WO2016167415A1 - Composition de caoutchouc dotée d'excellente capacité de remplissage - Google Patents

Composition de caoutchouc dotée d'excellente capacité de remplissage Download PDF

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WO2016167415A1
WO2016167415A1 PCT/KR2015/007971 KR2015007971W WO2016167415A1 WO 2016167415 A1 WO2016167415 A1 WO 2016167415A1 KR 2015007971 W KR2015007971 W KR 2015007971W WO 2016167415 A1 WO2016167415 A1 WO 2016167415A1
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weight
rubber composition
rubber
ethylene
parts
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PCT/KR2015/007971
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English (en)
Korean (ko)
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이동권
이문석
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주식회사 나라켐
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Priority claimed from KR1020150054172A external-priority patent/KR101712356B1/ko
Priority claimed from KR1020150080928A external-priority patent/KR101667564B1/ko
Application filed by 주식회사 나라켐 filed Critical 주식회사 나라켐
Publication of WO2016167415A1 publication Critical patent/WO2016167415A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/064—VLDPE

Definitions

  • the present invention is a rubber composition for removing contaminants remaining in a mold in the process of continuously molding the thermosetting resin, and imparting releasability to the mold after removal, in detail, the mobility in the mold of the rubber composition by a combination of specific components It is related with the rubber composition which improves (mobility) and is excellent in filling property.
  • the mold used to form the product by using the thermosetting resin as a raw material is compressed and heated to form a carbonized residue of the contaminants introduced during the work process, which acts as a contaminant during the subsequent work process. Not only does it cause some defects in the molding, but it also causes the quality of the product to deteriorate in the continuous molding process. Therefore, after a certain period of time or after a certain number of molding operations to remove the contaminants remaining in the mold (so-called "cleaning operation”) should be made.
  • U.S. Patent No. 3,476,599 proposes a thermosetting resin composition for mold cleaning, which uses a thermosetting resin as a base and adds an amino alcohol compound having an amino group and a hydroxyl group as a cleaning agent.
  • the amino group of the aminoalcohol-based compound which is a cleaning agent, is decomposed to generate an amine-based gas during curing of the sheet for cleaning, there is a problem of odor and smoke generation.
  • a rubber composition for mold cleaning using an uncrosslinked rubber including butadiene rubber (BR) and ethylene-propylene diene monomer rubber (EPDM) and using an imidazole compound or imidazoline compound as a cleaning agent is proposed.
  • the above problems have been solved to some extent, the odor due to decomposition of the curing agent (mainly organic peroxide) used for the crosslinking of the uncrosslinked rubber occurs badly, and thus the problem is not solved fundamentally. It is limited only to the sol-based or imidazoline-based compounds, and there is a limit in increasing the cleaning power.
  • release operation in addition to the cleaning operation, in order to facilitate the desorption of the thermosetting resin according to the repetitive operation, an operation for imparting mold release property to the mold (so-called “release operation") is essential.
  • the release operation directly affects the quality of the semiconductor device.
  • the release property imparted to the mold surface does not reach a certain level, it is difficult to repair not only the entire product but also many repairs. Since time is required, research has been conducted to maintain this for a long time while giving mold release property.
  • an uncrosslinked rubber including butadiene rubber (BR) and ethylene-propylene diene monomer rubber (EPDM) is used as the substrate, and instead of the cleaning agent, coating components, inorganic fillers,
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • a mold coating method by eluting a coating component (wax and additive) according to rubber curing through a rubber composition for mold coating further comprising a curing agent and the like.
  • FIG. 1 is a schematic diagram showing a release rubber mechanism and non-fill property of a conventional rubber composition
  • FIG. 2 is a photo showing a crosslinked rubber demolded from a mold in the process of FIG. 1.
  • 3 is a schematic diagram showing a process of manufacturing an EMC product through a mold coated through the process of FIG. 1 and a defect of the EMC product due to non-pilliness.
  • the release rubber composition 120 including the uncrosslinked rubber 121 and the coating component 122 is disposed in the mold 110, and then cured at a temperature of about 175 to 180 ° C.
  • the crosslinking reaction is performed and the crosslinked rubber 130 is removed, the mold 110 is coated with the coating component 122.
  • the method is a problem of product defects and contamination in the mold due to deterioration of the deformability that the rubber produced through the composition in the mold 110 does not easily fall out, and parts 110a that are indented in the mold during the release agent coating operation.
  • the rubber composition has a problem such as a decrease in mold releasability due to a non-fill phenomenon that is not sufficiently filled.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the rubber composition according to the present invention consists of a combination of specific components, and when such a rubber composition is used in a molding die, the cleaning power or deforming property of the cleaning rubber and the release rubber produced by the rubber composition. And it was confirmed that the filling property is excellent, the present invention has been completed.
  • Rubber composition according to the present invention for achieving this object, as a rubber composition for improving the releasability of the molding die,
  • Uncrosslinked rubber containing 60 to 100 parts by weight of butadiene rubber (BR), 0 to 40 parts by weight of ethylene-propylene diene monomer rubber (EPDM) and 5 to 40 parts by weight of a polymer additive having a melting temperature (T m ) of 100 ° C. or less;
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • T m melting temperature
  • the rubber composition according to the present invention is 60 to 100 parts by weight of butadiene rubber (BR), 0 to 40 parts by weight of ethylene-propylene diene monomer rubber (EPDM) and a polymer additive 5 to 40 having a melting temperature (T m ) of 100 ° C or less. Uncrosslinked rubber including parts by weight; And
  • the melting temperature refers to a peak point obtained through DSC (Differential Scanning Calorimeter) analysis, and the uncrosslinked rubber is crosslinked in the mold by the action of a curing agent when subjected to heat and pressure to clean the inside of the mold with a cleaning agent, or After the coating with wax and additives.
  • DSC Different Scanning Calorimeter
  • the rubber composition according to the present invention further includes polymer additives that satisfy specific conditions in butadiene rubber and ethylene-propylene diene monomer rubber, which are conventionally used as base materials for uncrosslinked rubber, thereby improving the mobility of the rubber composition, thereby making it easier to It is possible to improve the filling properties of the rubber, and thus it is possible to completely coat the inside of the mold with wax and additives to increase the deforming of the rubber produced through the composition. Furthermore, the deforming of the rubber is improved, so that the residue of the cleaning rubber remaining in the mold after the cleaning operation can be minimized. Furthermore, it is possible to improve the speed at which the cleaning agent flows out of the crosslinked rubber, and thus to completely clean the inside of the mold with the cleaning agent, thereby increasing the cleaning power of the mold.
  • the uncrosslinked rubber in the rubber composition may not contain ethylene-propylene diene monomer rubber as defined above, or may be included in an amount of 40 parts by weight or less, and in detail, in an amount of 5 to 30 parts by weight. May be included.
  • the polymer additive may be included in 5 to 40 parts by weight, specifically, 10 to 30 parts by weight.
  • the uncrosslinked rubber contains more than 40 parts by weight of the polymer additive, the crosslinking degree of the release rubber or the cleaning rubber produced by the rubber composition is lowered, so that the cleaning agent does not effectively act on the contaminants in the mold. There is a problem in that the releasability is lowered because the cleaning power is reduced or the amount of the wax and the additive coating decreases.
  • the uncrosslinked rubber contains less than 5 parts by weight of the polymer additive, the present invention provides a desired level of filling and deforming properties. There is a problem that is difficult to represent.
  • the polymer additive may have a melting temperature thereof in the range of 40 ° C to 100 ° C, and specifically 40 ° C to 90 ° C.
  • the polymer melting temperature exceeds 100 °C, the production temperature is high, the scorch (pre-crosslinking) occurs during the production of uncrosslinked rubber products, product defects occur, while the melting temperature of the polymer additive is 40 If it is less than °C, the surface of the product is sticky (sticky), the problem of the product sticking to the surface of the equipment during the production process, the product is not only difficult to produce, but also the hardness of the product is lowered, the filling performance is worsened .
  • the polymer additive may be a polyolefin-based elastomer or a copolymer composed of a monomer for polyolefin and an acrylic acid monomer and an ionomer thereof, or a copolymer composed of a monomer for polyolefin and an acrylate monomer.
  • a polyolefin-based elastomer or a copolymer composed of a monomer for polyolefin and an acrylic acid monomer and an ionomer thereof, or a copolymer composed of a monomer for polyolefin and an acrylate monomer.
  • the polyolefin elastomer is not particularly limited as long as it satisfies the conditions of the above-described polymer additives, for example, ultra low density polyethylene (VLDPE); Polybutene; Poly-4-methyl-1-pentene (TPX); Copolymers of propylene, butene, hexene and / or octene with ethylene; And it may be at least one selected from the group consisting of olefin-based thermoplastic elastomer.
  • VLDPE ultra low density polyethylene
  • TPX Poly-4-methyl-1-pentene
  • Copolymers of propylene, butene, hexene and / or octene with ethylene and it may be at least one selected from the group consisting of olefin-based thermoplastic elastomer.
  • the copolymer composed of the monomer for polyolefin and the acrylic acid monomer and the copolymer thereof for the ionomer or polyolefin monomer and the acrylate monomer thereof are not particularly limited as long as the melting temperature (T m ) described above satisfies the condition of 100 ° C. or less.
  • EAA Ethylene-acrylic acid copolymer
  • EAA ethylene-methacrylic acid copolymer
  • EMA ethylene-methacrylic acid copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EVA ethylene-alkylacrylic It may be at least one selected from the group consisting of a rate-acrylic acid copolymer, an ethylene-alkyl methacrylate-methacrylic acid copolymer, an ethylene-butyl acrylate copolymer (EBA), and an ethylene-vinylacetate copolymer (EVA).
  • the copolymer may have a composition including 60 to 96 wt% of the monomer for polyolefin and 4 to 40 wt% of the acrylic acid or acrylate or vinyl acetate monomer based on 100 wt% of the copolymer.
  • the polyolefin elastomer as the polymer additive may be an ethylene-propylene copolymer or an ethylene-butylene copolymer obtained by the reaction of an ethylene monomer and a propylene monomer or a butylene monomer.
  • the ethylene-propylene copolymer or ethylene-butylene copolymer satisfies the conditions of the polymer additive described above.
  • the waxes and additives for imparting releasability to the mold are not particularly limited as long as they have such a function, and for example, polyethylene and slip agents having a weight average molecular weight of 200 to 3000.
  • the anti blocking agent may be in a mixed form.
  • the slip agent for improving the deformability of the rubber is not particularly limited, for example, erucamide, oleamide, stearamide, behenamide , Ethylene bis stearamide (Ethylene-bis-stearamide), ethylene bis oleamide (Ethylene-bis-oleamide), may be stearyl erucamide (Stearyl erucamide).
  • the content of such waxes and additives, as described above, may be 5 to 60 parts by weight based on 100 parts by weight of the uncrosslinked rubber, less than 5 parts by weight outside the above range, it is difficult to give sufficient mold release property to the mold, If it is more than 60 parts by weight, there is a problem that excess wax is left as a stain on the surface of the mold acts as another contamination source, it is not preferable.
  • the cleaning agent which substantially removes contaminants from the mold, is not particularly limited so long as it has such a function, for example, methylene chloride, diethylene glycol monobutylether ), Acetoaldehyde, ethyl digylcol, ethanoic acid, formic acid, ammonium dodecylbenzene sulfonate, 1-methoxy-2 Propanol (1-methoxy-2-propanol), methyl alcohol, dodecylbenzene sulfonic acid, acetone, 2- (2-butoxyethoxy) ethanol diethylene glycol mono Butyl ether (2- (2-butoxyethoxy) ethanol diethylene glycol monobutylether (BDG), ethanol amine (MEA), 2-aminoethanol (MEA), 2-diethylaminoethanol (2-diethylamino ethanol : DEAE), 2-meth 2-methoxylethanol (EM), 2-ethoxylethanol, 2-propoxyethanol, dimethyl
  • the inventors of the present invention were able to confirm that a better cleaning effect is obtained when a mixture consisting of a combination of different cleaning compounds is used as the cleaning agent than when using one kind of cleaning compound as the cleaning agent.
  • a mixture of two or more of different kinds of cleaning compounds is used as the cleaning agent.
  • the mutual ratio of the mixed cleaning compounds is 1:99 to 99: 1 by weight, in detail may be in the range of 5:95 to 95: 5.
  • the content of the cleaner is 0.5 to 60 parts by weight, and less than 0.5 parts by weight makes it difficult to obtain sufficient cleaning power.
  • the amount of the cleaner is greater than 60 parts by weight, the excess cleaner is stained on the surface of the mold as another contaminant. Since there is a problem in working, it is not preferable.
  • the inventors of the present application confirmed that the cleaning power is further improved when the cleaning agent is further included in addition to the cleaning agent.
  • the rubber composition may further comprise a cleaning aid, and in particular, the cleaning aid may be a nonionic surfactant.
  • the nonionic surfactant may be an alkylamine ethoxylate compound having a molecular formula of C 23 H 38 N 2 O 8 .
  • Alkylamine ethoxylate compounds having a molecular formula of C 23 H 38 N 2 O 8 have a reversible surfactant, and in amine solution, these amine ethoxylates act as surfactants, but in acidic solutions they There is a characteristic of losing its surfactant activity. It is known that these properties can be used to facilitate the separation of emulsified oils from aqueous materials so that the compounds can be used primarily for industrial washing or metal cleaning.
  • the nonionic surfactant may be an alkylphenol ethoxylate-based compound of Formula 1 below, specifically, R may be an octylphenol ethoxylate-based compound having 8 carbon atoms, x May be an integer from 3 to 10.
  • R is alkyl having 4 to 10 carbon atoms and x is an integer of 1 to 55.
  • the alkylphenol ethoxylate-based compound of Formula 1 may be used in a wide range of temperatures as a material having wettability, detergency, and emulsification of oil for aqueous, and can be used in all forms of liquid, paste, powder, etc. There are properties that can be used in the compound. Accordingly, the compounds can be used for a variety of industrial cleanings, from soft household detergents to heavy-duty industrial products, and in particular, are known to have excellent effects on the cleaning of hard surfaces and metals.
  • the nonionic surfactant may be an alcohol alkoxylate compound having a molecular formula of C 12 H 30 O 2 , and specifically, may be a material of Formula 2 below.
  • the alcohol alkoxylate compound having a molecular formula of C 12 H 30 O 2 is a water-soluble nonionic surfactant having excellent performance and processability, and has excellent wettability, washability, and fast dissolution rate. Due to these properties, the compounds are known to be used in a variety of industries, from detergents and degreasing agents to hard surfaces and metals, as well as from household detergents to industrial laundry detergents.
  • the rubber composition according to the present invention including the cleaning aid has an advantage that, even if the amount of the cleaning agent is reduced compared to the conventional rubber composition, it may have better or similar cleaning power.
  • the amount of the cleaning aid is 0.1 to 7 parts by weight, and in detail, 0.5 to 3 parts by weight. Less than 0.1 part by weight makes it difficult to obtain the improved cleaning power, while more than 7 parts by weight may act as another contaminant, while the cleaning power is no longer improved, which is undesirable.
  • At least one of such detergents and cleaning aids may be included in the applied or impregnated state, or in the applied and impregnated state, to inorganic fillers and adsorbents, which will be described in more detail later, which are mainly present in a liquid state. This is because the cleaning agent or cleaning aid is difficult to be uniformly kneaded with the uncrosslinked rubber.
  • the inventors of the present application confirmed that the cleaning power is further improved when the cleaning agent and the cleaning aid further include an expansion agent which is an alcohol-based substance such as water and / or methanol or ethanol.
  • the cleaning operation is generally performed by placing a mold cleaning unit made of the rubber composition on a mold and applying a temperature of 150 to 200 ° C. and a pressure of 15 kgf / cm 2 to 100 kgf / cm 2 for 2 to 10 minutes. It is carried out by curing the unit into a shape in a mold.
  • the cleaning power may be further improved. This is because the temperature applied to the unit during the cleaning operation is higher than the boiling point of the expansion agent, and thus the expansion agent is evaporated at a temperature higher than the boiling point, thereby remaining in the unit. It is presumed that this is because it promotes the phenomenon of eluting to the surface, that is, the blooming effect. That is, when only the cleaning agent is used, even the cleaning agent which is present inside and does not effectively act on the contaminant may be eluted to the surface to contact the contaminant.
  • the content of the expanding agent may be 1 to 10 parts by weight based on 100 parts by weight of the uncrosslinked rubber. If it is less than 1 part by weight, it is difficult to obtain the above effect. If it is more than 10 parts by weight, the kneading operation is difficult and there is a problem of contaminating the mold surface, which is not preferable.
  • the inventors of the present application further show that when a strong acid such as hydrochloric acid, sulfuric acid, nitric acid, bromic acid, or strong alkali such as sodium hydroxide or potassium hydroxide is used in combination with a cleaning agent and a cleaning aid, a more enhanced cleaning effect is obtained.
  • a strong acid such as hydrochloric acid, sulfuric acid, nitric acid, bromic acid, or strong alkali such as sodium hydroxide or potassium hydroxide
  • cleaning catalysts Strong acids or strong bases (hereinafter, sometimes referred to as "cleaning catalysts") added together with the cleaning agents are assumed to serve as catalysts in the cleaning process. That is, in the rubber composition for mold cleaning containing only the cleaning agent and the cleaning aid component, the contaminants are crosslinked in a state in which the detergent directly dissolves the contaminants or the cleaner penetrates between the mold and the contaminants to weaken the adhesion between them.
  • the cleaning process proceeds in such a way that it is attached to and removed from the rubber.
  • the cleaning catalyst when used together with the cleaning agent and the cleaning aid, the cleaning catalyst enhances the penetration of the cleaning agent and the cleaning aid while promoting the crushing of the contaminants, and consequently, greatly improves the cleaning power.
  • the cleaning catalyst may be included in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the cleaning agent.
  • a strong acid or a strong base as described above may be selectively used, and KOH may be used in detail.
  • the content of the cleaning agent including the cleaning catalyst may also be 0.5 to 60 parts by weight, as described above.
  • the curing agent may be used as a component that induces such curing, and organic peroxides, phenol resins, and sulfur may be used.
  • organic peroxides may be an organic peroxide, and the type of organic peroxide may be selected according to the mold temperature in consideration of the half-life temperature.
  • Such organic peroxides include, but are not limited to, for example, 2,5-dimethyl-2,5-bis- (t-butylperoxy) (2,5-dimethyl-2,5-bis- ( t-butylperoxy)), dt-butylperoxide, 2,5-dimethyl-2,5-bis- (t-butylperoxy) -hexane (2,5-dimethyl-2,5-bis -(t-butylperoxy) -hexane), t-butyl cumyl peroxide (t-buthylcumylperoxide), bis- (t-butylperoxy-i-propyl) -benzene (bis- (t-buthylperoxy-i-propyl)- benzene), dicumylperoxide, 4,4-di-t-butylperoxy-n-butyl valerate (4,4-di-t-buthylperoxy-n-buthy
  • bis- (t-butylperoxy-i-propyl) benzene and 4,4-di-t-butylperoxy-n-butyl valerate are ethylene-propylene diene monomers (EPDM) and butyl rubber (BR) It is especially preferable for the mixed rubber cleaning composition.
  • the inorganic filler is a component that serves to increase the balance of the composition components with the increase in viscosity more excellent. That is, the viscosity of the composition is lowered by adding wax or detergent to the uncrosslinked rubber. By adding an inorganic filler, the Mooney viscosity can be increased to maintain the balance of various components.
  • examples of such inorganic fillers include silica, talc, alumina, potassium carbonate, calcium carbonate, aluminum hydroxide, titanium oxide, carbon black, and the like.
  • the rubber composition according to the present invention can be used for cleaning operations (work of putting a mold rubber sheet made of the rubber composition according to the invention into a mold and applying heat and pressure) or mold release work (mold release made of the rubber composition according to the present invention).
  • Adsorbents may also be included to adsorb and remove various odor and smoke components resulting from the operation of putting the rubber sheet into the mold and applying heat and pressure.
  • Such adsorbents have a high adsorption capacity and a large specific surface area for the odor and smoke components. Odor and smoke generated during operation are inevitably generated by various factors such as decomposition of the curing agent and decomposition of the cleaning agent, and the adsorbent having a fine pore and a large specific surface area is added to the composition according to the present invention. It can solve the problem caused by this.
  • the adsorbent has a specific surface area of at least 200 m 2 / g or more. Moreover, having many fine pores can exhibit more excellent adsorption force.
  • the adsorbent may include clay (mud), silica gel, activated carbon, zeolite, ion exchange resin, acidic clay, and the like, and in some cases, may be used in the form of a mixture of two or more thereof.
  • the adsorbent used in the present invention may be, in detail, zeolite, silica gel, or acidic clay having a specific surface area of not less than 200 m 2 / g, and more specifically, fine powder silica gel or zeolite. have. Fine powder silica gel can solve the problem of kneading with uncrosslinked rubber by pulverizing the particle size of silica gel from millimeter (mm) to micron ( ⁇ m).
  • Zeolite X type and zeolite Y type have a specific surface area (approximately 500 m2 / g or more) is large, but expensive, it can be mixed with zeolite A type to lower the production cost of the composition of the present invention.
  • activated carbon and ion exchange resin have a very large specific surface area (about 600 m 2 / g or more), the adsorption power is excellent, while each is black and expensive, and therefore it is preferable to use it in combination with other adsorbent components.
  • Such an adsorbent may also serve as an inorganic filler, and the content of the adsorbent and the inorganic filler may be 5 to 110 parts by weight based on 100 parts by weight of the uncrosslinked rubber.
  • the rubber composition according to the present invention may further participate in other compound (s) or mixture (s) within a range that does not impair its physical properties.
  • FIG. 1 is a schematic diagram showing a release rubber mechanism and non-fill properties of a conventional rubber composition
  • FIG. 2 is a photograph showing a crosslinked rubber demolded from a mold in the process of FIG. 1;
  • FIG. 3 is a schematic diagram showing a process of manufacturing an EMC product through a mold coated through the process of FIG. 1 and a defect of the EMC product due to non-pilliness;
  • Figure 4 is a schematic diagram showing a release rubber mechanism of the rubber composition excellent in filling and demolding according to an embodiment of the present invention
  • FIG. 5 is a photograph showing the crosslinked rubber demolded from the mold in the process of FIG.
  • Figure 4 is a schematic diagram showing a release rubber mechanism of the rubber composition excellent in filling and demolding according to an embodiment of the present invention
  • Figure 5 is a photo showing the cross-linked rubber demolded from the mold in the process of Figure 4 Is shown.
  • the release rubber composition 220 including the uncrosslinked rubber 221 and the coating component 222 is disposed in the mold 210, and then cured at a temperature of about 175 to 180 ° C.
  • the crosslinking reaction is performed and the crosslinked rubber 230 is removed, the inside of the mold 210 is coated with the coating component 222.
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n 30 g of butylvalate)
  • an inorganic filler 300 g of silica, 50 g of titanium oxide
  • a wax 80 g of polyethylene, 20 g of a slipping agent
  • Example 2 Except for using ultra low density polyethylene (VLDPE) in Example 1, 200 g of the ionomer of ethylene-methacrylic acid copolymer (EMAA) produced by reacting an ethylene monomer and an acrylic acid monomer in a weight ratio of 9: 1 was used. Was prepared in the same manner as in Example 1. At this time, the ionomer density of the ethylene-methacrylic acid copolymer (EMAA) is 0.95, the melting temperature is 70 °C.
  • VLDPE ultra low density polyethylene
  • EMA ethylene-methacrylic acid copolymer
  • Example 2 Except for using ultra low density polyethylene (VLDPE) in Example 1, except that 200 g of the ethylene-methacrylic acid copolymer (EMA) produced by reacting an ethylene monomer and a methacrylic acid monomer in a weight ratio of 9: 1 was used. Was prepared in the same manner as in Example 1. At this time, the density of the ethylene-methacrylic acid copolymer (EMA) is 0.94, the melting temperature is 72 °C.
  • VLDPE ultra low density polyethylene
  • EMA ethylene-methacrylic acid copolymer
  • Example 2 Except for using ultra low density polyethylene (VLDPE) in Example 1, except that 200g of ethylene-vinylacetate copolymer (EVA) produced by reacting the ethylene monomer and vinyl acetate monomer in a weight ratio of 9: 1 was used. A kneaded product was prepared in the same manner as in Example 1. At this time, the density of the ethylene-vinylacetate copolymer (EVA) is 0.95, the melting temperature is 75 °C.
  • VLDPE ultra low density polyethylene
  • EVA ethylene-vinylacetate copolymer
  • a kneaded product was prepared in the same manner as in Example 1, except that 200 g of the ethylene-butylene copolymer was used in place of the ultra low density polyethylene (VLDPE). In this case, the density of the ethylene-butylene copolymer is 0.88, the melting temperature is 64 °C.
  • VLDPE ultra low density polyethylene
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n 30 g of butylvalate)
  • an inorganic filler 300 g of silica, 50 g of titanium oxide
  • a wax 80 g of polyethylene, 20 g of a slipping agent
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n 30 g of butylvalate)
  • an inorganic filler 300 g of silica, 50 g of titanium oxide
  • a wax 80 g of polyethylene, 20 g of a slipping agent
  • a kneaded product was prepared in the same manner as in Example 1, except that ultra low density polyethylene (VLDPE) was not used in Example 1.
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 1, except that low density polyethylene (LDPE) was used instead of ultra low density polyethylene (VLDPE) in Example 1.
  • LDPE low density polyethylene
  • VLDPE ultra low density polyethylene
  • the density of the low density polyethylene (LDPE) is 0.921
  • the melting temperature is 110 °C.
  • a kneaded product was prepared in the same manner as in Example 1, except that an ethylene-methacrylic acid copolymer having a density of 0.93 and a melting temperature of 110 ° C. was used instead of the ultra low density polyethylene (VLDPE) as the polymer additive in Example 1. .
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 6, except that 400 g of ultra low density polyethylene (VLDPE) was used in Example 6.
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 6, except that 20 g of ultra low density polyethylene (VLDPE) was used in Example 6.
  • VLDPE ultra low density polyethylene
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n -30 g of butylvalate) and an inorganic filler (300 g of silica, 50 g of titanium oxide)
  • a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g
  • MEA monoethanolamine
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • Example 8 Except for using ultra low density polyethylene (VLDPE) in Example 8, 200 g of the ionomer of ethylene-methacrylic acid copolymer (EMAA) produced by reacting an ethylene monomer and an acrylic acid monomer in a weight ratio of 9: 1 was used. Was prepared in the same manner as in Example 8. At this time, the ionomer density of the ethylene-methacrylic acid copolymer (EMAA) is 0.95, the melting temperature is 70 °C.
  • VLDPE ultra low density polyethylene
  • EMA ethylene-methacrylic acid copolymer
  • Example 8 Except for using ultra low density polyethylene (VLDPE) in Example 8, except that 200 g of the ethylene-methacrylic acid copolymer (EMA) produced by reacting the ethylene monomer and methacrylic acid monomer in a weight ratio of 9: 1 was used. Was prepared in the same manner as in Example 8. At this time, the density of the ethylene-methacrylic acid copolymer (EMA) is 0.94, the melting temperature is 72 °C.
  • VLDPE ultra low density polyethylene
  • EMA ethylene-methacrylic acid copolymer
  • Example 8 Except for using ultra low density polyethylene (VLDPE) in Example 8, except that 200g of ethylene-vinylacetate copolymer (EVA) produced by reacting the ethylene monomer and vinyl acetate monomer in a weight ratio of 9: 1 was used. A kneaded product was prepared in the same manner as in Example 8. At this time, the density of the ethylene-vinylacetate copolymer (EVA) is 0.95, the melting temperature is 75 °C.
  • VLDPE ultra low density polyethylene
  • EVA ethylene-vinylacetate copolymer
  • a kneaded product was prepared in the same manner as in Example 8, except that 200 g of the ethylene-butylene copolymer was used in place of the ultra low density polyethylene (VLDPE). In this case, the density of the ethylene-butylene copolymer is 0.88, the melting temperature is 64 °C.
  • VLDPE ultra low density polyethylene
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n -30 g of butylvalate) and an inorganic filler (300 g of silica, 50 g of titanium oxide)
  • a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g
  • MEA monoethanolamine
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • VLDPE ultra low density polyethylene
  • BR butadiene rubber
  • EPDM ethylene-propylene diene monomer rubber
  • VLDPE ultra low density polyethylene
  • a curing agent (4,4-di-t-butylperoxy-n -30 g of butylvalate) and an inorganic filler (300 g of silica, 50 g of titanium oxide)
  • a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g
  • MEA monoethanolamine
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • a kneaded product was prepared in the same manner as in Example 8, except that the auxiliary cleaner (Triton RW 10 g) was applied and impregnated into the inorganic filler in Example 8.
  • the auxiliary cleaner Triton RW 10 g
  • a kneaded product was prepared in the same manner as in Example 15, except that 10 g of Triton XL-80N was used as the auxiliary cleaner in Example 15.
  • a kneaded product was prepared in the same manner as in Example 15, except that 10 g of Triton X-100 was used as the auxiliary cleaner in Example 15.
  • Example 15 In order to confirm the effect of the swelling agent, a kneaded product was prepared in the same manner as in Example 15 by further adding 25 g of water and ethanol to the composition of Example 15 one to one.
  • a kneaded product was prepared in the same manner as in Example 15 by further adding 5 g of KOH as a cleaning catalyst to the composition of Example 18.
  • a kneaded product was prepared in the same manner as in Example 8 except that the ultra low density polyethylene (VLDPE) was not used in Example 8.
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 8 except for using the low density polyethylene (LDPE) instead of the ultra low density polyethylene (VLDPE) in Example 8.
  • LDPE low density polyethylene
  • VLDPE ultra low density polyethylene
  • the density of the low density polyethylene (LDPE) is 0.921
  • the melting temperature is 110 °C.
  • a kneaded product was prepared in the same manner as in Example 8, except that an ethylene-methacrylic acid copolymer having a density of 0.93 and a melting temperature of 110 ° C. was used instead of the ultra low density polyethylene (VLDPE) as the polymer additive in Example 8. .
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 13, except that 400 g of ultra low density polyethylene (VLDPE) was used in Example 13.
  • VLDPE ultra low density polyethylene
  • a kneaded product was prepared in the same manner as in Example 13, except that 20 g of ultra low density polyethylene (VLDPE) was used in Example 13.
  • VLDPE ultra low density polyethylene
  • the kneaded material prepared in Examples 1 to 7, and Comparative Examples 1 to 5 was charged to an experimental mold (MQFP 28 x 28) and cured for 450 seconds at a pressure of 60 kg / cm 2 at 180 ° C., while releasing the mold. was performed 30 times.
  • the kneaded material prepared in Examples 1 to 7, and Comparative Examples 1 to 5 was charged to an experimental mold (MQFP 28 x 28) and cured for 450 seconds at a pressure of 60 kg / cm 2 at 180 ° C., while releasing the mold. was performed 30 times.
  • Example 18 Example 17> Example 16> Example 15> Examples 8 to 14> Comparative Example 6> Comparative Example 10> Comparative Example 9 Smell smoke Example 19> Examples 15 to 17> Examples 8 to 14> Comparative Example 6, Comparative Example 9, and Comparative Example 10 (Example 18 had a lot of smoke, but no smell.)
  • Comparative Example 9 which does not satisfy the content range of the present invention, the cleaning power is insufficient, so that it is difficult to play a role as the cleaning rubber, and in Comparative Example 10, the filling property and the cleaning power are somewhat improved compared to Comparative Example 6. It can be confirmed, but it can be seen that the markedly inferior filling and cleaning power compared to Examples 8 to 14.
  • the rubber composition of the present invention improves the mobility in the mold of the rubber composition by the combination of specific components, and as a result, the filling property is improved, thereby solving the problem of the non-fill phenomenon of the prior art, and the deforming of the release rubber It provides an excellent effect, not only to improve the mold release property, but also to improve the cleaning power by increasing the speed at which the cleaning agent emerges from the crosslinked rubber.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

La présente invention concerne une composition de caoutchouc comprenant du caoutchouc de butadiène, du caoutchouc de monomère diène d'éthylène-propylène, du caoutchouc non réticulé contenant un additif polymère particulaire capable d'améliorer la mobilité dans le moule de la composition de caoutchouc, d'un agent de lavage ou d'une cire, d'un agent de durcissement et d'une charge inorganique.
PCT/KR2015/007971 2015-04-17 2015-07-30 Composition de caoutchouc dotée d'excellente capacité de remplissage WO2016167415A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020150054172A KR101712356B1 (ko) 2015-04-17 2015-04-17 충진성 및 탈형성이 우수한 이형 고무 조성물
KR10-2015-0054172 2015-04-17
KR1020150080928A KR101667564B1 (ko) 2015-06-09 2015-06-09 충진성 및 세정력이 우수한 세정 고무 조성물
KR10-2015-0080928 2015-06-09

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0153071B1 (ko) * 1995-12-28 1998-12-01 유현식 내열성과 내후성이 우수한 열가소성 수지조성물
US20030175449A1 (en) * 2001-08-22 2003-09-18 Gerald Edson Waterproof, durable products made from recycled rubber products
JP2007530746A (ja) * 2004-03-29 2007-11-01 ピレリ・アンド・チ・ソチエタ・ペル・アツィオーニ 細分化された形にある加硫ゴムを含む熱可塑性エラストマー材料
KR20100033540A (ko) * 2007-07-17 2010-03-30 다우 글로벌 테크놀로지스 인크. 높은 ｅｓｃｒ을 나타내고 모노비닐리덴 방향족 중합체 및 에틸렌／알파―올레핀 공중합체를 포함하는 조성물
KR20100138878A (ko) * 2008-03-31 2010-12-31 닛뽕 카바이도 고교 가부시키가이샤 금형 이형 회복용 고무계 조성물

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2633101B2 (ja) * 1991-04-12 1997-07-23 日東電工株式会社 金型再生用組成物
EP0757077A1 (fr) * 1995-08-01 1997-02-05 Advanced Elastomer Systems, L.P. Compositions élastomères thermoplastiques très molles
JP3764239B2 (ja) * 1996-12-10 2006-04-05 日東電工株式会社 半導体装置成形用金型洗浄剤組成物およびそれを用いた金型クリーニング方法
CN100473686C (zh) * 2004-07-28 2009-04-01 纳拉化学株式会社 模具洗净及脱模用橡胶组合物
JP6116789B2 (ja) * 2009-07-17 2017-04-19 日立化成株式会社 半導体装置成形用金型洗浄シートおよびそれを用いた半導体装置成形用金型のクリーニング方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0153071B1 (ko) * 1995-12-28 1998-12-01 유현식 내열성과 내후성이 우수한 열가소성 수지조성물
US20030175449A1 (en) * 2001-08-22 2003-09-18 Gerald Edson Waterproof, durable products made from recycled rubber products
JP2007530746A (ja) * 2004-03-29 2007-11-01 ピレリ・アンド・チ・ソチエタ・ペル・アツィオーニ 細分化された形にある加硫ゴムを含む熱可塑性エラストマー材料
KR20100033540A (ko) * 2007-07-17 2010-03-30 다우 글로벌 테크놀로지스 인크. 높은 ｅｓｃｒ을 나타내고 모노비닐리덴 방향족 중합체 및 에틸렌／알파―올레핀 공중합체를 포함하는 조성물
KR20100138878A (ko) * 2008-03-31 2010-12-31 닛뽕 카바이도 고교 가부시키가이샤 금형 이형 회복용 고무계 조성물

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JP2016204624A (ja) 2016-12-08
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CN106046447A (zh) 2016-10-26
JP6628222B2 (ja) 2020-01-08
CN106046447B (zh) 2020-05-19

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