strength, rubber hardness (durometer hardness), and 90% vulcanization time at a mold temperature of 175 ° C. are defined in a specific range. Is disclosed. In this mold release recovery resin composition, it is said that generation of voids and chipping is eliminated while providing mold release properties, and further, mold release properties after mold release recovery can be sustained for a long time. . In the mold release recovery resin composition, for example, fatty acid amide is used as a release agent.
Japanese Unexamined Patent Application Publication No. 2012-201695 discloses a technique using polyethylene oxide as a release agent in an epoxy resin composition for sealing.

However, the conventional mold release recovery resin composition is molded and the mold release recovery resin composition is brittle in the step of imparting mold release properties to the surface inside the mold, so that the mold release after molding There is a problem that the mold release recovery resin composition itself cracks and sticks to the upper and lower surfaces of the molding die. That is, establishment of the technique for improving workability | operativity at the time of removing the mold release recovery resin composition from a shaping | molding die is calculated | required.
In other words, the mold release recovery resin composition used for the mold release treatment as described above needs to stably provide mold release properties to the inner surface of the mold. The mold recovery resin composition itself contains a large amount of a release agent. As a result, the strength of the mold release recovery resin composition itself decreases.

JP 2010-149358 also discloses a mold release recovery resin composition in which a sheet-like substrate is bonded. The mold release recovery resin composition disclosed in Japanese Patent Application Laid-Open No. 2010-149358 is said to have improved workability when it is removed from the mold after recovery from release. However, the resin composition for mold release recovery is separated at the interface between the sheet-like substrate and the mold release recovery resin composition in the step of imparting release properties to the surface inside the mold. Therefore, the workability improvement effect upon removal from the molding die is insufficient.

The present invention has been made in view of the above circumstances. Under such circumstances, the brittleness is improved and the strength is high, and the occurrence of cracking and the occurrence of sticking to the upper and lower surfaces of the molding die when the mold release property is given to the surface inside the molding die. There is a need for a mold release recovery resin composition and a mold release recovery method that are suppressed and have excellent workability when removed from a mold.

The present invention includes the following aspects.
(1) A mold release recovery resin composition comprising ethylene-propylene rubber, butadiene rubber, a vulcanizing agent, and a monounsaturated fatty acid amide release agent.

(2) The mold release recovery resin composition according to (1), wherein the monounsaturated fatty acid amide release agent is erucic acid amide.

(3) The mold release recovery resin composition according to (1) or (2), further comprising a polyethylene wax release agent.

(4) The content ratio (NW: PEW ratio [mass ratio]) of the monounsaturated fatty acid amide release agent (NW) and the polyethylene wax release agent (PEW) is 1:40 to 40: 1. The mold release recovery resin composition according to (3), which is preferably in the range of 1:20 to 20: 1.

(5) The mold release recovery resin composition according to any one of (1) to (4), further including a metal soap type release agent.

(6) The metal soap release agent is zinc laurate, calcium laurate, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc myristate, calcium montanate, zinc montanate, aluminum montanate, The mold release recovery resin composition according to (5), which is at least one metal soap type release agent selected from the group consisting of calcium behenate, magnesium behenate, and zinc behenate.

(7) The mold release recovery resin composition according to (6), wherein the metal soap mold release agent is aluminum stearate.

(8) A step of applying the mold release recovery resin composition according to any one of (1) to (7) to the inner surface of the mold, and the mold release recovery resin composition Is a mold release recovery method that includes a step of heating the mold to which is applied, and a step of taking out the resin composition for recovery of mold release after heating.

According to the present invention, the brittleness is improved and the strength is high, and the occurrence of cracking and sticking to the upper and lower surfaces of the molding die when the mold release property is imparted to the surface inside the molding die is suppressed. There are provided a mold release recovery resin composition and a mold release recovery method that are excellent in workability at the time of removal from a mold.

Hereinafter, the mold release recovery resin composition and mold release recovery method of the present invention will be described in detail.

The mold release recovery resin composition of the present invention is composed of an ethylene-propylene rubber, a butadiene rubber, a vulcanizing agent, and a monounsaturated fatty acid amide release agent. The mold release recovery resin composition of the present invention preferably contains a polyethylene wax release agent or a metal soap release agent, and may be constituted using other components as necessary.

In the mold release recovery resin composition of the present invention, by including a specific release agent, the strength of the mold release recovery resin composition itself is increased, and the mold release on the surface inside the mold. Occurrence of cracks in the process of imparting properties and sticking to the upper and lower surfaces of the molding die are suppressed. Thereby, workability | operativity at the time of removing from a shaping die is improved.

The mold release recovery resin composition of the present invention is, for example, a mold surface generated in a molding step of a curable resin composition selected from the group consisting of epoxy resin, silicone resin, phenol resin, and polyimide resin. After removing the dirt, the mold release recovery resin composition is molded and used as a mold release recovery resin composition for imparting release properties to the inner surface of the mold.

(Ethylene-propylene rubber)
The mold release recovery resin composition of the present invention contains at least one ethylene-propylene rubber. The ethylene-propylene rubber is a synthetic rubber containing at least a structural unit derived from ethylene and a structural unit derived from propylene by copolymerization of at least ethylene and propylene, and ethylene-propylene in which ethylene and propylene are copolymerized. In addition to rubber, ethylene-propylene-diene rubber obtained by copolymerization of ethylene, propylene and diene monomer is included.

The ethylene-propylene rubber contained in the mold release recovery resin composition has a mass ratio of the content of structural units derived from ethylene to the content of structural units derived from propylene (hereinafter simply referred to as “ethylene / propylene ratio”). Is also in the range of 55/45 (1.22) to 60/40 (1.50). When the ethylene / propylene ratio is 55/45 or more, good tensile strength can be obtained after vulcanization. Further, when the ethylene / propylene ratio is 60/40 or less, the temperature dependence of the raw rubber strength is suppressed, and the processability can be kept good.

The ethylene / propylene ratio in the ethylene-propylene rubber was determined by isolating the ethylene-propylene rubber from the resin composition for mold release recovery using HPLC (high performance liquid chromatograph) by a conventional method, and analyzing the ¹ H-NMR. Using (proton nuclear magnetic resonance spectrum), it can be calculated by measuring at a resonance frequency of ¹ H: 500 MHz.

The ethylene-propylene rubber preferably further contains a structural unit derived from a diene component in addition to a structural unit derived from ethylene and a structural unit derived from propylene. Examples of the diene component include ethylidene norbornene (ENB), methylidene norbornene, dicyclopentadiene, vinylidene norbornene, and the like. Among these, the diene component preferably contains at least one selected from the group consisting of ethylidene norbornene and dicyclopentadiene, and more preferably contains ethylidene norbornene, from the viewpoint of imparting releasability to a molding die. preferable.

When the ethylene-propylene rubber further contains a structural unit derived from the diene component, the content of the structural unit derived from the diene component is preferably 6.5% by mass to 9.5% by mass in the total mass. 7.0 mass% to 9.0 mass% is more preferable, and 7.5 mass% to 8.5 mass% is still more preferable.
When the ethylene-propylene rubber further contains a structural unit derived from a diene component, the iodine value of the ethylene-propylene rubber is preferably 12 to 22, and more preferably 14 to 18.

The ethylene-propylene rubber contains 6.5% by mass to 9.5% by mass of a structural unit derived from ethylidene norbornene in addition to a structural unit derived from ethylene and a structural unit derived from propylene. More preferably, the structural unit derived from ethylidene norbornene is contained in an amount of 7.0 to 9.0% by mass in the total mass.

The content of the ethylene-propylene rubber is 10% by mass in the mold release recovery resin composition from the viewpoint of the ability to impart releasability to the inner surface of the mold and the strength of the resin composition. It is preferably ˜80% by mass, more preferably 15% by mass to 30% by mass. The mold release recovery resin composition may contain one kind of ethylene-propylene rubber or a combination of two or more kinds.

As the ethylene-propylene rubber, for example, (product names) EPT4021 and EPT4010M manufactured by Mitsui Chemicals, Inc. (product names) EP35 and EP65 manufactured by JSR Corporation can be used.

(Butadiene rubber)
The mold release recovery resin composition of the present invention contains at least one butadiene rubber.
There is no restriction | limiting in particular in butadiene rubber, It can select suitably from the butadiene rubber used normally. Among these, Mooney has a high cis structure in which the content of cis 1,4 bonds is 90% by mass or more from the viewpoint of the ability to impart releasability to the inner surface of the molding die and the strength of the resin composition. A butadiene rubber having a viscosity ML (1 + 4) of 100 ° C. of 20 to 60 is preferable, and a butadiene rubber having the high cis structure and a Mooney viscosity ML (1 + 4) of 100 ° C. of 30 to 45 is more preferable.
The butadiene rubber may be used alone or in combination of two or more.

As the butadiene rubber, for example, (product names) BRO1 and BR51 manufactured by JSR Corporation, and (product names) UBEPL BR150 and UBEPL BR130B manufactured by Ube Industries, Ltd. can be used.

Since the mold release recovery resin composition of the present invention includes the ethylene-propylene rubber and the butadiene rubber, the mold release recovery can be performed when imparting release properties to the inner surface of the mold. It is possible to keep the strength of the resin composition appropriate. In addition, even if a large amount of the release agent described later is included, the strength of the mold release recovery resin composition can be maintained, the mold release recovery resin composition does not become brittle, cracks and mold on the mold It has excellent characteristics that the occurrence of sticking to the lower surface can be suppressed, and the mold release recovery resin composition can be easily detached from the molding die.

A preferred mass ratio of the ethylene-propylene rubber content to the butadiene rubber content (ethylene-propylene rubber / butadiene rubber ratio) contained in the mold release recovery resin composition is 15/85 to 45 / A range of 55. When the ethylene-propylene rubber / butadiene rubber ratio is 15/85 or more, the mold release recovery resin composition is unlikely to become brittle. Therefore, for example, after the release property imparting operation, in the operation of removing the cured mold release recovery resin composition from the molding die, occurrence of cracks and the like can be further reduced. Further, when the ethylene-propylene rubber / butadiene rubber ratio is 45/55 or less, when imparting releasability to the heated mold, the cured mold release recovery resin composition has a Sticking to the lower surface is further suppressed, and it is effective in reducing the time required for the release work.
Furthermore, when the ethylene-propylene rubber / butadiene rubber ratio is within the above range, the mold release agent described later is appropriately used as the mold release recovery resin composition when producing the mold release recovery resin composition. scatter. Therefore, the mold release agent does not bleed out during storage of the mold release recovery resin composition, and it is possible to suppress a decrease in performance of imparting releasability to the inner surface of the mold or the occurrence of performance variations. it can.

In the mold release recovery resin composition, the mass ratio of the ethylene-propylene rubber content to the butadiene rubber content is ¹ H-NMR (proton nuclear magnetic resonance) of the mold release recovery resin composition. spectra) ^{with, 1} H resonance frequency: it can be calculated by measuring at 500 MHz.

(Vulcanizing agent)
The mold release recovery resin composition of the present invention contains at least one vulcanizing agent.
The vulcanizing agent can be appropriately selected from commonly used vulcanizing agents. Examples of the vulcanizing agent include di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane. Dialkyl peroxides such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2 Organic peroxidation of peroxyketals such as bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane Thing, etc. are mentioned.
Commercially available products may be used as the vulcanizing agent, and examples thereof include (trade name) Perhexa V-40 and Perhexa 25B-40 manufactured by NOF Corporation.
One vulcanizing agent may be used alone, or two or more vulcanizing agents may be used in combination to adjust the vulcanization speed.

The content of the vulcanizing agent in the mold release recovery resin composition can be appropriately selected according to the type of the vulcanizing agent. Among them, the content of the vulcanizing agent is preferably 0.1 to 6 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass in total of the ethylene-propylene rubber and the butadiene rubber. preferable. When the content of the vulcanizing agent is 0.1 parts by mass or more, the ability to impart releasability to the inner surface of the molding die is further improved. Moreover, there exists a tendency which can suppress generation | occurrence | production of an odor more as content of a vulcanizing agent is 6 mass parts or less.

(Monounsaturated Fatty Acid Amide Release Agent)
The mold release recovery resin composition of the present invention contains at least one monounsaturated fatty acid amide release agent (hereinafter also simply referred to as “amide release agent”). By including a specific amide release agent in the mold release recovery resin composition, it is presumed that the mold release recovery resin composition does not become brittle and can maintain high strength. Therefore, when the mold release recovery resin composition is removed from the mold after giving the mold release property to the inner surface of the mold, cracking of the mold release recovery resin composition may occur. Occurrence of the suppressed and cured mold release recovery resin composition on the upper and lower surfaces of the molding die can also be suppressed. Therefore, the workability at the time of providing mold release properties to the inner surface of the molding die is improved.

Amide release agents are also widely used in mold cleaning resin compositions used during mold cleaning. However, the mold release recovery resin composition used after the mold cleaning is compared with the mold cleaning resin composition used at the time of mold cleaning, in order to impart release properties to the inner surface of the mold, It is necessary to include a large amount of release agent. For example, the mold cleaning resin composition usually contains about 5 parts by weight of a release agent with respect to 100 parts by weight of the total amount of unvulcanized rubber such as ethylene-propylene rubber and butadiene rubber. On the other hand, the mold release recovery resin composition contains 20 parts by mass or more of a release agent with respect to 100 parts by mass of the total amount of unvulcanized rubber. If the content of the release agent is less than 20 parts by mass, the release property cannot be sufficiently imparted to the inner surface of the molding die. However, if an excessive mold release agent (for example, 10 parts by mass or more of the mold release agent with respect to 100 parts by mass of the resin composition) is included in the resin composition, there is a problem that the strength of the resin composition itself decreases. . When such a resin composition is thermoformed, it becomes brittle and the workability when removing the resin composition from the molding die after imparting releasability to the inner surface of the molding die is reduced. Therefore, in the mold release recovery resin composition, when the mold release recovery resin composition is removed from the mold after the mold release is given to the inner surface of the mold and the mold release property is given. It was difficult to balance workability.
The mold release recovery resin composition of the present invention provides a release property to the mold mold inner surface by selecting an appropriate mold release agent, and the mold release recovery resin from the mold. It has an excellent feature of satisfying both workability when removing the composition.

Since the monounsaturated fatty acid amide release agent used in the present invention is a monounsaturated fatty acid amide, the melting point is low and the dispersibility in rubber can be kept good. In particular, the monounsaturated fatty acid amide release agent in the present invention has good compatibility with rubber and good dispersion in rubber, so that the monounsaturated acid having 18 to 22 carbon atoms can be used. The amide compound is preferred. Preferred examples of the monounsaturated fatty acid amide release agent include erucic acid amide and oleic acid amide, and erucic acid amide is particularly preferable. For example, erucic acid amide and oleic acid amide, which are amide compounds of monounsaturated acids having 18 to 22 carbon atoms, have a melting point of 70 ° C. to 85 ° C. The monounsaturated fatty acid amide release agent melts well at a temperature in the vicinity of 70 ° C., which is the temperature during kneading of the rubber, and is uniformly kneaded into the rubber. By this, a mold release agent can be favorably disperse | distributed in the resin composition for mold release recovery, Therefore Uniform mold release property can be provided. In contrast, stearic acid amide and behenic acid amide, which are saturated fatty acid amide compounds having 18 to 22 carbon atoms, have a melting point of 100 ° C. to 140 ° C.

Erucamide is preferable in that the strength of the mold release recovery resin composition is improved and the workability at the time of removal from the mold is improved.
For example, a mold release recovery resin composition that does not contain an amide-based mold release agent removes the mold release recovery resin composition from the mold after imparting release properties to the inner surface of the mold. When the both ends of the removed resin composition are held with both hands and bent at 180 degrees, the resin composition is fragile, so that the resin composition is easily cracked.
The present inventor includes a monounsaturated fatty acid amide release agent, particularly erucic acid amide, in the mold release recovery resin composition, and holds the both ends of the resin composition with both hands and bends 180 degrees. Even if it tried, it discovered that high intensity | strength was acquired so that a resin composition might not be cracked. Therefore, the mold release recovery resin composition of the present invention is characterized by excellent workability when the resin composition is removed from the mold.
As erucic acid amide, for example, (trade name) Alfro P-10 and E-10 manufactured by NOF CORPORATION can be used.

The content of the monounsaturated fatty acid amide release agent in the mold release recovery resin composition is 3 to 60 parts by mass with respect to 100 parts by mass in total of the ethylene-propylene rubber and butadiene rubber. Parts, more preferably 10 parts by weight to 50 parts by weight, particularly preferably 15 parts by weight to 40 parts by weight.

(Polyethylene wax release agent)
The mold release recovery resin composition of the present invention preferably further contains at least one polyethylene wax release agent. By using this polyethylene wax mold release agent in combination with a monounsaturated fatty acid amide mold release agent, the effect of improving the brittleness of the mold release recovery resin composition is high and the strength can be kept high. The effect of imparting releasability to the inner surface is excellent.

Examples of the polyethylene wax-based release agent include oxidized polyethylene wax and non-oxidized polyethylene wax. The oxidized polyethylene wax is preferable in that the mold release recovery resin composition is less likely to become brittle and is excellent in imparting release properties.

Examples of the oxidized polyethylene wax include LicoWAX® PED521, 191 manufactured by Clariant, CERAFLOUR (registered trademark) 928, 950 manufactured by Big Chemie Japan, and Mitsui High Wax® 210MP manufactured by Mitsui Chemicals. it can.

The content of the polyethylene wax release agent in the mold release recovery resin composition is preferably 5 to 80 parts by mass with respect to 100 parts by mass in total of the ethylene-propylene rubber and the butadiene rubber. More preferably, it is 10 to 40 parts by mass.

Further, when the amide release agent and the polyethylene wax release agent are used in combination, the ratio of the amide release agent (NW) to the polyethylene wax release agent (PEW) (NW: PEW ratio [mass] The ratio]) is preferably in the range of 1:40 to 40: 1, and more preferably in the range of 1:20 to 20: 1.
When the NW: PEW ratio is in the range of 1:40 or more, higher strength can be obtained and mold release properties can be more effectively imparted. Further, when the NW: PEW ratio is in the range of 40: 1 or less, it is advantageous in terms of workability at the time of removal from the molding die.

(Metal soap release agent)
It is preferable that the mold release recovery resin composition of the present invention further contains at least one metal soap release agent. The metal soap release agent can effectively impart release properties to the molding die when using the mold release recovery resin composition. Furthermore, the metal soap mold release agent functions as a processing aid that effectively disperses the additive when the mold release recovery resin composition itself is manufactured, and the efficiency at the time of manufacture is improved. preferable.

Examples of metal soap release agents include zinc laurate, calcium laurate, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc myristate, calcium montanate, zinc montanate, aluminum montanate, and behen. It can be selected from the group consisting of calcium acid, magnesium behenate, and zinc behenate. The metal soap release agents may be used alone or in combination of two or more.

As the metal soap release agent used in the present invention, aluminum stearate is particularly preferable. Although the detailed mechanism is unknown, when aluminum stearate is included as a metal soap type mold release agent, it is formed by heating due to the synergistic effect of the monounsaturated fatty acid amide type mold release agent and the metal soap type mold release agent. This is presumably because the strength of the mold release recovery resin composition after the work of imparting release properties is more effectively improved.

The mold release recovery resin composition of the present invention may contain a release agent other than an amide release agent, an oxidized polyethylene wax release agent, and a metal soap release agent. Examples of such release agents include organic fatty acid ester release agents and synthetic wax release agents.

The total content of the release agent in the mold release recovery resin composition is preferably 20 parts by mass to 50 parts by mass with respect to 100 parts by mass in total of the ethylene-propylene rubber and the butadiene rubber. More preferably, it is 23 to 45 parts by mass.

(Other ingredients)
The mold release recovery resin composition of the present invention may further include other components other than the above-described components.

The mold release recovery resin composition of the present invention preferably contains an inorganic filler in that the strength of the mold release recovery resin composition can be more easily controlled. There is no restriction | limiting in particular in an inorganic filler, It can select suitably from the inorganic filler used normally. Specific examples of the inorganic filler include silica, alumina, calcium carbonate, aluminum hydroxide, and titanium oxide. Among them, the inorganic filler is at least one selected from the group consisting of silica and titanium oxide in that the damage to the mold is slight and the strength of the mold release recovery resin composition can be appropriately controlled. Species are preferred.

As long as the effect of the present invention is not hindered, the mold release recovery resin composition may contain other additives such as a surfactant, a vulcanization aid, a vulcanization accelerator, and a vulcanization acceleration aid as necessary. Can further be included.
Examples of the vulcanization aid include acrylic acid monomer and sulfur.
Examples of the vulcanization accelerator include guanidine series such as diphenylguanidine and triphenylguanidine, aldehyde-amine series such as formaldehyde-paratoluidine condensate, acetaldehyde-aniline reaction product, and aldehyde-ammonia series, 2-mercaptobenzothiazole, Examples include thiazoles such as dibenzothiazyl disulfide.
Examples of the vulcanization acceleration aid include magnesia, resurge, lime and the like.

As long as the resin composition for mold release recovery does not hinder the effects of the present invention, for example, petals, bitumen, iron black, ultramarine, carbon black, lithopone, titanium yellow, cobalt blue, Hansa yellow, quinacridone red, etc. It may further contain inorganic or organic pigments. By using such inorganic or organic pigments, it is possible to discriminate between the mold release recovery resin composition and the mold cleaning resin composition used before the mold release imparting operation. Becomes easier.

The method for preparing the mold release recovery resin composition is not particularly limited. For example, it can be prepared by adding a vulcanizing agent and a release agent to a mixed dough containing ethylene-propylene rubber and butadiene rubber and kneading them. At that time, an additive typified by an inorganic filler or the like can also be added.
The kneading means is not particularly limited, and can be appropriately selected from commonly used kneading means and kneading methods. For example, examples of the kneading means include a pressure kneader, a Banbury mixer, and a roll mixer.

The form of the mold release recovery resin composition is not particularly limited, and is preferably, for example, a sheet. When the mold release recovery resin composition is in the form of a sheet, it can be easily cooled in a short time. Further, by quickly cooling the kneaded resin composition, vulcanization due to preheating during kneading can be suppressed, and stable performance can be obtained. When the mold release recovery resin composition is molded into a sheet shape, the thickness and size thereof are not particularly limited, and can be appropriately selected according to the purpose. For example, the thickness can be 3 mm to 10 mm, and preferably 5 mm to 7 mm.

The usage form of the mold release recovery resin composition is not particularly limited, and for example, it is preferably used as a compression type. Thereby, after giving mold release properties to the inner surface of the molding die, it is possible to easily remove the mold release recovery resin composition from the molding die.

Next, the mold release recovery method of the present invention will be described.
The mold release recovery method of the present invention includes a step of applying the mold release recovery resin composition of the present invention described above to the inner surface of a mold (hereinafter also referred to as “applying step”), A step of heating the mold provided with the mold release recovery resin composition (hereinafter also referred to as “heating step”), and a step of taking out the mold release recovery resin composition after heating. is doing. The mold release recovery method may have other steps as necessary.
By using the mold release recovery resin composition of the present invention described above, the occurrence of cracks and the occurrence of sticking to the upper and lower surfaces of the mold when imparting mold release properties to the surface inside the mold Is suppressed, and the workability when removing from the molding die is excellent.

[Granting process]
The application step in the present invention is a step of applying the mold release recovery resin composition to the inner surface of the molding die. The details of the configuration and preferred embodiments of the mold release recovery resin composition used in this step are as described above.

The method for applying the mold release recovery resin composition to the inner surface of the molding die is not particularly limited, and a known method can be adopted. As a method of providing, for example, it can be performed by a known method such as compression molding or transfer molding of a mold release recovery resin composition molded into a sheet shape.
When the mold release recovery resin composition is applied to the inner surface of the molding die, it can be applied so as to cover a part or the entire surface of the cavity portion of the molding die. In the mold release recovery method, since the resin spreads uniformly over the entire inner surface of the mold during molding, a metal cleaning resin composition should be applied so as to cover the entire surface of the cavity of the mold. Is preferred.

[Heating process]
The heating step is a step of heating the mold release recovery resin composition applied to the inner surface of the molding die.
The heating method and heating conditions (temperature, time, number of times, etc.) are not particularly limited, and are publicly known according to the shape and type of the mold and the type of the resin composition for mold release recovery according to the present invention. These methods and conditions can be selected as appropriate.

Of the heating conditions, the heating temperature is, for example, from the viewpoint of simplicity, in the heating step of the present invention, using the same method and the same temperature as when molding the molding resin with a mold. It is preferable to heat the resin composition for mold recovery. Thereby, it is not necessary to overheat or cool the mold for mold release, and mold formation can be started immediately after imparting mold release properties to the mold.
The temperature in the heating step is preferably 160 ° C. to 190 ° C., more preferably 170 ° C. to 180 ° C.

The heating time is not particularly limited as long as the mold release recovery resin composition is sufficiently vulcanized and evenly spread over the entire inner surface of the mold. The time is preferably 150 seconds to 500 seconds, and more preferably 180 seconds to 360 seconds.

In the mold release recovery method, the applying step and the heating step may be repeated a plurality of times. The number of repetitions of the applying step and the heating step (hereinafter also referred to as “shot number”) is preferably 2 to 7 times, and more preferably 2 to 5 times.

Hereinafter, examples and comparative examples will be given to specifically explain the effects of the present invention. However, the present invention is not limited to these examples.

[Example 1]
In a 3000 ml jacketed pressure kneader, 450 g of ethylene-propylene rubber (Mitsui Chemicals, trade name: EPT4021, ethylene / propylene ratio = 55/45) and butadiene rubber (trade name: JSR BR01) 1050 g was added and pressure-kneaded for about 3 minutes while cooling. The mixed dough became sticky and the temperature was about 80 ° C.
Next, 375 g of erucic acid amide (manufactured by NOF Corporation, trade name: Alfro P-10), which is a monounsaturated fatty acid amide release agent, white carbon (trade name: Nippon Sil LP, manufactured by Tosoh Silica Corporation) 750 g of inorganic filler), black pigment (Mitsubishi Chemical Co., Ltd., Diamond Black), and titanium oxide (Ishihara Sangyo Co., Ltd., trade name: CR-80) 75 g were added and kneaded for about 3 minutes.
Finally, 90 g of n-butyl 4,4-bis (t-butylperoxy) valerate (manufactured by NOF Corporation, trade name: Perhexa V-40, purity 40%) was added as a vulcanizing agent, and about 1 Kneaded for a minute. During this time, the temperature of the kneaded material was adjusted so as not to exceed 100 ° C. The obtained kneaded material was quickly passed through a pressure roll, processed into a sheet shape, and cooled to 25 ° C. or lower to obtain a sheet-shaped mold release recovery resin composition having a thickness of 6 mm.

-Evaluation-
About the obtained resin composition for mold release recovery, the effect of imparting releasability to the inner surface of the molding die, the strength of the resin composition, and the release to the inner surface of the molding die are as follows. The workability of removing the resin composition from the molding die after imparting properties was evaluated. The evaluation results are shown in Table 1.
In any case, the evaluation was performed under the condition that the mold temperature was 175 ° C.
The unit in the composition of Table 1 is “parts by mass”, and “−” indicates that it is not blended.

[Evaluation test on effect of imparting releasability to the inner surface of the molding die]
PDIP-14L (8 pot-48 cavity) with a commercially available biphenyl epoxy resin molding material (manufactured by Sumitomo Bakelite Co., Ltd., trade name: EME-7351T) and a plunger with a tip made of cemented carbide. ) Was shot for 500 shots to form dirt on the inner surface of the molding die.
The molding die having a dirt on the inner surface thereof is repeatedly molded using a mold cleaning resin composition (manufactured by Nippon Carbide Industries Co., Ltd., trade name: Nicaret RCC ID grade), and the molding die interior The surface dirt was removed. Then, using the resin composition for mold release recovery produced in Example 1, it was heated at 175 ° C. and subjected to compression molding to impart release properties to the inner surface of the mold. After imparting releasability, the effect of imparting releasability to the inner surface of the molding die was evaluated by the number of continuous moldings (shots) of the processing of the epoxy resin molding material.
At this time, the case where the number of continuous moldings is 700 times or more is “excellent”, the case where the number of continuous moldings is 500 times or more and less than 700 times is “good”, and the number of continuous moldings is 300 times or more and less than 500 times. The product was evaluated as “possible” and the number of continuous moldings of less than 300 was evaluated as “impossible”.

[Evaluation test on strength of resin composition]
The strength of the resin composition was evaluated as follows. The mold release recovery resin composition was heat-molded to impart release properties to the inner surface of the mold, and then the mold release recovery resin composition was removed from the mold. The removed resin composition was bent at 180 degrees with both hands at both ends in the longitudinal direction. At this time, the resin composition that does not break is “excellent”, and some cracks are generated in the folded part, but those that can be folded at 180 degrees are “good”, the resin composition breaks, etc. Those that could not be bent at 180 degrees were evaluated as “impossible”.

[Evaluation test on workability when removing from molding die]
The mold release recovery resin composition is heat-molded to give mold release properties to the inner surface of the mold, and then the mold release recovery resin composition is removed from the mold. evaluated. Evaluation was made as “excellent” when the mold release recovery resin composition itself did not crack or stick to the upper and lower surfaces of the mold, and had excellent workability when removed from the mold. Resin composition for mold release recovery itself has some cracking and sticking to the upper and lower surfaces of the molding die, but the degree is small. If the allowable range is “OK”, it is necessary to clean the molding die again due to cracks in the mold release recovery resin composition itself and sticking to the upper and lower surfaces of the molding die. The case where the drop was extremely low was regarded as “impossible”.

[Example 2]
In Example 1, gold was used in the same manner as in Example 1 except that 45 g of aluminum stearate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name: Al-St (103)) was used as the metal soap release agent. A mold release recovery resin composition was obtained and evaluated in the same manner.

[Examples 3 to 9]
In Example 1, a mold release recovery resin composition was obtained in the same manner as in Example 1 except that the composition of the mold release recovery resin composition was changed as shown in Table 1 below. The evaluation was performed in the same manner.

[Comparative Example 1]
In Example 1, in place of the monounsaturated fatty acid amide release agent, zinc stearate (made by NOF Corporation, trade name: zinc stearate) which is a metal soap release agent as shown in Table 1 below. A mold release recovery resin composition was obtained in the same manner as in Example 1 except that 375 g of GF-200) was used, and evaluated in the same manner.

[Comparative Example 2]
In Example 1, instead of the monounsaturated fatty acid amide release agent, as shown in Table 1 below, zinc stearate, which is a metal soap release agent (manufactured by NOF Corporation, trade name: zinc steer) Rate GF-200) and an oxidized polyethylene wax-based mold release agent (manufactured by Clariant, trade name: LicoWAX PED521), and the composition was changed as shown in Table 1 below. Thus, a mold release recovery resin composition was obtained and evaluated in the same manner.

[Comparative Example 3]
In Example 1, in place of the monounsaturated fatty acid amide release agent, as shown in Table 1 below, a metal soap release agent calcium behenate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name: CS-) 7) and an oxidized polyethylene wax-based release agent (manufactured by Clariant, trade name: LicoWAX PED521), and the composition was changed in the same manner as shown in Table 1 below. A mold release recovery resin composition was obtained and evaluated in the same manner.

[Comparative Example 4]
In Example 1, instead of the monounsaturated fatty acid amide release agent, as shown in Table 1 below, a metal soap release agent calcium behenate (product name: CS-7, manufactured by Nitto Kasei Kogyo Co., Ltd.) The resin composition for mold release recovery was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 1 below, and evaluated in the same manner.

As is apparent from the results shown in Table 1, the sheet-shaped mold release recovery resin composition according to the embodiment of the present invention has an increased strength of the mold release recovery resin composition. Cracking and sticking to the upper and lower surfaces of the mold during the process of imparting mold release to the inner surface of the mold are suppressed, and workability when removing the mold release recovery resin composition from the mold is improved. It was.
Further, as can be seen from the results of Example 2, mold release recovery using a combination of erucic acid amide, which is a monounsaturated fatty acid amide release agent, and aluminum stearate, which is a metal soap release agent. In the resin composition for use, the strength was further increased, and the workability when removing the mold release recovery resin composition from the mold was improved more effectively.
Furthermore, as shown in Example 4, mold release recovery using a combination of erucic acid amide, which is a monounsaturated fatty acid amide release agent, and oxidized polyethylene wax, which is a polyethylene wax release agent In the resin composition, the strength is further increased, and the workability when removing the mold release recovery resin composition from the mold is excellent, and more than the mold release recovery resin composition of Example 2 Furthermore, the effect of imparting releasability to the inner surface of the molding die was excellent. This was a better result than the mold release recovery resin composition of Example 3 which further contained a metal soap release agent. However, even when a metal soap release agent is further contained in addition to the amide release agent and the polyethylene wax release agent, the content ratio of the polyethylene wax release agent is high as in Example 5. As a result, the effect of imparting releasability to the inner surface of the molding die tended to be improved.

The mold release recovery resin composition of the present invention includes, for example, a molding mold generated in a molding process of a curable resin composition selected from the group consisting of epoxy resins, silicone resins, phenol resins, and polyimide resins. Molding can be imparted to the inner surface of the molding die by molding after removing the dirt on the surface. By using the mold release recovery resin composition of the present invention, sealing molding of the curable resin composition can be continuously carried out for several hundred shots.

The disclosure of Japanese application 2012-203644 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

A mold release recovery resin composition comprising ethylene-propylene rubber, butadiene rubber, a vulcanizing agent, and a monounsaturated fatty acid amide release agent.
The mold release recovery resin composition according to claim 1, wherein the monounsaturated fatty acid amide release agent is erucic acid amide.
Furthermore, the mold release recovery resin composition of Claim 1 or Claim 2 containing a polyethylene wax type mold release agent.
The content ratio (NW: PEW ratio [mass ratio]) of the monounsaturated fatty acid amide release agent (NW) and the polyethylene wax release agent (PEW) is in the range of 1:20 to 20: 1. The mold release recovery resin composition according to claim 3.
The mold release recovery resin composition according to any one of claims 1 to 4, further comprising a metal soap release agent.
The metal soap release agent is zinc laurate, calcium laurate, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc myristate, calcium montanate, zinc montanate, aluminum montanate, calcium behenate 6. The mold release recovery resin composition according to claim 5, which is at least one metal soap type mold release agent selected from the group consisting of magnesium behenate and zinc behenate.
The mold release recovery resin composition according to claim 6, wherein the metal soap mold release agent is aluminum stearate.
A step of applying the mold release recovery resin composition according to any one of claims 1 to 7 to the inner surface of the molding die;
Heating the mold provided with the mold release recovery resin composition,
A step of taking out the mold release recovery resin composition after heating;
Mold release recovery method.