WO2016175571A1 - Thermoplastic resin composition for wearable device, and molded product using same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition for a wearable device, and a molded product using the same, which comprise (A) a polyurethane-based thermoplastic elastomer and (B) a polyamide-based thermoplastic elastomer.

Description

Thermoplastic resin composition for wearable device and molded article using same

The present invention relates to a thermoplastic resin composition for a wearable device and a molded article using the same. More specifically, the thermoplastic resin composition for wearable devices optimized for wearable devices having excellent tensile and tear strength, hardness, high temperature tensile strength, and weather resistance by mixing a polyurethane-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer at an optimum ratio; It relates to a molded article using the same.

Recently, wearable devices such as smart watches are being released, and the size of the wearable device market is continuously growing.

Wearable devices include glasses, shoes / insoles, rings, belts, wristwatches / bands / bracelets necklaces, earsets, clothing, badges, etc. It forms a lot of products.

In the past, thermosetting resins such as ethylene propylene rubber (EPDM) and silicone rubber were used for smart bands and watches.

However, thermosetting resins require a vulcanization process and thus have low productivity, making it difficult to mass produce a large variety of products, and there are also environmental problems.

In order to solve such a problem, recently, thermoplastic elastomers are mainly used.

Thermoplastic elastomers can be injection molded to facilitate product production, recyclability, and environmentally friendly advantages.

However, in the case of most thermoplastic elastomers, the tensile and tear strengths are low or susceptible to ultraviolet rays (UV) at room temperature and high temperature, so that deformation or discoloration of the product form is likely to occur.

Therefore, in order to solve such a problem, it is required to develop a material suitable for wearable devices of recent trends in production of a large variety of products due to high tensile and tear strength at high temperature and high temperature, high UV stability, and high productivity.

An object of the present invention is a wearable device capable of simultaneously solving the problem of lowering the tear strength at the high temperature of the conventional polyurethane-based thermoplastic elastomer and low productivity of the thermosetting resin by mixing the polyurethane-based thermoplastic elastomer and the polyamide-based thermoplastic elastomer at an optimum ratio. It is to provide a thermoplastic resin composition and a molded article using the same.

Another object of the present invention is to add an ethylene copolymer, excellent tensile / tear strength at room temperature and high temperature, while ensuring optimum hardness and excellent productivity, the thermoplastic resin composition for wearable devices optimized for wearable devices and It is to provide a molded article using the same.

Another object of the present invention is to configure each component with an optimal material, and by adding a UV stabilizer, etc., not only to realize the strength and processability suitable for wearable devices exposed to the outside and in contact with the human body, but also durability and long-term use The present invention also provides a thermoplastic resin composition for wearable devices having excellent weather resistance and a molded article using the same.

One aspect of the present invention relates to a thermoplastic resin composition for a wearable device. In one embodiment, the thermoplastic resin composition for a wearable device includes (A) a polyurethane-based thermoplastic elastomer; And (B) a polyamide-based thermoplastic elastomer.

In one embodiment, the polyurethane-based thermoplastic elastomer (A) is a compound containing at least one of alkanediol, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol and polycarbonate polyol having 2 to 10 carbon atoms and poly It can be prepared by reacting isocyanate.

In one embodiment, the polyamide-based thermoplastic elastomer (B) is copolyamide, isophthalic acid, 3,3'-dimethyl-4,4'-diamino made from terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine. Copolyamides prepared from dicyclohexylmethane and lauryllactam, terephthalic acid, isophthalic acid, copolyamides prepared from 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and lauryllactam and 3 And at least one of copolyamides prepared from, 3'-dimethyl-4,4'-diaminodihexoxymethane and lauryllactam.

In one embodiment, the weight ratio of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B) may be about 1: 0.3 to about 1: 3.

In one embodiment, the thermoplastic resin composition further includes an additive (C), and the additive (C) may include an ethylene copolymer.

In one embodiment, the additive (C) may comprise one or more of styrene-ethylene-butylene-styrene copolymer (SEBS), ethylene-octene copolymer (EOR), and ethylene-methylacrylate copolymer (EMA). Can be.

In one embodiment, the additive (C) may be included in an amount of about 30 parts by weight to about 50 parts by weight based on 100 parts by weight of the total of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B).

In one embodiment, the thermoplastic resin composition further includes (D) a UV stabilizer, and the UV stabilizer (D) is added to 100 parts by weight of the total of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). For example, about 0.2 part by weight to about 1 part by weight may be included.

In one embodiment, about 20% to about 80% by weight of the polyurethane-based thermoplastic elastomer (A) and about 20% to about 80% by weight of the polyamide-based thermoplastic elastomer (B).

Another aspect of the present invention relates to a molded article comprising the thermoplastic resin composition.

In one embodiment, the molded article may have a tensile strength of about 60 kgf / cm 2 to about 200 kgf / cm 2 measured at 100 ° C. according to ISO 527.

In one embodiment the molded article has a hardness (Shore D) of about 20 to about 50, a tensile strength of about 100 kgf / cm 2 to about 400 kgf / cm 2 measured at 23 ° C. according to ISO 527 standard, based on ISO 34 Based on the tear strength measured at 23 ℃ may be about 40N / mm to about 150N / mm.

In one embodiment the molded article may satisfy the following formula 1:

[Equation 1]

90 <TS ₂₃ -TS ₁₀₀ <130

(In Formula 1, TS ₂₃ is the tensile strength measured at 23 ° C based on ISO 527 standard (kgf / ㎠), and TS ₁₀₀ is the tensile strength measured at 100 ° C based on ISO 527 standard. kgf / cm 2) value).

According to the present invention, by mixing the polyurethane-based thermoplastic elastomer and the polyamide-based thermoplastic elastomer in an optimum ratio, there is an advantage that can solve the problems of lowering the tear strength at a high temperature of the conventional polyurethane and low productivity of the thermosetting resin at the same time.

In addition, by including the polyamide-based thermoplastic elastomer in an optimum ratio, by adding a thermoplastic elastomer to it, it is possible to ensure excellent hardness and excellent productivity while maintaining excellent tensile / tear strength at room temperature and high temperature, optimized for wearable devices Has been an advantage.

In addition, by constituting each component of the optimum material and adding a UV stabilizer, not only the strength and workability suitable for wearable devices exposed to the outside and in contact with the human body but also excellent durability and weather resistance in long-term use have.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms, and only the embodiments make the disclosure of the present invention complete, and the general knowledge in the art to which the present invention belongs. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used in a sense that can be commonly understood by those skilled in the art. In addition, terms that are defined in a commonly used dictionary are not ideally or excessively interpreted unless they are clearly specifically defined.

One aspect of the present invention relates to a thermoplastic resin composition for a wearable device. First, the thermoplastic resin composition for wearable devices of the present invention includes (A) a polyurethane-based thermoplastic elastomer and (B) a polyamide-based thermoplastic elastomer. This is a blending to overcome the low tensile / tear strength at high temperatures of polyurethane and the weak design factor, low productivity of thermoset resins, each of which will be described in detail below.

(A) Polyurethane Thermoplastic Elastomer

Polyurethane-based thermoplastic elastomer (A) according to an embodiment of the present invention can be used as long as the elastomer material having a thermoplastic containing polyurethane. The polyurethane-based thermoplastic elastomer (A) is included to implement suitable physical properties for the wearable device in combination with the polyamide-based thermoplastic elastomer (B) to be described later.

In one embodiment, the polyurethane-based thermoplastic elastomer (A) is a hard segment block in which an aromatic chain or aliphatic chain is connected by a urethane bond and at least one of polyester, polyether, polyolefin, polycaprolactone and polycarbonate It may be a block copolymer comprising a soft segment block containing.

The polyurethane-based thermoplastic elastomer (A) may be prepared from an isocyanate compound having two or more NCO groups and a compound having two or more hydroxyl groups. For example, the polyurethane-based thermoplastic elastomer (A) is a compound containing two or more of alkanediol, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol, and polycarbonate polyol having 2 to 10 carbon atoms and two It can be prepared by reacting the isocyanate compound having the above NCO group. For example, it may be prepared by reacting polycaprolactone polyol and polyisocyanate. In one embodiment, the polyurethane-based thermoplastic elastomer (A) may be prepared by reacting polyisocyanate, polyol and chain extender.

In one embodiment the polyurethane-based thermoplastic elastomer (A) can be prepared by the reaction of polyisocyanate, polyol and chain extender component.

The polyisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'- diisocyanate, 2,2 ′ -Diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropanediisocyanate, m-phenylenediisocyanate, p Aromatic diisocyanates such as -phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, tetra Methylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyane Aliphatic diisocyanates such as citrate, trimethylhexamethylene diisocyanate and lysine diisocyanate, cyclohexane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diisocyanate Alicyclic diisocyanates such as phenylmethane diisocyanate, tetramethyl xylene diisocyanate and norbornane diisocyanate methyl, biuret, dimer, trimer, dimer and trimer of the isocyanate, carbodiimide and uretone. The adduct body obtained by reaction with a simple body, a biol or more functional polyol, etc. and the said isocyanate can be used.

Furthermore, polyisocyanate which stabilized a part of isocyanate group by the blocking agent which has one active hydrogen in a molecule | numerator, such as methanol, n-butanol, benzyl alcohol, aceto acetate, epsilon caprolactam, methyl ethyl ketone oxime, phenol, and cresol, Can be used. These can be used 1 type or in mixture of 2 or more types.

The polyol may be a polymer polyol having a number average molecular weight of about 500 to about 10000. In one embodiment, the polyol may be an alkanediol having 2 to 10 carbon atoms, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, and the like. These can be used 1 type or in mixture of 2 or more types. For example, it may be a polycaprolactone polyol.

In one embodiment, the polyester polyol may be prepared by reacting a polycarboxylic acid with a low molecular polyol. At this time, it can manufacture by using together diamine or amino alcohol. In one embodiment, the polycarboxylic acid may be succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, phthalic acid alkyl esters, trimellitic acid, maleic acid, fumaric acid or itaconic acid. have. In another embodiment, the polyester polyol may be obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone, and caprolactone using the low molecular weight polyol as an initiator.

As the low molecular weight polyol, those having a number average molecular weight of less than 500 can be used. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1 , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 1,8-octanediol, 1,9- Nonanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2 -Ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eichoic acid-1,2-ethylene glycol, 2-n-octacoic acid-1,2-ethylene Glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, or ethylene oxide or propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, 3-hydroxy-2,2-dimethylpropyl-3- Low molecular polyols such as hydroxy-2,2-dimethylpropionate, trimethylolpropane, glycerin, pentaerythritol.

As said diamine or amino alcohol, low molecular weight amino alcohols, such as low molecular polyamines, such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophoronediamine, monoethanolamine, diethanolamine, and triethanolamine, can be used. Moreover, the lactone polyester polyol obtained by ring-opening polymerization of cyclic ester (lactone) monomers, such as (epsilon) -caprolactone and (gamma) -valerolactone, can be used using a low molecular polyol, a low molecular polyamine, and a low molecular amino alcohol as an initiator.

As a specific example of the said polyester polyol, a polyether ester polyol can be used. The polycarbonate polyol is a de-alcohol reaction between a low molecular weight polyol used for the synthesis of the polyester polyol, diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. Phenol reaction or the like.

The polycaprolactone polyol may be prepared by ring-opening polymerization of a caprolactone monomer under a catalyst. For example, the polycaprolactone polyol may be prepared by ring-opening polymerization of ε-caprolactone using the low molecular polyol or the low molecular polyamine as an initiator.

As said polyether polyol, the low molecular polyol, low molecular polyamine, and low molecular amino alcohol used for the said polyester polyol can be used as an initiator. For example, the initiator and ethylene oxide, propylene oxide, tetrahydrofuran and the like can be prepared by ring-opening polymerization. In one embodiment, the polyether polyol may use one or more of polyethylene glycol, poly (1,2-propanediol) and polytetramethylene ether glycol.

The polyolefin polyol may include at least one of polyethylene polyol, polypropylene polyol, polybutadiene polyol, and polyisoprene polyol. In another embodiment, as the polyolefin, hydroxyl-containing polybutadiene, hydrogenated hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydrogenated hydroxyl-containing polyisoprene, hydroxyl-containing chlorinated polypropylene, or hydroxyl-containing chlorinated polyethylene can be used.

The polycarbonate polyol may be prepared by reacting the low molecular polyol with chloroformate ester or phosgene. In another embodiment, the low molecular polyol may be prepared by a transesterification reaction with a carbonate ester.

In addition, the chain extender can use an active hydrogen-containing compound having a number average molecular weight of less than 500. Low molecular polyols, low molecular polyamines or low molecular aminoalcohols can be used. The low molecular polyols, low molecular polyamines and low molecular amino alcohols may be the same as those described above.

A well-known manufacturing method, for example, a one shot method, a prepolymer method, a batch reaction method, a continuous reaction method, etc. can be used for manufacture of the polyurethane-type thermoplastic elastomer (A) of this invention.

The polyurethane-based thermoplastic elastomer (A) may be included in an amount of about 20% by weight to about 80% by weight based on 100% by weight of the polyamide-based thermoplastic elastomer (B). When included in the above range, it is possible to implement the hardness and workability suitable for wearable devices, excellent tensile strength and tear strength and high temperature tensile strength. For example, about 30% to about 70% by weight may be included. For example, about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79 or 80% by weight.

(B) Polyamide Thermoplastic Elastomer

The polyamide-based thermoplastic elastomer (B) used in the present invention may be used in combination with the polyurethane-based thermoplastic elastomer (A) to use a polyamide-based thermoplastic elastomer material capable of improving the strength, processability, and the like.

Polyamide-based thermoplastic elastomers (B) are copolyamides, isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane made from terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine and Copolyamides prepared from lauryllactam, terephthalic acid, isophthalic acid, copolyamides prepared from 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and lauryllactam, and 3,3'- And at least one of copolyamides prepared from dimethyl-4,4′-diaminodihexoxymethane and lauryllactam.

The polyamide-based thermoplastic elastomer (B) may be in the form of a block copolymer including a hard segment (x1) made of a polyamide component and a soft segment (x2) made of a poly (alkylene oxide) glycol component. It will not specifically limit, if it is a polymer which has an acidamide bond (-CO-NH-) in a principal chain as a polyamide component used for formation of a hard segment (x1). Such polyamide components are usually produced by known methods such as ring-opening polymerization of lactam compounds having a ring structure, polymerization of aminocarboxylic acids, and polycondensation of dicarboxylic acids and diamine compounds. Therefore, the polyamide component is used as homopolyamide, copolyamide, or the like. The lactam compound used in the ring-opening polymerization may be ε-caprolactam, ω-laurolactam, or the like.

Moreover, as aminocarboxylic acid, aminocapronic acid, aminoenanthate, aminocaprylic acid, aminofelargonic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, and 12-aminodo Decanoic acid and the like.

Examples of the dicarboxylic acid in the case of polycondensation of the dicarboxylic acid and the diamine compound include adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, 2-methyl terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. are mentioned. As the diamine compound, ethylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,3,4-trimethylhexamethylenediamine, 2,4, 4-trimethylhexamethylenediamine, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, paraphenylenediamine, metaphenylenediamine and the like.

The polyamide component may be at least one of nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12, 6T, 6 / 6.6, 6/12, 6 / 6T, and 6T / 6I. Can be used. The ends of these polyamide components may also be capped with carboxylic acids, amines, and the like. Aliphatic monocarboxylic acids, such as capric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid, are mentioned as said carboxylic acid. The amine may be an aliphatic primary amine such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, or behenylamine.

 The number average molecular weight of the polyamide component may be about 500 to about 10,000. For example, about 500 to about 5,000. When using two or more polyamide components in one embodiment, the number average molecular weight measurement of the mixed polyamide component may be in the above range.

As the poly (alkylene oxide) glycol component used in the formation of the soft segment (x2), a known polymer such as a polymer represented by the following general formula (1) may be used alone or in combination of two or more:

[Formula 1]

HO (CH ₂ CH ₂ O) m (CH ₂ CH (X) O) n H

(In Formula 1, X represents a hydrogen atom (-H) or a substituent -CH ₃ , -CH ₂ Cl, -CH ₂ Br, -CH ₂ I or -CH ₂ OCH ₃ , n≥0, m≥ 0, and (n + m) ≥20, where n and m are integers.)

In one embodiment, the poly (alkylene oxide) glycol component is polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, Block or random copolymers of poly (hexamethylene oxide) glycol, polyethylene oxide, polypropylene oxide, ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, or bisphenol A And alkylene oxide adducts. For example, alkylene oxide adducts of polyethylene glycol and bisphenol A can be used.

In addition, both ends of the poly (alkylene oxide) glycol component may be aminated and / or carboxylated.

The number average molecular weight of the poly (alkylene oxide) glycol component may preferably be about 200 to about 20,000. For example, about 300 to about 10,000. For example, from about 300 to about 4,000. When using 2 or more types of poly (alkylene oxide) glycol components in one embodiment, the number average molecular weight measurement value of the mixed poly (alkylene oxide) glycol component should just be in the said range.

The polyamide-based thermoplastic elastomer (B) can be obtained by polymerizing the polyamide component and the poly (alkylene oxide) glycol component under reduced pressure or under normal pressure.

In one embodiment, from about 10 wt% to about 95 wt% of the polyamide component and about 5 wt% of the poly (alkylene oxide) glycol component relative to 100 wt% of the sum of the polyamide component and the poly (alkylene oxide) glycol component % To about 90% by weight. When included in the above range, the compatibility and physical properties of the prepared polyamide-based thermoplastic elastomer and the polyurethane thermoplastic elastomer may be excellent. For example, about 20 wt% to about 90 wt% of the polyamide component and about 10 wt% to about 80 wt% of the poly (alkylene oxide) glycol component may be included. Other examples include about 30% to about 70% by weight of the polyamide component and about 30% to about 70% by weight of the poly (alkylene oxide) glycol component.

In one embodiment, an antimony catalyst, a tin catalyst, a titanium catalyst, a zirconium catalyst, a metal acetate catalyst, or the like may be used in the polymerization.

In addition, at the time of superposition | polymerization of a polyamide component and a poly (alkylene oxide) glycol component, dicarboxylic acid, a diamine compound, etc. can be used together as a polymerization raw material. As said dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, etc. can be used. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, dipe Oxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, and the like. The alicyclic dicarboxylic acid may be 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, or the like. The aliphatic dicarboxylic acid may be succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, or the like. For example, it may be terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid or dodecanedicarboxylic acid. In addition, these dicarboxylic acids can be used individually by 1 type or in combination of 2 or more types.

As the diamine compound, an aromatic diamine compound, an alicyclic diamine compound, and an aliphatic diamine compound may be used. The aromatic diamine compound may be p-phenylenediamine, m-phenylenediamine, diaminodiphenylether, diaminodiphenylmethane, and the like, and the alicyclic diamine compound may be piperazine, diaminodicyclohexylmethane, cyclohexyl Diamine and the like, and the aliphatic diamine compound may be hexamethylenediamine, ethylenediamine, propylenediamine, octamethylenediamine, or the like. For example, hexamethylenediamine. These diamine compounds can be used individually or in combination of 2 or more types.

In one embodiment, the poly is obtained by polymerization of a polyamide component and a poly (alkylene oxide) glycol component or polymerization of a polyamide component, a poly (alkylene oxide) glycol component, and a dicarboxylic acid or diamine compound. The bond of the hard segment (x1) and the soft segment (x2) of the amide thermoplastic elastomer (B) depends on the terminal structure of the soft segment (x2), and may usually be an ester bond or an amide bond.

The polyamide-based thermoplastic elastomer (B) comprises (1) a polyamide obtained by polymerization of an aminocarboxylic acid having 6 or more carbon atoms or polymerization of a lactam compound, or a diamine compound and a dicarboxylate having 6 or more carbon atoms. Polyamide obtained using (2) polyethylene glycol having a number average molecular weight of 200 to 20,000, or (3) dicarboxylic acid having 4 to 20 carbon atoms, wherein the polyether ester unit is about the entire polymer. From 10 wt% to about 95 wt% polyetheresteramide.

The reduced viscosity ηsp / c (measured using 25 ° C., 0.5 g / 100 ml formic acid solution) of the polyamide-based thermoplastic elastomer (B) may be 0.5 dl / g to 3.0 dl / g. For example, about 1.0 dl / g to about 2.5 dl / g. Although molecular weight may fall by the thermal deterioration at the time of manufacture of the composition of this invention at the time of shaping | molding process, the reduced viscosity (eta) sp / c in a final product may be 0.3 dl / g or more.

In one embodiment, the polyamide-based thermoplastic elastomer (B) may be included in an amount of about 20% by weight to about 80% by weight based on 100% by weight of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). When included in the above range, it is possible to implement the hardness and workability suitable for wearable devices, excellent tensile strength and tear strength and high temperature tensile strength. For example, about 30% to about 70% by weight may be included. For example, about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79 or 80% by weight.

In one embodiment, the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B) may be included in a weight ratio of about 1: 0.3 to about 1: 3. Within the ratio, the thermoplastic resin composition may have excellent room temperature tensile strength and tear strength and high temperature tensile strength, and may realize hardness, strength, weather resistance, productivity, and durability that are most suitable for wearable devices.

(C) additive

The additive (C) used in the present invention may include an ethylene copolymer. For example, one or more of styrene-ethylene-butylene-styrene copolymer (SEBS), ethylene-octene copolymer (EOR), and ethylene-methylacrylate copolymer (EMA) can be included. When the additive is included, the thermoplastic resin for a wearable device of the present invention may improve flow characteristics while maintaining excellent physical properties, thereby maximizing durability and weather resistance and productivity due to frequent detachment or external environment to the body.

In one embodiment, the additive (C) may be included in an amount of about 30 parts by weight to about 50 parts by weight based on 100 parts by weight of the total of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). When included in the above range it can maximize the durability, weather resistance and productivity of the thermoplastic resin for wearable devices. For example, about 40 parts by weight to about 45 parts by weight may be included. For example, about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 parts by weight may be included. .

The polyamide-based thermoplastic elastomer (B) in the thermoplastic resin composition for a wearable device of the present invention may be included in a higher content than the additive (C).

(D) UV stabilizer

The UV stabilizer (D) used in the present invention can be used as long as it is a substance capable of improving resistance to UV. For example, it may include an amine compound. For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-butanetetracarboxylate, 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine, and N, N'-bis ( One or more of the polycondensates of 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine.

In one embodiment, the UV stabilizer (D) may be included in an amount of about 0.2 part by weight to about 1 part by weight based on 100 parts by weight of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). When included in the above range can improve the UV resistance without deteriorating the thermoplastic resin properties of the present invention. For example, about 0.3 parts by weight to about 0.5 parts by weight may be included. For example, about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 part by weight may be included.

Wearable For devices  Molded article comprising a thermoplastic resin composition

Another aspect of the present invention relates to a molded article comprising the thermoplastic resin composition for wearable devices.

In one embodiment, the molded article may have a tensile strength of about 60 kgf / cm 2 to about 200 kgf / cm 2 at 100 ° C. measured according to ISO 527. For example, about 70 kgf / cm 2 to about 150 kgf / cm 2.

In one embodiment the molded article has a Shore D hardness of about 20 to about 50, a tensile strength at about 23 ° C., measured according to ISO 527, and is about 100 kgf / cm 2 to 400 kgf / cm 2, based on ISO 34 The tear strength measured at a temperature of 23 ° C may be about 40 N / mm to about 150 N / mm. For example, Shore D hardness is about 25 to about 45, tensile strength at 23 ° C. is about 150 kgf / cm 2 to about 275 kgf / cm 2, and tear strength is about 50 N / mm to about 125 N / mm Can be. It may be suitable for use in wearable devices in the hardness, tensile strength and tear strength of the above range.

In one embodiment, the molded article may satisfy the following formula 1:

[Equation 1]

90 <TS ₂₃ -TS ₁₀₀ <130

(In Formula 1, TS ₂₃ is the tensile strength measured at 23 ° C based on ISO 527 standard (kgf / ㎠), and TS ₁₀₀ is the tensile strength measured at 100 ° C based on ISO 527 standard. kgf / cm 2) value).

When the molded article satisfies the range of Equation 1, it may be suitable for use in a wearable device.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Example  And Comparative example

Specifications of (A) polyurethane thermoplastic elastomer, (B) polyamide thermoplastic elastomer, (C) additive and (D) UV stabilizer used in Examples and Comparative Examples of the present invention are as follows.

(A) Polyurethane thermoplastic elastomer: A polyurethane thermoplastic elastomer prepared by reacting polycaprolactone polyol and polyisocyanate was used.

(B) Polyamide-based thermoplastic elastomer: Polyamide-based thermoplastic elastomers prepared from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and lauryllactam were used.

(C) Additives: (C1) Dow Corning's TPSiV product was used in which a polyurethane-based thermoplastic elastomer and silicone were mixed. (C2) Styrene-ethylene-butylene-styrene copolymer (SEBS) was used. (C3) Ethylene-octene copolymer (EOR) was used. (C4) Ethylene-methylacrylate copolymer (EMA) was used.

(D) UV stabilizer: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate was used.

After the ingredients were added and dry mixed according to the contents of Table 1, pellets were prepared by processing at a nozzle temperature of 250 ° C. to 310 ° C. using a twin screw extruder having a φ = 36 mm. The prepared pellets were dried at 80 ° C. for at least 4 hours to prepare test specimens. In Table 1 below, the polyurethane-based thermoplastic elastomer (A), the polyamide-based thermoplastic elastomer (B) and the additive (C) are in weight percent, and the UV stabilizer (D) is the components (A), (B) and (C). The sum is expressed in parts by weight based on 100 parts by weight.

		Example						Comparative example
		One	2	3	4	5	6	One	2	3	4	5	6	7
(A)		70	50	30	20	20	20	100	-	-	-	-	-	-
(B)		30	50	70	50	50	50	-	100	100	-	-	-	-
(C)	(C1)	-	-	-	-	-	-	-	-	-	100	-	-	-
	(C2)	-	-	-	30	-	-	-	-	-	-	100	-	-
	(C3)	-	-	-		30	-	-	-	-	-	-	100	-
	(C4)	-	-	-	-	-	30	-	-	-	-	-	-	100
(D)		0.3	-	0.3	-	0.3	-	0.3	-	0.3	-	0.3	-	0.3

(Unit: parts by weight)

The specimens obtained by the composition of the components shown in Table 1 were evaluated for hardness, room temperature tensile strength (23 ° C.), high temperature tensile strength (100 ° C.), and tear strength in the following manner. same.

Property evaluation method

(1) Hardness (Shore A or Shore D): With respect to the specimens of Examples 1 to 6 and Comparative Examples 1 to 7 as Shore A or Shore D, which are surface hardness according to ISO 868 Measured.

(2) Room temperature tensile strength: The specimens of Examples 1 to 6 and Comparative Examples 1 to 7 were measured at a test temperature of 23 ° C. and a test speed of 50 mm / min according to the ISO 527 measuring method.

(3) High Temperature Tensile Strength: The specimens of Examples 1 to 6 and Comparative Examples 1 to 7 were measured at a test temperature of 100 ° C. and a test speed of 50 mm / min according to the ISO 527 measuring method.

(4) Tear strength: The specimens of Examples 1 to 6 and Comparative Examples 1 to 7 were measured at a test temperature of 23 ° C. and a test speed of 50 mm / min according to the ISO 34 method.

	Example						Comparative example
	One	2	3	4	5	6	One	2	3	4	5	6	7
Shore A or Shore D	23D	35D	45D	25D	27D	30D	70 A	70D	24D	80A	50 A	45A	60A
Room temperature tensile strength (23 ℃) (kgf / cm 2 )	200	250	275	175	150	170	256	400	28	90	58	62	52
High Temperature Tensile Strength (100 ℃) (kgf / cm 2 )	95	130	150	75	70	75	40	230	15	53	25	23	24
Tear strength (N / mm)	100	115	125	50	65	60	80	136	24	43	30	32	28

As shown in Table 2, the thermoplastic resin compositions of Examples 1 to 6 according to the present invention were excellent in both tensile strength at room temperature and high temperature due to synergistic effects of blending, and also suitable for wearable devices. It is measured by easy numerical processing, and it has high tear strength, so it can be seen that it is excellent in wearable device use environment such as frequent detachment from the body.

In contrast to the present invention, Comparative Examples 1 to 7 using only one of (A) polyurethane-based thermoplastic elastomer, (B) polyamide-based thermoplastic elastomer, or (C) additive have hardness, room temperature tensile strength, high temperature tensile strength and phosphorus. It was confirmed that all the thermal strengths were not satisfied.

In particular, in the case of Comparative Example 1, and Comparative Examples 4 to 7 to which only the polyurethane-based thermoplastic elastomer (A) or the additive (C) component is applied, the tensile and tear strength at a high temperature are significantly lowered to less than half of the above examples, which is a human body. It was found that the heat generated in the present invention is not suitable for the wearable device because it significantly lowers the durability when applied to the wearable device that is always present.

On the other hand, Comparative Examples 2 and 3, in which only polyamide-based thermoplastic elastomer (B) is applied, have high hardness and are difficult to process, and thus are difficult to be applied to shaped articles such as bands (Comparative Example 2). It was found that the tensile and tear strength at were significantly low, which makes them unsuitable for wearable devices.

Through the results of Table 2, the tensile strength / tear strength and the optimum hardness at room temperature and high temperature, which is significantly superior in the combination of the components of the present invention and the content ratio between the components is realized, the critical significance optimized for wearable devices Proven.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (13)

1. (A) polyurethane-based thermoplastic elastomers; And (B) a polyamide-based thermoplastic elastomer. A thermoplastic resin composition for a wearable device, comprising: a polyamide-based thermoplastic elastomer;
2. The compound of claim 1, wherein the polyurethane-based thermoplastic elastomer (A) comprises at least one of alkanediol, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol and polycarbonate polyol having 2 to 10 carbon atoms And a polyisocyanate reacting to prepare a thermoplastic resin composition for a wearable device.
3. 2. The polyamide-based thermoplastic elastomer (B) according to claim 1, wherein the polyamide-based thermoplastic elastomer (B) is made of terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine, copolyamide, isophthalic acid, 3,3'-dimethyl-4,4'- Copolyamides prepared from diaminodicyclohexylmethane and lauric lactam, terephthalic acid, isophthalic acid, copolyamides prepared from 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and lauryllactam And copolyamides prepared from 3,3′-dimethyl-4,4′-diaminodihexoxymethane and lauryllactam.
4. The thermoplastic resin composition of claim 1, wherein the weight ratio of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B) is about 1: 0.3 to about 1: 3.
5. The method of claim 1, further comprising (C) an additive,

   The additive (C) is a thermoplastic resin composition for a wearable device containing an ethylenic copolymer.
6. The method of claim 5, wherein the additive (C) comprises at least one of styrene-ethylene-butylene-styrene copolymer (SEBS), ethylene-octene copolymer (EOR), and ethylene-methylacrylate copolymer (EMA). Thermoplastic resin composition for wearable devices.
7. The wearable according to claim 5, wherein the additive (C) is included in an amount of about 30 parts by weight to about 50 parts by weight based on 100 parts by weight of the total of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). Thermoplastic resin composition for the device.
8. The method of claim 1 further comprising (D) a UV stabilizer,

   The UV stabilizer (D) is about 0.2 parts by weight to about 1 part by weight based on 100 parts by weight of the total of the polyurethane-based thermoplastic elastomer (A) and the polyamide-based thermoplastic elastomer (B). .
9. The thermoplastic resin composition of claim 1, further comprising about 20% to about 80% by weight of the polyurethane-based thermoplastic elastomer (A) and about 20% to about 80% by weight of the polyamide-based thermoplastic elastomer (B). .
10. The molded article containing the thermoplastic resin composition of any one of Claims 1-9.
11. The molded article of claim 10, wherein the molded article has a tensile strength of about 60 kgf / cm 2 to about 200 kgf / cm 2 measured at 100 ° C. according to ISO 527.
12. The method according to claim 10, wherein the molded article has a hardness (Shore D) of about 20 to about 50, a tensile strength of about 100 kgf / ㎠ to about 400 kgf / ㎠ measured at 23 ℃ based on ISO 527 standard, ISO 34. A molded article characterized in that the tear strength measured at 23 [deg.] C. is about 40 N / mm to about 150 N / mm based on 34 criteria.
13. The molded article of claim 10, wherein the molded article satisfies Equation 1 below.

    [Equation 1]

    90 <TS ₂₃ -TS ₁₀₀ <130

    (In Formula 1, TS ₂₃ is the tensile strength measured at 23 ° C based on ISO 527 standard (kgf / ㎠), and TS ₁₀₀ is the tensile strength measured at 100 ° C based on ISO 527 standard. kgf / cm 2) value).