KR20180014806A - Thermoplastic Silicone Elastomer and Method for the Preparation Thereof - Google Patents

Abstract

The present invention relates to a thermoplastic silicone elastomer and a preparation method thereof, and more specifically, to a thermoplastic silicone elastomer having low hardness and excellent mechanical properties such as tensile strength, tear strength, abrasion resistance and permanent compression strain, and having smooth surface properties without surface stickiness; and to a preparation method of the thermoplastic silicone elastomer.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic silicone elastomer,

More particularly, the present invention relates to a thermoplastic silicone elastomer having a low hardness and excellent mechanical properties such as tensile strength, tear strength, abrasion resistance, permanent compression strain, and smooth surface characteristics ≪ / RTI > and a process for their preparation.

Thermoplastic elastomers (TPE) are polymeric materials having both plastic and rubbery properties. They have elastomeric and mechanical properties, but can be reworked at elevated temperatures unlike conventional thermoset rubbers. Thermoplastic elastomers are greatly advantageous over chemically cross-linked rubbers because they enable recycling of components due to such reworkability, which greatly reduces scuffing.

In general, two major types of thermoplastic elastomers are known. The block copolymer thermoplastic elastomer not only contains a 'hard' plastic segment having a melting point or glass transition temperature higher than the ambient temperature, but also a 'soft' polymer segment having a melting point or glass transition temperature much lower than room temperature. In such a system, the hard segments aggregate to form a different microphase and act as a physical bridge to the soft phase, imparting rubber-like properties at room temperature. At elevated temperatures, the hard segment is melted or softened to flow the copolymer and can be processed like a conventional thermoplastic resin.

Alternatively, a thermoplastic elastomer, also referred to as a simple mixture (physical mixture), can be obtained by homogeneously mixing the elastomeric component with the thermoplastic resin. Even when the elastomer component is crosslinked during the mixing process, a thermoplastic elastomer known as Thermoplastic vulcanizate (TPV) is produced in the art. Since the crosslinked elastomeric phase of the thermoplastic vulcanizate is insoluble and inflexible at elevated temperatures, thermoplastic vulcanizates generally have improved oil resistance and solvent resistance as well as reduced permanent compression strain compared to simple mixtures.

Typically, the thermoplastic vulcanizate is formed by a process known as dynamic vulcanization wherein the elastomer and the thermoplastic matrix are mixed and the elastomer is cured during the mixing process under the aid of a crosslinking agent and / or catalyst. Many of these thermoplastic vulcanizates are known in the art, some of which may be organic polymers in which the crosslinked elastomer component is a silicone polymer while the thermoplastic component is not a silicone.

On the other hand, the thermoplastic polyester elastomer (TPEE) has excellent impact resistance at low temperatures, and is excellent in oil resistance, chemical resistance, and mechanical properties. Therefore, the thermoplastic urethane elastomer and the thermoplastic polyamide elastomer, which are widely used in the electric / It is an elastic body used for parts of the system. As such thermoplastic polyester elastomer, a polyetherester-based block copolymer resin composition is typical and is mainly produced by a polymerization process.

Such a polyetherester elastomer has long been used as a hard segment of polybutylene terephthalate (PBT) as a hard segment, a polyoxyalkylene (PTMEG) polyoxyalkylene series as a hard segment, It has been known that it is manufactured as a segment and has been practically used.

Generally, a polymer material having low hardness is widely used in electronic goods such as a smart phone, a smart watch, a smart band, an earphone, or a remote control, and sports and leisure goods.

Various attempts have been made to produce a low-hardness elastomer composition containing a phthalate plasticizer and a non-phthalate plasticizer in a polyetherester elastomer for lowering the hardness of the polyetherester elastomer.

Korean Patent Laid-Open No. 2004-0034769 discloses an elastomer having low hardness. However, a phthalate plasticizer having environmental haze is used. In Korean Patent Publication No. 2000-0060104, a mixture of an elastomer and a plasticizer is mixed with a low- However, in the case of the polyetherester elastomer, when a molded product is injected after mixing with a general plasticizer, there is a phenomenon that plasticizer is exposed to the outside of the molded product after a certain period of time. In Korean Patent Laid-Open Nos. 2000-007680 and 1997-0059209, polyvinyl chloride and a plasticizer were used, but the materials were harmful.

As described above, the polyetherester elastomer belongs to an engineering elastomer such as a conventional thermoplastic polyurethane or a thermoplastic polyamide ester, and although it has excellent physical properties, it can not realize a low hardness and thus has a limited application.

Thus, the present inventors have discovered a process for the production of a reworkable thermoplastic silicone elastomer prepared from a polyetherester elastomer and a silicone elastomer by a dynamic vulcanization process using a radical initiator, a crosslinking aid and a compatibilizer, without using a plasticizer. The thermoplastic silicone elastomer produced by such a production method has lower hardness and excellent thermal properties while minimizing deterioration of mechanical properties than conventional polyether ester elastomers.

Korean Patent Publication No. 2004-0034769 Korean Patent Publication No. 2000-0060104 Korean Patent Publication No. 2000-007680 Korean Patent Publication No. 1997-0059209

The main object of the present invention is to solve the above-mentioned problems and to provide a thermoplastic resin composition which has low hardness and excellent mechanical properties such as tensile strength, tear strength, abrasion resistance and permanent compression strain and has smooth surface characteristics without surface stickiness A process for producing the elastomer and a thermoplastic silicone elastomer produced by the process.

(I) a diorganosiloxane rubber having a degree of plasticity of 30 or more as measured by ASTM D926 measurement method and having at least two alkenyl groups in the molecule (A), a silicone elastomer resin (B), a crosslinking auxiliary (C), and an epoxy functional polysiloxane, a glycidyl ester polymer and an organofunctional (Ii) mixing a radical initiator (E) with the mixture of step (i), and (iii) mixing the (ii) at least one compatibilizing agent selected from the group consisting of ) Vulcanizing the diorganosiloxane rubber (A ') in a mixture of at least one diorganosiloxane rubber (A').

In a preferred embodiment of the present invention, the silicone base (A) may be characterized in that the reinforcing filler (A ") is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the diorganosiloxane rubber (A ' have.

In a preferred embodiment of the present invention, the step (i) comprises 2 to 60 wt% of the silicone base (A), 35 to 95 wt% of the polyetherester elastomer resin (B), 0.5 to 10 wt% And 0.5 to 10% by weight of the compatibilizing agent (D) are melted and mixed.

In a preferred embodiment of the present invention, the step (ii) may be performed by mixing 0.1 to 5% by weight of the radical initiator (E) based on the total weight of the mixture of the step (i).

In one preferred embodiment of the present invention, the silicon-based diorganopolysiloxane (A ') is a copolymer comprising a dimethylsiloxane unit and a methylvinylsiloxane unit or a copolymer consisting of a dimethylsiloxane unit and a methylhexenylsiloxane unit , And the silicon-based reinforcing filler (A ") is pyrolytic silica.

In a preferred embodiment of the present invention, the polyetherester elastomer resin (B) is a polyetherester elastomer resin, wherein the ester forming derivative of the dicarboxylic acid or dicarboxylic acid constituting the hard segment of the polyetherester elastomer is terephthalic acid, isophthalic acid, naphthalene- , 6-dicarboxylic acid, diethyl terephthalate, and dimethyl terephthalate.

In one preferred embodiment of the present invention, the polyetherester elastomer resin (B) is a polyetherester elastomer resin wherein the diol constituting the hard segment of the polyetherester elastomer is at least one selected from the group consisting of ethylene glycol, 1,3-propylene diol, 1,4-butanediol, Hexamethylene glycol, heptane methylene glycol, and 1,4-cyclohexane dimethanol.

In a preferred embodiment of the present invention, the polyetherester elastomer resin (B) is a polyetherester elastomeric resin wherein the polyalkylene oxide which constitutes the soft segment of the polyetherester elastomer is selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and poly And oxyoxymethyleneglycol. ≪ Desc / Clms Page number 7 >

In one preferred embodiment of the present invention, the polyetherester elastomer resin (B) may be characterized in that the content of the polyalkylene oxide (polyalkylene oxide) constituting the soft segment of the polyetherester elastomer is 20 to 80% by weight have.

In one preferred embodiment of the present invention, the crosslinking auxiliary (C) is selected from the group consisting of TAIC (Trially Isocyanurate), TAC (Triallyl cyanurate), TMPTMA (Trimethylopropane Trimethacrylate), TMPTA (Trimethylolpropane Triacrylate), ZDA (Zinc diacrylate) And at least one selected from the group consisting of

In one preferred embodiment of the present invention, the epoxy functional polysiloxane has an epoxy index of 0.35 Eq / kg to 5.5 Eq / kg.

In one preferred embodiment of the present invention, the epoxy-functional polysiloxane may be at least one selected from compounds represented by the following formulas (3) and (4).

(3)

[Chemical Formula 4]

In the above formulas (3) and (4), R is an aldehyde group, and n and m are each independently an integer of 10 to 200.

In one preferred embodiment of the present invention, the glycidyl ester polymer is characterized in that it comprises a first repeating unit derived from at least one glycidyl ester monomer and a second repeating unit derived from at least one? -Olefin monomer can do.

In a preferred embodiment of the present invention, the glycidyl ester polymer may be characterized in that the glycidyl ester monomer is glycidyl acrylate or glycidyl methacrylate.

In one preferred embodiment of the invention, the glycidyl ester polymer is selected from the group consisting of an olefin-glycidyl (meth) acrylate polymer, an olefin-vinyl acetate-glycidyl (meth) acrylate polymer, and an olefin-glycidyl ) Acrylate-alkyl (meth) acrylate polymers.

In one preferred embodiment of the present invention, the glycidyl ester polymer is characterized by being a random ethylene / acrylic acid ester / glycidyl methacrylate copolymer or random ethylene / acrylic acid ester / glycidyl methacrylate terpolymer .

In one preferred embodiment of the present invention, the organofunctional grafted polyolefin is a homopolymer of an olefin and an organofunctional grafting monomer, a copolymer of an organofunctional grafting monomer and a terpolymer of an organofunctional grafting monomer And the like.

In one preferred embodiment of the present invention, the organofunctional grafting monomer comprises at least one organic functional group selected from the group consisting of carboxylic acid, carboxylic acid salt, amide, imide, ester, anhydride, epoxy, alkoxy and oxazoline Containing ethylenic unsaturated hydrocarbon.

In one preferred embodiment of the present invention, the organofunctional grafted polyolefin is selected from the group consisting of poly (ethylene-co-vinyl acetate) grafted maleic anhydride, polypropylene grafted maleic anhydride, polyethylene-polypropylene grafted male Maleic anhydride grafted EPDM rubber, maleic anhydride grafted SEBS copolymer, and the like.

In a preferred embodiment of the present invention, the radical initiator (E) is an organic peroxide.

Another embodiment of the present invention provides a thermoplastic silicone elastomer produced by the process for producing the thermoplastic silicone elastomer.

The process for producing a thermoplastic silicone elastomer according to the present invention is a process for producing a thermoplastic silicone elastomer having a low hardness and having a smooth surface property with excellent mechanical properties such as tensile strength, tear strength, abrasion resistance and permanent compression strain, It can be economically manufactured and can be usefully applied to parts and members in various fields such as automobiles, electronic appliances, electric power, electric wires, home appliances, medical, sports, and the like.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

(I) a diorganosiloxane rubber (A ') having a degree of plasticity of 30 or more as measured by the ASTM D926 measurement method and having at least two alkenyl groups in the molecule, and a reinforcing filler (A "), (A), a polyetherester elastomer resin (B), a crosslinking assistant (C), and an epoxy functional polysiloxane, a glycidyl ester polymer, and an organofunctional grafted polyolefin (Ii) mixing the radical initiator (E) with the mixture of step (i), and (iii) mixing the diorganosiloxane rubber ( A ') of the thermoplastic silicone elastomer.

More specifically, the process for preparing a thermoplastic silicone elastomer according to the present invention comprises homogeneously mixing a polyetherester elastomer resin and a silicone elastomer using a crosslinking assistant and a compatibilizing agent without using a plasticizer, and applying a radical initiator thereto By dynamic vulcanization, a thermoplastic silicone elastomer having low hardness and excellent surface properties such as tensile strength, tear strength, abrasion resistance, permanent compression strain and mechanical properties without surface stickiness can be economically produced.

Hereinafter, the present invention will be described in detail.

The thermoplastic silicone elastomer according to the present invention is produced by first preparing a diorganosiloxane rubber (A ') having a degree of plasticity of 30 or more as measured by the ASTM D926 measurement method and having at least two alkenyl groups in the molecule and a reinforcing filler (A (B); the crosslinking auxiliary (C); and the compatibilizer (D) are melted and mixed at 150 to 230 ° C for 10 to 60 minutes [(i) ].

If the melt mixing conditions of the silicone base (A), the polyetherester elastomer resin (B), the crosslinking aid (C) and the compatibilizing agent (D) are less than 150 ° C or less than 10 minutes, The ester elastomer is not melted and the compatibility with the silicone base is low, so that the surface properties are deteriorated and the properties are deteriorated. When the temperature is more than 230 ° C. or more than 60 minutes, the polyetherester elastomer resin May be thermally decomposed to deteriorate physical properties.

The silicone base (A) is a homogeneous mixture of the diorganosiloxane rubber (A ') and the reinforcing filler (A ").

The diorganosiloxane rubber (A ') may be a high-gloss polymer or copolymer having two or more, preferably two to twenty, alkenyl groups in the molecule. The alkenyl group is specifically exemplified by vinyl, allyl, butenyl, pentenyl, hexenyl, decenyl, etc., and preferably the alkenyl group may be vinyl or hexenyl.

The position of the alkenyl functional group of the diorganosiloxane rubber (A ') is not critical, and it may be bonded at the molecular chain terminal, at a position other than the terminal end in the molecular chain, or at both positions, The presence in the diorganosiloxane rubber in an amount of 0.001 to 3% by weight, preferably 0.01 to 1% by weight, .

The residual (i.e., non-alkenyl) silicon-bonded organic groups in the diorganosiloxane rubber (A ') are independently selected from hydrocarbon or halogenated hydrocarbon groups that do not contain aliphatic unsaturation. These include alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl, cycloalkyl groups such as cyclohexyl and cycloheptyl, aryl groups of 6 to 12 carbon atoms, And xylyl), aralkyl groups having 7 to 20 carbon atoms (e.g., benzyl and phenethyl), and halogenated alkyl groups having 1 to 20 carbon atoms (e.g., 3,3,3-trifluoropropyl and chloromethyl) . Of course, these groups will understand that the diorganosiloxane rubber (A ') has a lower glass transition temperature (or melting point) than room temperature, so that the rubber is selected to be elastomeric. It is preferable that at least 50 mol%, more preferably at least 90 mol%, of the non-unsaturated silicon-bonded organic groups in component (A ') consist of methyl.

Accordingly, the diorganosiloxane rubber (A ') may be a homopolymer or a copolymer containing such an organic group. Examples thereof include rubbers comprising dimethylsiloxane units and methylvinylsiloxane units; A rubber comprising a dimethylsiloxane unit and a methylhexenylsiloxane unit; A rubber comprising a dimethylsiloxy unit and a phenylmethylsiloxy unit; A rubber comprising a dimethylsiloxy unit and a diphenylsiloxy unit; And rubbers comprising dimethylsiloxy units, diphenylsiloxy units, and phenylmethylsiloxy units, including a dimethylsiloxane unit and a methylvinylsiloxane unit; A rubber comprising a dimethylsiloxane unit and a methylhexenylsiloxane unit is preferred. In addition, the molecular structure is not critical, and linear and partially branched straight chains can be exemplified, and a linear structure is preferred.

Specific examples of such diorganosiloxane rubbers (A ') include trimethylsiloxy-terminated dimethylsiloxane-methylhexenylsiloxane copolymers; Dimethylhexenylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxane copolymer; Trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer; Trimethylsiloxy-terminated methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer; Dimethylvinylsiloxy-terminated dimethylpolysiloxanes; Dimethylvinylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer; Dimethylvinylsiloxy-terminated methylphenyl polysiloxanes; Dimethylvinylsiloxy-terminated methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer; And similar copolymers in which one or more terminal groups are dimethylhydroxy siloxane. Preferred diorganosiloxane rubbers (A ') for use at low temperatures include methylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers and diphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers, especially those having a molar content of about 93 mol %.

The diorganosiloxane rubber (A ') may also be composed of a combination of two or more organopolysiloxanes. More preferably, the diorganosiloxane rubber (A ') is a homopolymer of polydimethylsiloxane wherein each end of the molecule is terminated with a vinyl group, or a homopolymer containing at least one vinyl group along the main chain.

On the other hand, the diorganosiloxane rubber (A ') may have a degree of plasticity of 30 or more as measured by ASTM (Tested by the American Society for Testing and Materials) method D926. The degree of plasticity is defined as the thickness (mm) × 100 of the specimen after a compressive load of 49 Newtons is applied to the cylindrical specimen having a volume of 2 cm ³ and a height of 10 mm at 25 ° C for 3 minutes.

If the degree of plasticization of the diorganosiloxane rubber (A ') is less than 30, the thermoplastic silicone elastomer produced by the dynamic vulcanization according to the present invention exhibits poor uniformity and has a high silicone content (for example, 50 to 70 % By weight), there is a region consisting substantially of only silicon and a region substantially consisting of only thermoplastic resin, and the composition is fragile and fragile. These rubbers are much more viscous than the silicone fluids used in the prior art. For example, the silicone tested in the aforementioned U.S. Patent No. 4,500,688 has a viscosity upper limit of 100,000 cS (0.1 m ² / s), and the plasticity of such low viscosity fluids is not easily measured by ASTM D926, It is determined that the degree of oxidation corresponds to about 24.

Although there is no absolute upper limit of the plasticity of the diorganosiloxane rubber (A '), if the value is generally limited in consideration of the workability in a conventional mixing apparatus, the degree of plasticization is preferably 100 to 200, and most preferably 120 to 185 Lt; / RTI >

Since the process for producing the unsaturated group-containing diorganosiloxane rubber (A ') having high illuminance is well known, a specific manufacturing method will be omitted in the present specification. For example, conventional methods for preparing alkenyl functional polymers include base-catalyzed equilibrium of cyclic and / or linear diorganopolysiloxanes in the presence of similar alkenyl functional species.

On the other hand, the reinforcing filler (A ") is a finely divided filler known to strengthen the diorganosiloxane rubber (A ') such as pyrolytic silica, precipitated silica, silica airgel, titanium dioxide having a specific surface area of 50 m ² / And are selected from finely divided thermally stable minerals.

Particularly, pyrolytic silica is a preferable reinforcing filler based on a high specific surface area capable of reaching 450 m ² / g, and pyrolytic silica having a specific surface area of 50 to 400 m ² / g, preferably 200 to 380 m ² / g, , And the surface is treated to be hydrophobic, as is typically done in the silicone rubber field. This treatment can be carried out by reacting silica with a liquid organosilicon compound containing a hydrolyzable precursor of silanol groups or silanol groups.

Compounds used as filler treating agents, also known as anti-creeping agents or plasticizers in the silicone rubber field include low molecular weight liquid hydroxy- or alkoxy-terminated polydiorganosiloxanes, hexaorganodisiloxane, cyclodimethyl Silazane, hexaorganodisilazane, and the like. The treating compound has an average degree of polymerization (DP) of 2 to about 100, preferably about 2 to about 10, and is used in an amount of about 5 to 50 parts by weight based on 100 parts by weight of the silica filler. In addition, when the diorganosiloxane rubber (A ') is the preferred vinyl functional or hexenyl functional polydimethylsiloxane, such a treating agent is preferably a hydroxy-terminated polydimethylsiloxane.

The reinforcing filler (A ") is used in an amount of 5 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the diorganopolysiloxane rubber (A '). (A ') are mixed homogeneously to prepare a silicone base A. If the reinforcing filler (A' ') is mixed in an amount of less than 5 parts by weight based on 100 parts by weight of the diorganopolysiloxane rubber (A') , There is no effect of increasing the strength and improving the thermal properties, and if it exceeds 200 parts by weight, the permanent compression strain of the reinforcing filler may be lowered.

In the present invention, the content of the silicone base (A) is 2 to 60% by weight, preferably 2 to 50% by weight based on the total weight of the composition. When the content is less than 2% by weight, an elastic body When the content is more than 60% by weight, the content of the silicon base increases and the thermoplastic properties deteriorate.

In the present invention, the polyetherester elastomer resin (B) is composed of a hard segment composed of a short chain polyester and a soft segment composed of a long chain polyester. The hard segment comprises an aromatic dicarboxylic acid and a short chain diol component, and the soft segment is composed of an aromatic dicarboxylic acid and a polyalkylene oxide component. That is, in summary, the polyetherester elastomer resin is synthesized from the following three raw materials. An aromatic dicarboxylic acid component which is an aromatic dicarboxylic acid or an ester forming derivative thereof, an aliphatic diol having 2 to 10 carbon atoms or an alicyclic diol and a polyalkylene oxide long chain diol.

The aromatic dicarboxylic acid that can be used in the present invention may be terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, or 4,4'-diphenoxyethane Dicarboxylic acid, and the ester-forming derivative of an aromatic dicarboxylic acid is at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, diethyl terephthalate, diethyl isophthalate, diethyl phthalate, di- Diisopropyl terephthalate, di-t-butyl terephthalate, butyl benzyl terephthalate, diethyl 2,6-naphthalene-dicarboxylate, diethyl 2,7-naphthalene dicarboxylate , Or dimethyldiphenyl-4,4'-dicarboxylate. Preferred examples of the aromatic dicarboxylic acid and its ester-forming derivative include at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, dimethylterephthalate and diethyl terephthalate .

The content of the aromatic dicarboxylic acid and the ester-forming derivative thereof used in the present invention is preferably 20 to 70% by weight based on the weight of the polyetherester elastomer. When the content is more than 70% by weight, the hardness of the composition of the present invention is increased. When the content is less than 20% by weight, the synthesis time is long.

The diol component of the polyetherester elastomer of the present invention is at least one diol selected from the group consisting of aliphatic diols having 2 to 10 carbon atoms and alicyclic diols. Preferably an aliphatic diol such as ethylene glycol, 1,3-propylene diol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol or heptane methylene glycol and an alicyclic diol of 1,4-cyclohexane dimethanol And most preferably ethylene glycol (m = 2) and 1,4-butanediol (m = 2), wherein m is an integer of 2 to 10, 4) is used.

[Chemical Formula 1]

HO- (CH _{2) m} -0H

In the above formula (1), m is an integer of 2 to 10.

On the other hand, the polyalkylene oxide (polyalkylene oxide) component of the polyetherester elastomer of the present invention uses a compound represented by the following formula (2) wherein m 'is 2 to 10.

(2)

HO - [- (CH ₂ ) _{m '} -O-] _n -H

M 'is an integer of 2 to 10, and n is an integer of 4 to 20.

The preferred polyalkylene oxide component is selected from the group consisting of polyoxyethylene glycol (PEG), polyoxypropylene glycol, polyoxyterteramethyleneglycol (PTMG) and polyoxyoctamethylene glycol At least one selected can be used. When PTMG, a long-chain diol component, is used, the polyetherester elastomer exhibits excellent elasticity and elastic recovery properties, low permanent compression strain and low temperature impact strength. PEG exhibits a low elastic recovery rate, but exhibits excellent performance in heat resistance.

The content of the polyalkylene oxide used in the present invention is preferably 20 to 80% by weight based on the weight of the polyetherester elastomer. When the content is less than 20% by weight, the hardness of the composition of the present invention becomes high, and when it is more than 80% by weight, the time for synthesis becomes long.

The molecular weight of the polyetherester elastomer resin (B) of the present invention is not limited, but a commercialized polyetherester elastomer resin having a weight average molecular weight of 200 to 3,000 g / mol is used. In particular, a weight average molecular weight of 500 to 2000 g / mol is used, more preferably 1000 to 2000 g / mol.

Generally, the hard segment of the polyetherester elastomer is composed of a short chain ester. The soft segment of the polyetherester elastomer is comprised of a long chain ester and the end of the polyether portion of the long chain ester is linked to the dicarboxylic acid via an ester linkage so that the soft segment and the hard segment are connected together. In the present invention, for convenience, the soft segment is defined as comprising an ester linkage at the end of its polyether moiety. Specifically, it is composed of a hard segment composed of a polyetherester elastomer, i.e., polybutylene terephthalate, and a soft segment composed of polyoxytetramethylene ether glycol (PTMG).

The polyetherester elastomer resin (B) is 35 to 95% by weight, preferably 50 to 80% by weight, based on the total weight of the mixture. If the content of the polyetherester elastomer resin is less than 35% by weight, thermoplastic properties may not be exhibited. If the content of the polyetherester elastomer resin exceeds 95% by weight, the content of the silicone rubber may fall and the silicone property may not be exhibited. .

In the present invention, the crosslinking auxiliary (C) may be included for the purpose of increasing crosslinking efficiency during crosslinking, uniform crosslinking, and improving compatibility with a silicon substrate.

Examples of the crosslinking auxiliary (C) include trially isocyanurate (TAIC), trially cyanurate (TAC), trimethylopropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), zinc diacrylate (ZDA), and Zinc dimethacrylate And preferably one or more of TAIC and ZDA can be used.

The crosslinking auxiliary (C) has excellent crosslinking efficiency during use, uniform crosslinking is performed, and compatibility with the silicone base (A) during crosslinking can be further improved.

The content of the crosslinking assistant (C) may be 0.5 to 10% by weight, preferably 1 to 5% by weight based on the total weight of the mixture. If the amount of the crosslinking aid is less than 0.5% by weight, the crosslinking efficiency may be lowered. If the amount is more than 10% by weight, the crosslinking density may be too high, resulting in poor processability.

In the present invention, the compatibilizer (D) is used for increasing the compatibility between the silicone base (A) and the polyetherester elastomer resin (B), and 0.5 to 10% by weight based on the total weight of the composition can be used , Preferably 1 to 5% by weight in terms of compatibility. If the compatibilizer (D) is used in an amount of less than 0.5% by weight based on the total weight of the composition, the compatibility between the desired polyetherester elastomer resin (B) and the silicone base (A) On the other hand, if the content of the polyetherester elastomer resin (B) exceeds 10 wt%, the compatibility of the polyetherester elastomer resin (B) with the silicone base (A) is excellent, but the production cost may be increased due to an increase in price.

The compatibilizing agent (D) is preferably a polyfunctional polysiloxane, a glycidyl ester polymer, and an organofunctional grafted polyolefin in terms of compatibility between the polyetherester elastomer resin (B) and the silicone base (A) It may be at least one selected.

The epoxy functional polysiloxane may be represented by, for example, the following formulas (3) and (4), and the epoxy index of the epoxy functional polysiloxane may be 0.35 to 5.5 Eq / kg. If the epoxy index is less than 0.35 Eq / kg, the function as a compatibilizing agent may be deteriorated. If the epoxy index is more than 5.5 Eq / kg, the crosslinking density may be high and moldability may be deteriorated.

(3)

[Chemical Formula 4]

In the above formula 3 and 4, and R is an aldehyde group, n and m is an integer from 10 to 200 each independently, preferably, R is _{-CH 2 CH 2 CH 2 OCH 2} - , and, n and m are each independently It is an integer from 50 to 150.

In addition, the glycidyl ester polymer is defined as a polymer comprising repeating units derived from one or more glycidyl ester monomers. The glycidyl ester polymer may be a homopolymer, a copolymer or a terpolymer. The glycidyl ester monomer of the glycidyl ester polymer is a glycidyl ester of an ethylenically unsaturated carboxylic acid (e.g., acrylic acid, methacrylic acid and itaconic acid), and examples thereof include glycidyl acrylate, Cidyl methacrylate, and glycidyl itaconate.

Representative examples of glycidyl ester polymers suitable for use in the present invention are the glycidyl esters described in U.S. Patent No. 5,981,661, which is incorporated herein by reference as a glycidyl ester impact modifier, wherein the glycidyl ester polymer comprises one or more glycidyl And a second repeating unit derived from a first repeating unit derived from an ester monomer and at least one? -Olefin monomer (e.g., ethylene, propylene, 1-butene, 1-pentene). Preferably, the glycidyl ester monomer is glycidyl acrylate or glycidyl methacrylate. Suitable glycidyl ester polymers may optionally contain repeat units derived from one or more other monoethylenically unsaturated monomers copolymerizable with glycidyl ester monomers in minor amounts, i.e., up to about 50% by weight.

The term " monoethylenically unsaturated " as used herein means having one ethylenic unsaturation position per molecule. Suitable copolymerizable monoethylenically unsaturated monomers include, for example, vinylaromatic monomers such as styrene and vinyltoluene, vinyl esters such as vinyl acetate and vinyl propionate, and (C1-C20) alkyl (meth) Acrylates (e.g., butyl acrylate, methyl methacrylate, cyclohexyl methacrylate).

As used herein, the term "(C1-C20) alkyl" means a straight or branched alkyl group having from 1 to 20 carbon atoms per group such as methyl, ethyl, decyl, eicosyl, cyclohexyl, Methacrylate " refers collectively to an acrylate compound and a methacrylate compound. Suitable glycidyl ester copolymers can be prepared, for example, by copolymerization initiated with conventional free radicals.

More preferred glycidyl ester polymers as compatibilizers in the present invention are olefin-glycidyl (meth) acrylate polymers, olefin-vinyl acetate-glycidyl (meth) acrylate polymers, and olefin-glycidyl Acrylate-alkyl (meth) acrylate polymers. Most preferably, a random ethylene / acrylic acid ester / glycidyl ether such as LOTADER ^占 AX 8900 resin, Rotador ^占 AX 8930 and LOTADER ^占 GMA product marketed by Arkema as Rotador ^占 8840, ≪ / RTI > dime methacrylate copolymer or terpolymer.

On the other hand, organofunctional grafted polyolefins are homopolymers, copolymers or terpolymers of olefins and organofunctional grafting monomers. Representative examples of suitable olefins include ethylene, propylene, butylene and the like; Olefin mixtures, e. G. Mixtures of ethylene, propylene and dienes, so-called EPDM. The olefin may also be selected from C5-C20 hydrocarbon alpha-olefins, vinyl acetate, alkyl acrylates or alkyl methacrylates and the alkyl group may be methyl, ethyl, propyl, butyl, and the like.

Suitable examples of the hydrocarbon? -Olefin include 1-hexene, 1-octene and 1-decene, and examples of the alkyl group of the alkyl acrylate include methyl, ethyl, propyl and butyl. Organofunctional grafting monomers may be selected from ethylenically unsaturated hydrocarbons containing organic functional groups such as carboxylic acids, carboxylic acid salts, amides, imides, esters, anhydrides, epoxies, alkoxy and oxazolines. The oxazoline group is a compound represented by the formula (6).

[Chemical Formula 6]

In the above formula (6), the ring may contain at least one substituent selected from a hydrocarbon group having 1 to 4 carbon atoms.

Examples of the ethylenically unsaturated hydrocarbon containing carboxylic acid and anhydride include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride Acid anhydrides) or citraconic anhydride, nadic anhydride, myristic acid anhydride and tetrahydrophthalic anhydride, with maleic anhydride being particularly preferred. Examples of such unsaturated acid derivatives are salts, amides, imides and esters, such as monosodium malate, disodium malate, acrylamide, maleimide, glycidyl methacrylate and dimethyl fumarate. Examples of the epoxy functional monomer include allyl glycidyl ether, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, and 1,2-epoxy-5-hexene. The oxazoline functional monomer is vinyl oxazoline. Preferred grafting monomers for use in organofunctional grafted polyolefin compatibilizers are selected from maleic anhydride and maleic anhydride derivatives.

Preferred examples of the organic functional grafted polyolefin compatibilizer include poly (ethylene-co-vinyl acetate) -grafted maleic anhydride, polypropylene-grafted maleic anhydride, polyethylene-polypropylene-grafted Maleic anhydride, grafted maleic anhydride, maleic anhydride grafted EPDM rubber, maleic anhydride grafted SEBS (styrene-ethylene / butene-styrene triblock copolymer), and most preferably maleic anhydride from grafted EPDM, or the same company is a maleic anhydride grafted polypropylene, which is commercially available as Fusabond ^®. The content of unsaturated grafting monomers may be from 0.1 to 10% by weight, preferably from 0.3 to 4% by weight, in the grafted polymer.

Then, the radical initiator (E) is mixed with the mixture of the silicon base (A), the polyetherester elastomer resin (B), the crosslinking auxiliary (C) and the compatibilizing agent (D).

The radical initiator (E) initiates the vulcanization crosslinking reaction using the thermally activated organic peroxide. The organic peroxide is advantageous for the vulcanization crosslinking reaction by lowering the processing temperature in the vulcanization crosslinking reaction.

An example of such an organic peroxide is a dialkyl peroxide, a ketal peroxide, an aralcohol peroxide, a peroxide ether or a peroxide ester. Examples of suitable peroxides for use in the peroxide curing system include 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, di-tert-butylperoxide, 2,5 (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, butyl 4,4-di (tert-butylperoxy) - (tert-butylperoxy) valerate, 1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxybenzoate, 2,5-bis (tert-butylperoxy) -2,5-dimethylbenzoyl peroxide, di-2-methylbenzoyl peroxide, Dimethyl hexane, or mixtures thereof.

The content of the radical initiator (E) is preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight based on the total weight of the silicone base (A), the polyetherester elastomer resin (B), the crosslinking aid (C) If the content is less than 0.1% by weight, the crosslinking property may be deteriorated and the mechanical properties may be deteriorated. If the content is more than 5% by weight, the crosslinking reaction may occur excessively to cause color discoloration or decomposition, The problem of falling may occur.

When the radical initiator (E) is mixed as described above, the diorganosiloxane rubber (A ') is vulcanized in the mixture to prepare a thermoplastic silicone elastomer (step (iii)). At this time, the vulcanization is performed at 100 to 200 ° C, preferably 150 to 190 ° C.

The process for preparing a thermoplastic silicone elastomer according to the present invention may be carried out by adding (i) additives known in the art such as UV stabilizers, antioxidants, heat stabilizers, processing aids and pigments to the object of the present invention Or in step (ii).

Among these additives, IRGANOX (registered trademark) 259 (hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), IRGANOX (registered trademark) 1010 (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid, 2,2-bis [[3- [3,5- 1,3-propanediyl ester), IRGANOX (registered trademark) 1076 (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate), Irganox (registered trademark) 1098 N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), IRGANOX B215 (IRGANOX TM 1010 and tris tert-butylphenyl) phosphite, a 50/50 blend of IRGANOX TM B225 (IRGANOX TM 1010 and tris (2,4-di-tert-butylphenyl) phosphite), and A 50/50 blend of IRGANOX (R) B1171 (IRGANOX (R) 1098 and tris (2,4-di-tert-butylphenyl) phosphite) It can be purchased from the BASF Company.

The pigments include both transparent pigments such as inorganic silicon pigments (e.g., silica pigments) and pigments used to apply conventional compositions. Conventional pigments include metal oxides such as titanium dioxide and iron oxide; Metal hydroxides; Metal flakes, such as aluminum flakes; Chromate, for example, lead chromate; Sulfide; Sulfate; Carbonates; Carbon black; Silica; talc; Clay; Phthalocyanine blue and green, organogel red; Organo maroon and other organic pigments and dyes. Particularly preferred are pigments stable at high temperatures.

The pigments are blended into a kneading pigment (millbase) by mixing the pigments with a dispersing resin, which is generally miscible with, or may be the same as, the material with which the pigment is to be incorporated.

Other additives, such as inorganic fillers, anti-skid agents, plasticizers, nucleating agents, etc., which are generally required or not used, may also be incorporated.

The thermoplastic silicone elastomer produced by the above production method can be processed by a conventional method, for example, extrusion, vacuum molding, injection molding, blow molding or compression molding. In addition, such compositions can be reworked with little or no degradation in mechanical properties.

The thermoplastic silicone elastomer according to the present invention has a low hardness and is excellent in mechanical properties such as tensile strength, tear strength, abrasion resistance, and compression set, and has smooth surface properties without surface stickiness, It can be usefully applied to parts and members of various fields such as electric wires, household appliances, medical care, sports, and the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. The following examples are only illustrative of the present invention and do not limit the scope of protection of the present invention.

[ Example  And Comparative Example ]

(A), a polyetherester elastomer resin (B), a crosslinking aid (C), a compatibilizing agent (D) and an antioxidant were melt-mixed at 200 ° C for 20 minutes using a kneader Respectively. The radical initiator (E) was dry blended into the melt-mixed mixture and then vulcanized at 200 DEG C and 300 rpm using a twin-screw extruder having? 30 mm and L / D = 40 to prepare a thermoplastic silicone elastomer pellet . The pellets were dried at 80 ° C for 2 hours and then injected at a molding temperature of 200 ° C and a mold temperature of 25 ° C in an extruder to prepare physical specimens.

division Example 1
(weight%) Example 2
(weight%) Example 3
(weight%) Example 4
(weight%) Example 5
(weight%) Example 6
(weight%) Example 7
(weight%) Comparative Example 1
(weight%) Comparative Example 2
(weight%) Silicon base
(A) 16.7 35.5 34.5 16.7 35.5 34.5 34.5 17.7 36.5 The polyetherester elastomer resin (B) 80 60 60 80 60 60 60 80 60 Crosslinking aid (C) 2 3 3 2 3 3 3 2 3 The compatibilizer (D1) One One 2 - - - - - - The compatibilizer (D2) - - - One One 2 - - - The compatibilizer (D3) - - - - - - 2 - - Antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Radical initiator
(E) 0.2 0.4 0.4 0.2 0.4 0.4 0.4 0.2 0.4

(1) Silicone base (A): HTV SH0050U product of KCC [ASTM D926 measured plasticizer degree 220]

(2) Polyetherester elastomer resin (B): LG Chemie KEYFLEX BT 1030D [Shore hardness (ASTM D2240) 80A]

(3) Crosslinking aid (C): TAIC M-60 product of Nippon Kasei Chemical Co. [TAIC]

(4) a compatibilizer (D1): Damiani poly kemsa FD480 [socks Monotype of formula 1 (R is _{-CH 2 CH 2 CH 2 OCH 2} - , n is 100 Im);

5 compatibilizer (D2): Arkema Inc., Lotader ^® AX 8900 glycidyl ester polymer

(6) compatibilizer (D3): DuPont Fusabond 416D

(7) Antioxidant: Songwon Ind Co., Songnox 1010 product

(8) Radical initiator (E): 2,5-Bis (tert-butylperoxy) -2,5-dimethylhexane, product of Arkema Luperox 101XL45

The following physical properties of the specimens prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were measured and shown in Tables 3 and 4.

(1) Hardness: Measured according to the evaluation method defined in ISO 868.

(2) Melt index: Measured under the load condition of 10 kg at 190 ° C according to the evaluation method specified in ISO 1133.

(3) Specific gravity: Measured according to the method specified in ISO 1183.

(4) Tensile strength and elongation: The tensile strength and elongation were measured using a universal test machine (UTM) according to the evaluation method defined in ISO 37.

(5) Tear strength: Measured according to the evaluation method specified in ISO 34.

(6) Taber Abrasion: Measured according to the evaluation method specified in ASTM D3389.

(7) Permanent compression strain: Measured according to the evaluation method defined in ISO 815 under conditions of 23 ° C and 22 hours.

division Hardness
Resin flowability
(190 < 0 > C, 10 kg) importance The tensile strength Elongation Phosphorus strength
Taber Abrasion
(mg / 1000 cycles) Permanent compressive strain
(23 < 0 > C, 22 hr) unit Shorea g / 10 min - MPa % kN / m kJ / m ² % Example 1 73 48 1.08 19.7 600 40.4 67 22 Example 2 67 65 1.12 11.7 500 27.2 135 29 Example 3 67 65 1.11 13.2 450 30.1 98 23 Example 4 73 46 1.08 20.5 600 40.7 60 22 Example 5 67 56 1.12 12.3 550 27.8 137 29 Example 6 67 48 1.11 13.1 550 30.7 93 25 Example 7 68 60 1.11 11.4 500 28.8 104 31 Comparative Example 1 74 70 1.10 13.1 400 27.4 81 33 Comparative Example 2 68 73 1.14 6.1 350 18.9 165 32

As shown in Table 2, it was found that the thermoplastic silicone elastomers prepared in Examples 1 to 7 had higher compatibility than the thermoplastic silicone elastomers prepared in Comparative Examples 1 and 2 in similar compositions, and thus had excellent physical properties.

Therefore, the process for producing a thermoplastic silicone elastomer according to the present invention is advantageous in that it does not use a plasticizer, has a low hardness, is excellent in mechanical properties such as tensile strength, tear strength, abrasion resistance and compression set, It is possible to economically produce the thermoplastic silicone elastomer having the characteristics of the present invention.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (21)

(i) a silicone base (A) containing a diorganosiloxane rubber (A ') and a reinforcing filler (A') having a degree of plasticity of 30 or more as measured by the ASTM D926 measurement method and having two or more alkenyl groups in the molecule At least one compatibilizing agent (D) selected from the group consisting of a polyetherester elastomer resin (B), a crosslinking auxiliary (C), and an epoxy functional polysiloxane, a glycidyl ester polymer and an organofunctional grafted polyolefin, Melt mixing;
(ii) mixing the mixture of step (i) with a radical initiator (E); And
(iii) vulcanizing the diorganosiloxane rubber (A ') in the mixture of step (ii).
The method according to claim 1,
Wherein the silicone base (A) contains 5 to 200 parts by weight of a reinforcing filler (A ") relative to 100 parts by weight of the diorganosiloxane rubber (A ').
The method according to claim 1,
Wherein step (i) comprises: 2 to 60 wt% of silicone base (A), 35 to 95 wt% of polyetherester elastomer resin (B), 0.5 to 10 wt% of crosslinking auxiliary (C) By weight based on the total weight of the thermoplastic silicone elastomer.
The method according to claim 1,
Wherein step (ii) comprises mixing 0.1 to 5% by weight of a radical initiator (E) based on the total weight of the mixture of step (i).
The method according to claim 1,
The silicon-based diorganopolysiloxane (A ') is a rubber selected from a copolymer consisting of dimethylsiloxane units and methylvinylsiloxane units or a copolymer consisting of dimethylsiloxane units and methylhexenylsiloxane units, the silicon-based reinforcing filler ( A ") is pyrolytic silica.
The method according to claim 1,
The polyetherester elastomer resin (B) is a resin composition wherein the ester-forming derivative of the dicarboxylic acid or dicarboxylic acid constituting the hard segment of the polyetherester elastomer is terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, di Wherein the thermoplastic silicone elastomer is at least one selected from the group consisting of ethyl terephthalate and dimethyl terephthalate.
The method according to claim 1,
The polyetherester elastomer resin (B) is a resin composition in which the diol constituting the hard segment of the polyetherester elastomer is selected from the group consisting of ethylene glycol, 1,3-propylene diol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, heptane methylene glycol and 1 , And 4-cyclohexane dimethanol. The method of producing a thermoplastic silicone elastomer according to claim 1,
The method according to claim 1,
The polyetherester elastomer resin (B) is a resin composition wherein the polyalkylene oxide constituting the soft segment of the polyetherester elastomer is selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and polyoxyoctamethylene glycol Wherein the thermoplastic silicone elastomer is at least one kind of thermoplastic silicone elastomer.
9. The method of claim 8,
Wherein the polyetherester elastomer resin (B) has a content of polyalkylene oxide (polyalkylene oxide) which is a soft segment of the polyetherester elastomer is 20 to 80% by weight.
The method according to claim 1,
The crosslinking auxiliary (C) is at least one selected from the group consisting of TAIC (Trially Isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane Trimethacrylate), TMPTA (Trimethylolpropane Triacrylate), ZDA (Zinc diacrylate) and ZDMA ≪ / RTI > wherein the thermoplastic silicone elastomer is a thermoplastic silicone elastomer.
The method according to claim 1,
Wherein the epoxy functional polysiloxane has an Epoxy Index of 0.35 Eq / kg to 5.5 Eq / kg.
The method according to claim 1,
Wherein the epoxy functional polysiloxane is at least one selected from compounds represented by the following formulas (3) and (4): < EMI ID =
(3)

[Chemical Formula 4]

In the above formulas (3) and (4), R is -CH ₂ CH ₂ CH ₂ OCH ₂ -, and n and m are each independently an integer of 10 to 200.
The method according to claim 1,
Wherein the glycidyl ester polymer comprises a first recurring unit derived from at least one glycidyl ester monomer and a second recurring unit derived from at least one? -Olefin monomer.
14. The method of claim 13,
Wherein the glycidyl ester polymer is a glycidyl ester monomer, wherein the glycidyl ester monomer is glycidyl acrylate or glycidyl methacrylate.
14. The method of claim 13,
The glycidyl ester polymer may be selected from the group consisting of an olefin-glycidyl (meth) acrylate polymer, an olefin-vinyl acetate-glycidyl (meth) acrylate polymer, and an olefin-glycidyl (meth) acrylate- Wherein the thermoplastic silicone elastomer is at least one selected from the group consisting of latex polymers.
14. The method of claim 13,
Wherein the glycidyl ester polymer is a random ethylene / acrylic acid ester / glycidyl methacrylate copolymer or a random ethylene / acrylic acid ester / glycidyl methacrylate terpolymer.
The method according to claim 1,
Wherein the organofunctional grafted polyolefin is selected from the group consisting of homopolymers of olefins and organic functional grafting monomers, copolymers of organic functional grafting monomers and ternary copolymers of organic functional grafting monomers Of the thermoplastic silicone elastomer.
18. The method of claim 17,
Wherein the organic functional grafting monomer is an ethylenically unsaturated hydrocarbon comprising at least one organic functional group selected from the group consisting of carboxylic acid, carboxylic acid salt, amide, imide, ester, anhydride, epoxy, alkoxy and oxazoline Of the thermoplastic silicone elastomer.
18. The method of claim 17,
The organofunctional grafted polyolefin is selected from the group consisting of poly (ethylene-co-vinyl acetate) grafted maleic anhydride, polypropylene grafted maleic anhydride, polyethylene-polypropylene grafted maleic anhydride, maleic anhydride grafted Ethylene-butylene-styrene (SEBS) copolymer grafted with maleic anhydride, ethylene-propylene rubber (EPDM), and maleic anhydride-grafted styrene- Of the thermoplastic silicone elastomer.
The method according to claim 1,
Wherein the radical initiator (E) is an organic peroxide.
20. The thermoplastic silicone elastomer produced by the process for producing a thermoplastic silicone elastomer according to any one of claims 1 to 20.