WO2016167415A1

WO2016167415A1 - Rubber composition with excellent filling ability

Info

Publication number: WO2016167415A1
Application number: PCT/KR2015/007971
Authority: WO
Inventors: 이동권; 이문석
Original assignee: 주식회사 나라켐
Priority date: 2015-04-17
Filing date: 2015-07-30
Publication date: 2016-10-20
Also published as: CN106046447B; JP2016204624A; CN106046447A; TW201637808A; TWI664065B; JP6628222B2

Abstract

The present invention relates to a rubber composition comprising butadiene rubber, ethylene-propylene diene monomer rubber, non-crosslinked rubber containing a particular polymer additive capable of improving the in-mold mobility of the rubber composition, a washing agent or wax, a hardening agent, and an inorganic filler.

Description

Rubber composition with good filling

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.

As a method capable of efficiently performing such a cleaning operation, a sheet containing a cleaning component has been developed, and much research has been conducted on the composition used for producing such a sheet. 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. However, since 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.

To this end, 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. Although 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.

On the other hand, 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.

In particular, in the EMC molding process for semiconductor manufacturing, the release operation directly affects the quality of the semiconductor device. When 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.

Conventionally, in order to impart releasability to a mold, a method of mixing natural cannober wax or dimethyl silicone oil powdered in a powder state with a solvent such as nucleic acid and placing it in a high pressure spray container and spraying directly on the surface of the mold, wax to an epoxy resin compound And a method of coating a large amount of and coating it in a low pressure transfer molding method.

However, when the above methods are used, they may not be uniformly applied to the inside of the mold, thereby reducing the releasability, causing environmental pollution due to the use of a nucleic acid solvent, or excessive costs due to the low pressure transfer molding method. do.

As one solution to this problem, as in the cleaning operation, 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, There has been proposed 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.

Specifically, FIG. 1 is a schematic diagram showing a release rubber mechanism and non-fill property of a conventional rubber composition, and 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.

1 to 3, 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. When the crosslinking reaction is performed and the crosslinked rubber 130 is removed, the mold 110 is coated with the coating component 122.

However, 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.

Therefore, there is a high demand for a rubber composition that reduces manufacturing costs and provides an environment-friendly working environment when cleaning a mold or releasing agent coating, and exhibits excellent cleaning or deforming and filling properties.

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.

As will be described later, 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; And

Based on 100 parts by weight of the uncrosslinked rubber, 5 to 60 parts by weight of wax, 0.5 to 10 parts by weight of a curing agent, and 5 to 110 parts by weight of an inorganic filler and an adsorbent;

Characterized in that it comprises a.

In addition, 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

5 to 60 parts by weight of a detergent, 0.5 to 10 parts by weight of a curing agent, and 5 to 110 parts by weight of an inorganic filler and an adsorbent, based on 100 parts by weight of the uncrosslinked rubber;

Characterized in that it comprises a.

Here, 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.

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.

Outside the above range, when 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. On the other hand, when 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.

In one specific example, 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.

Outside of the above range, when the polymer melting temperature exceeds 100 ℃, 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 ℃, 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 .

In one specific example, 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. Can be.

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. Thus, copolymers of low density polyethylene (LDPE), ultra low density polyethylene (VLDPE) or monomers for polyolefins and acrylic acid monomers and their ionomers or monomers for polyolefins and acrylate monomers having a melting temperature exceeding 100 ° C. In the case of, may not be suitable for the polymer additive of the present invention.

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. , Ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA) and ionomer thereof, ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), 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).

For example, 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.

In one specific example, 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. Of course, the ethylene-propylene copolymer or ethylene-butylene copolymer satisfies the conditions of the polymer additive described above.

Substantially, 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. Here, 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.

On the other hand, 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 sulfoxide (DMS), 2- (2-aminoethylamino Ethanol (2- (2-aminoethylamino) ethanol), N-methylpyrrolidinone (NMP), 1-phenoxy-2-propanol (PGPhE), mesityl One or two or more mixtures selected from the group consisting of oxides, 4-hydroxy-4-methyl-2-pentanone, and amine alcohol compounds And methylene chloride, acetone, 2-methoxyethanol (EM), dimethyl sulfoxide (DMS), N-methylpinolidinone (NMP), 1-phenoxy-2-propanol (PGPhE), Mesityl oxide, 4-hydrocy-4-methyl-2-pentanone may be one or a mixture of two or more selected from the group consisting of.

Furthermore, 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. Thus, more specifically, a mixture of two or more of different kinds of cleaning compounds is used as the cleaning agent.

At this time, 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.

As described above, 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. When 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.

On the other hand, 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. Thus, the rubber composition may further comprise a cleaning aid, and in particular, the cleaning aid may be a nonionic surfactant.

In one example, 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.

In another example, 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.

(One)

Where

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.

In another example, 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.

[CH ₃ CH ₂ OCH ₂ (CH ₂ ) ₆ CH ₂ OH] * [CH ₄ ] * [CH ₄ ] (2)

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.

Such a cleaning aid is not known a clear mechanism, such as what interaction with the cleaning agent, but by using it with the cleaning agent, as can be seen in the experimental example described later, the cleaning power compared to their addition amount It can be seen that it is significantly improved. Therefore, 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.

Furthermore, 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. In this case, when the expansion agent is added together with the cleaning agent, 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.

When such an expanding agent is further included in the rubber composition according to the present invention, 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.

Furthermore, 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. Confirmed. 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. On the other hand, when the cleaning catalyst is 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. As such a cleaning catalyst, 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.

When the uncrosslinked rubber is cured while crosslinking occurs due to heat and pressure, the curing agent may be used as a component that induces such curing, and organic peroxides, phenol resins, and sulfur may be used. In detail, it 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-buthylvalerate), t-butylperoxybenzo T-buthylperoxybenzoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane (1,1-di-t-buthylperoxy-3,3,5-trimethylcyclohexane), dibenzoyl Peroxide (di-benzoylperoxide), bis- (2,4-dichlorobenzoyl) -peroxide (bis- (2,4-dichlorobenzoyl) -peroxide) and the like can be used. Of these, 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 content of such a curing agent, as described above, based on 100 parts by weight of the uncrosslinked rubber, 0.5 to 10 parts by weight, less than 0.5 parts by weight can not achieve the onset of curing or promotion of curing rate, than 10 parts by weight If too large, excessive crosslinking occurs, such that the tear strength is greatly reduced, and thus mechanical properties are generally lowered, which is not preferable.

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.

In some cases, 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.

Examples of 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. Among these, 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 (μm). Zeolite X type and zeolite Y type have a specific surface area (approximately 500 ㎡ / 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. On the other hand, since 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.

In addition, 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.

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.

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; 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;

5 is a photograph showing the crosslinked rubber demolded from the mold in the process of FIG.

Hereinafter, although described with reference to the drawings according to an embodiment of the present invention, this is for easier understanding of the present invention, the scope of the present invention is not limited thereto.

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.

4 to 5, 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. When 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.

At this time, unlike the conventional rubber composition, even the portion (210a) indented in the mold is sufficiently filled with the rubber composition, non-fill phenomenon does not occur, it is excellent in the de-formation as shown in Figure 5 neat The crosslinked rubber in the form is demolded from the mold.

Although the specifics of the present invention will be described in detail with reference to the following Examples, the scope of the present invention is not limited thereto.

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 200 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a wax (80 g of polyethylene, 20 g of a slipping agent) were kneaded in a kneader and a roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.87, the melting temperature is 60 ℃.

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 ℃.

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 ℃.

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 ℃.

Example 5

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 ℃.

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 300 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a wax (80 g of polyethylene, 20 g of a slipping agent) were kneaded in a kneader and a roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.87, the melting temperature is 59 ℃.

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 100 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a wax (80 g of polyethylene, 20 g of a slipping agent) were kneaded in a kneader and a roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.885, the melting temperature is 80 ℃.

Comparative Example 1

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.

Comparative Example 2

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. In this case, the density of the low density polyethylene (LDPE) is 0.921, the melting temperature is 110 ℃.

Comparative Example 3

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. .

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.

Comparative Example 5

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.

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 200 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g) was kneaded in a kneader and roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.87, the melting temperature is 60 ℃.

Example 9

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 ℃.

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 ℃.

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 ℃.

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 ℃.

Example 13

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 300 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g) was kneaded in a kneader and roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.87, the melting temperature is 59 ℃.

To 700 g of butadiene rubber (BR), 300 g of ethylene-propylene diene monomer rubber (EPDM) and 100 g of ultra low density polyethylene (VLDPE) are mixed and added, and 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), and a mixed detergent (30 g of monoethanolamine (MEA), 25 g of N-methylpyrrolidone (NMP), dimethyl sulfoxide ( DMSO) 35 g) was kneaded in a kneader and roll mill. In this case, the density of the ultra low density polyethylene (VLDPE) is 0.885, the melting temperature is 80 ℃.

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.

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 18

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.

Example 19

In order to confirm the effect of the cleaning catalyst, 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.

Comparative Example 6

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.

Comparative Example 7

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. In this case, the density of the low density polyethylene (LDPE) is 0.921, the melting temperature is 110 ℃.

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. .

Comparative Example 9

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.

Comparative Example 10

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.

Experimental Example 1

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 number of times the non-fill phenomenon occurred in this release operation was measured, and the results are shown in Table 1 below.

비고Remarks	횟수Count	비고Remarks	횟수Count
실시예 1Example 1	00	실시예 7Example 7	22
실시예 2Example 2	22	비교예 1Comparative Example 1	1212
실시예 3Example 3	00	비교예 2Comparative Example 2	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 4Example 4	1One	비교예 3Comparative Example 3	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 5Example 5	22	비교예 4Comparative Example 4	이형성 부족으로 인한 제품의 몰드내 접착력 상승. 제품 제거시 찢어짐Increasing adhesion in the mold due to lack of release. Tear when removing the product
실시예 6Example 6	1One	비교예 5Comparative Example 5	1010

Experimental Example 2

The number of times that the mold was not demolded during the release operation was measured, and the results are shown in Table 2 below.

비고Remarks	횟수Count	비고Remarks	횟수Count
실시예 1Example 1	00	실시예 7Example 7	22
실시예 2Example 2	00	비교예 1Comparative Example 1	1111
실시예 3Example 3	00	비교예 2Comparative Example 2	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 4Example 4	00	비교예 3Comparative Example 3	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 5Example 5	00	비교예 4Comparative Example 4	이형성 부족으로 인한 제품의 몰드내 접착력 상승. 제품 제거시 찢어짐Increasing adhesion in the mold due to lack of release. Tear when removing the product
실시예 6Example 6	00	비교예 5Comparative Example 5	1010

Referring to Tables 1 and 2 above, it can be seen from the results of experiments using Comparative Examples 2 and 3 that the use of additives with melting temperatures above 100 ° C. made it impossible to produce release rubber.

In addition, in the case of Examples 1 to 7, it can be seen that the filling and deformability is significantly improved compared to Comparative Example 1 without using the polymer additive.

Furthermore, in the case of Comparative Example 4, which does not satisfy the content range of the present invention, the release property is insufficient, it is difficult to produce the product, in the case of Comparative Example 5, compared to Comparative Example 1 to confirm that the degree of filling and deformability is somewhat improved However, it can be seen that the remarkably inferior filling and deformability compared to Examples 1 to 7.

Experimental Example 3

The kneaded mixtures prepared in Examples 8 to 14 and Comparative Examples 6 to 10 were charged to an experimental mold (MQFP 28 x 28) contaminated with epoxy molding compound (EMC), and were pressed for 450 seconds at a pressure of 60 kg / cm 2 at 180 ° C. While curing, a cleaning operation was performed on the mold.

The number of times non-fill phenomenon occurred during this cleaning operation was measured, and the results are shown in Table 3 below.

비고Remarks	횟수Count	비고Remarks	횟수Count
실시예 8Example 8	00	실시예 7Example 7	1414
실시예 9Example 9	22	비교예 6Comparative Example 6	1212
실시예 10Example 10	00	비교예 7Comparative Example 7	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 11Example 11	1One	비교예 8Comparative Example 8	제품 생성 불가-스코치 발생Unable to create product-generate a scratch
실시예 12Example 12	22	비교예 9Comparative Example 9	44
실시예 13Example 13	1One	비교예 10Comparative Example 10	1010

Experimental Example 4

The kneaded materials prepared in Examples 8 to 19, and Comparative Examples 6 to 10 were charged to an experimental mold (MQFP 28 x 28) contaminated with epoxy molding compound (EMC) and 450 at 60 kg / cm ² pressure at 180 ° C. The cleaning operation was performed on the mold while curing for a second. This operation was repeated until the contaminants on the mold were completely removed.

This cleaning operation was confirmed the degree of occurrence of irritating odor and fumes, and the cleaning power for the contaminants of the mold was confirmed and the results are shown in Table 4 below. The following results are averaged by performing the same method five times.

세정력Cleaning power	실시예19≥실시예18>실시예17≥실시예16≥실시예15>실시예8∼실시예14>비교예6>비교예10>비교예9Example 19> Example 18> Example 17> Example 16> Example 15> Examples 8 to 14> Comparative Example 6> Comparative Example 10> Comparative Example 9
냄새 연기Smell smoke	실시예19≥실시예15∼실시예17>실시예8∼실시예14>비교예6,비교예9,비교예10 (실시예18은 연기발생은 많았으나, 냄새는 없음.)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.)

Referring to Table 3, through the experimental results in the case of using Comparative Examples 7 and 8, it can be confirmed that the production of the cleaning rubber is not possible when using an additive with a melting temperature of more than 100 ℃.

In addition, in the case of Examples 8 to 14, it can be seen that the filling and cleaning power is significantly improved compared to Comparative Example 6 without using the polymer additive.

Furthermore, in 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.

Moreover, in the case of using the cleaning aid as in Examples 15 to 19, there are no odors and mists generated during the cleaning operation, and Examples 18 and 19 including them, rather than Example 15, which do not include the swelling agent or the cleaning catalyst. It can be seen that the cleaning power in the case of using the rubber composition according to the present invention is more excellent.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

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.

Claims

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; And

Based on 100 parts by weight of the uncrosslinked rubber, 5 to 60 parts by weight of wax, 0.5 to 10 parts by weight of a curing agent, and 5 to 110 parts by weight of an inorganic filler and an adsorbent;

Rubber composition comprising a.
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; And

5 to 60 parts by weight of a detergent, 0.5 to 10 parts by weight of a curing agent, and 5 to 110 parts by weight of an inorganic filler and an adsorbent, based on 100 parts by weight of the uncrosslinked rubber;

Rubber composition comprising a.
The rubber composition according to any one of claims 1 to 3, wherein the uncrosslinked rubber contains 10 to 30 parts by weight of a polymer additive.
The rubber composition according to any one of claims 1 to 3, wherein the polymer additive has a melting temperature of 90 ° C or lower.
The polymer additive according to any one of claims 1 to 3, wherein the polymer additive comprises a polyolefin-based elastomer or a copolymer composed of a monomer for polyolefin and an acrylic acid monomer and an ionomer or monomer for polyolefin thereof. A rubber composition, characterized in that the copolymer (copolymer) consisting of acrylate monomers.
The method of claim 5, wherein the polyolefin-based elastomer, Ultra low density polyethylene (VLDPE); Polybutene; Poly-4-methyl-1-pentene (TPX); Copolymers of propylene, butene, hexene and / or octene with ethylene; And at least one selected from the group consisting of olefinic thermoplastic elastomers.
The copolymer of claim 5, wherein the copolymer is an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer (EMAA), an ionomer of an ethylene-methacrylic acid copolymer, an ethylene-methacrylic acid copolymer ( EMA), ethylene-ethylacrylate copolymer (EEA), ethylene-alkylacrylate-acrylic acid copolymer, ethylene-alkylmethacrylate-methacrylic acid copolymer, ethylene-butylacrylate copolymer (EBA), ethylene-vinyl Rubber composition, characterized in that at least one selected from the group consisting of acetate copolymers (EVA).
The method of claim 5, wherein the copolymer is obtained by the reaction of 60 to 96% by weight of the monomer for polyolefin and 4 to 40% by weight of the acrylic acid or acrylate or vinyl acetate monomer based on 100% by weight of the copolymer Rubber composition.
The rubber composition according to claim 1, wherein the polymer additive is an ethylene-propylene copolymer or an ethylene-butylene copolymer.
The rubber composition according to claim 1, wherein the wax is in the form of a mixture of polyethylene and a slip agent having a weight average molecular weight of 200 to 3000.
3. The rubber composition of claim 2, wherein the detergent is a mixture of different cleaning compounds.
3. The rubber composition of claim 2, wherein the rubber composition further comprises a cleaning aid.
3. The rubber composition of claim 2, wherein the rubber composition further comprises an expanding agent.
3. The rubber composition according to claim 2, wherein the rubber composition further comprises a cleaning catalyst of strong acid or strong alkali.
The rubber composition according to any one of claims 1 to 2, wherein the curing agent is an organic peroxide.
The method of claim 1, wherein the inorganic filler is one or two or more mixtures selected from the group consisting of silica, talc, alumina, potassium carbonate, calcium carbonate, aluminum hydroxide, titanium oxide, carbon black. Rubber composition, characterized in that.
Mold release rubber sheet, characterized in that the rubber composition according to any one of claims 1 to 2.