KR20190075506A - Thermoplastic elastomer resin composition comprising mica and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic elastomer resin composition containing a mica and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic elastomer resin composition having significantly improved metal texture and surface glossiness by including a thermoplastic elastomer resin and mica having average particle diameters of a specific range in a specific range of content, thereby improving extrusion processability while maintaining good mechanical properties; and a molded article comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic elastomer resin composition containing mica and a molded article comprising the thermoplastic elastomer resin composition,

The present invention relates to a thermoplastic elastomer resin composition containing a mica and a molded article comprising the same, and more particularly, to a thermoplastic elastomer resin composition containing a thermoplastic elastomer resin and a mica having an average particle diameter within a specific range in a specific range, And at the same time, the extrusion processability is improved, and the metal texture and the surface gloss are remarkably improved, and a molded article comprising the thermoplastic elastomer resin composition.

The thermoplastic elastomer resin has excellent heat resistance, chemical resistance, and durability, and has been actively used for satisfying requirements such as durability and heat resistance of automobile parts, which are getting higher and higher. Particularly, the constant velocity joint boots belonging to the suspension system, the gearbox bellows belonging to the steering apparatus, the air ducts and the intercooler pipes around the engine, and the interior materials are mainly used for various applications such as dashboard skins or buttons, A thermoplastic polyester elastomer resin is used.

Of these, parts such as constant velocity joint boots, gearbox bellows, air ducts and intercooler pipes are manufactured by blow molding, and the viscosity of the thermoplastic elastomer resin is required for this purpose.

There are various methods for increasing the viscosity of the thermoplastic elastomer resin depending on the manufacturer and the processing method. For example, there are a solid-state polymerization method in which pellets of a thermoplastic elastomer resin produced through melt polymerization are made high in viscosity using high heat and vacuum, and a method in which a high molecular weight chain extender is used to make a high viscosity in an extruder There is an extrusion method.

In general, when the thermoplastic elastomer resin is made highly viscous by using the solid phase polymerization method, the quality of the resultant product is excellent and the side reaction products and the like can be easily removed by an additional vacuum process. On the other hand, There is a disadvantage in that a long reaction time is further required and it is difficult to produce the product by easily changing the viscosity increase level.

 On the other hand, in the case of a molded article using a thermoplastic elastomer resin composition containing mica (mica), it has been used as an automobile interior mat and a watch band because it has an advantage in realizing surface color due to the reflection of the surface, There is a problem that it is difficult to lower the physical properties and improve the surface gloss.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a thermoplastic elastomer resin composition having excellent mechanical properties and improved extrusion processability, To provide a molded article.

In order to solve the above technical problems, the present invention provides a thermoplastic elastomer composition comprising: a thermoplastic elastomer resin; And mica particles, wherein the mica particles have an average particle diameter of 10 to 100 m on the basis of d50, and the content of the mica particles is 0.5 to 5 parts by weight based on 100 parts by weight of the composition. Parts by weight of the thermoplastic elastomer resin composition.

According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic elastomer resin composition of the present invention.

The thermoplastic elastomer resin composition of the present invention has excellent surface properties (metal texture and surface gloss), excellent workability, moldability and dimensional stability, and excellent mechanical properties such as tensile strength, impact strength and elongation, It can be useful for portable devices.

Hereinafter, the present invention will be described in more detail.

As used herein, " parts by weight " means parts by weight.

The resin composition of the present invention comprises (1) a thermoplastic elastomer resin and (2) mica particles. In addition, the resin composition of the present invention may optionally further comprise (3) a dispersing additive and / or (4) one or more other additives.

(1) Thermoplastic elastomer ( TPE ) Suzy

The thermoplastic elastomer resin composition of the present invention comprises a thermoplastic elastomer (TPE) resin as a base resin.

The thermoplastic elastomer resin that can be included in the resin composition of the present invention is not limited as long as it can be applied as a non-coated metallic material. As the thermoplastic elastomer (TPE) resin, a conventional TPE resin may be used singly or in combination of two or more thereof .

Examples of the thermoplastic elastomer resin include a thermoplastic polyester elastomer (TPEE) (including a thermoplastic copolyester elastomer), a thermoplastic styrene-butadiene elastomer (TPE-S), a thermoplastic polyurethane (TPU) Can be used.

According to one embodiment of the present invention, a TPEE resin may be used as the thermoplastic elastomer resin, and the TPEE resin may be one commonly used, and may contain a plasticizer and have a controlled hardness. However, And may be variously selected depending on the article to be applied.

The TPEE is a thermoplastic polymer having a hard segment hard segment and a soft segment soft block copolymerized.

In one embodiment, the hard segment comprises polymerized units of an aromatic dicarboxylic compound and a diol, and the soft segment comprises polymerized units of a polyalkylene oxide.

Examples of the aromatic dicarboxylic compound include terephthalic acid (TPA), isophthalic acid (IPA), 1,5-dinaphthalenedicarboxylic acid (1,5-NDCA) 2,6-dinaphthalenedicarboxylic acid (2,6-NDCA), dimethyl terephthalate (DMT), dimethyl isophthalate, or a combination thereof may be used DMT can be preferably used.

The diol may be a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms. Examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, Hexanediol, 1,4-cyclohexanedimethanol, or a combination thereof. Of these, 1,4-butanediol can be preferably used.

The polyalkylene oxide may be selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol (PTMEG), and combinations thereof. Preferably, PTMEG can be used.

According to one embodiment, the thermoplastic polyester elastomer may be branched by a branching agent, which improves the stability of the strand during the production of TPEE by increasing the melt tension, . The branching agent may be selected from, for example, glycerol, pentaerythritol, neopentylglycol, or a combination thereof, preferably glycerol.

The TPEE which can be used in the present invention can be generally produced by melt polymerization comprising two steps of an oligomerization reaction and a polycondensation reaction, preferably a branched thermoplastic polyester-based elastomer.

In one embodiment, the branched TPEE can be prepared by charging the components described above into a reactor and then carrying out an oligomerization reaction in the presence of a suitable catalyst (e.g., tetra-n-butoxy titanium (TBT) And the polycondensation reaction. The oligomerization reaction may be carried out at 140 to 215 ° C for 3 to 4 hours, and the polycondensation reaction may be carried out at 210 to 250 ° C for 4 to 5 hours The process can be proceeded to stepwise depressurization from 760 torr to 0.3 torr for a period of time.

In one embodiment, considering the mechanical strength, flexibility, etc., the soft segment content in the TPEE is preferably 5 to 75% by weight, more preferably 30 to 70% by weight based on 100% by weight of total TPEE. If the soft segment content in the TPEE is too small, the hardness of the TPEE is increased and the flexibility is not expected. On the contrary, if the soft segment content is excessively high, it is difficult to expect a high heat resistance performance.

According to one embodiment, the TPEE may have an intrinsic viscosity of 1.7 to 2.2 dl / g, more preferably 1.9 to 2.0 dl / g.

In the resin composition of the present invention, the content of the thermoplastic elastomer resin may be, for example, 60 to 99 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer resin composition of the present invention. More specifically, the content of the thermoplastic elastomer resin in the total 100 parts by weight of the composition is at least 65 parts by weight, at least 70 parts by weight, at least 75 parts by weight, at least 80 parts by weight, at least 85 parts by weight, at least 90 parts by weight, or at least 95 parts by weight And may be 98.5 parts by weight or less, 98 parts by weight or less, or 97.5 parts by weight or less.

(2) Mica (Mica) particles

The thermoplastic elastomer resin composition of the present invention comprises mica (mica) particles.

The above-mentioned mica particles are contained in the resin composition, and serve to improve surface gloss while imparting a metal texture.

The mica particles used in the present invention may be used singly or in combination of two or more. The kind, shape and size of the mica particles to be used may be selected according to the appearance characteristics required in the molded article to which the thermoplastic elastomer resin composition of the present invention is applied. The surface of the mica particles may also be coated or surface treated.

The average particle diameter of the mica particles used in the present invention may be 10 to 100 mu m, preferably 10 to 90 mu m, more preferably 10 to 100 mu m on the basis of d50 (an intermediate value to which 50% or more of the mica particles belong) To 80 [mu] m. When the average particle size of the mica particles is less than 10 m, it may be difficult to realize the desired appearance of metal texture and surface gloss (shine). When the average particle size of the mica particles exceeds 100 m, And the mica grains tend to be oriented or deviated. As a result, weld lines and flow marks due to mica particles are generated during injection molding to deteriorate the appearance of molded articles, and mechanical properties such as tensile strength, flexural strength and elongation are poor , Dispersibility and processability may be poor.

In the resin composition of the present invention, the content of the mica particles is more than 0.5 parts by weight to less than 5 parts by weight based on 100 parts by weight of the total amount of the thermoplastic elastomer resin composition of the present invention. More specifically, the content of the mica particles in the total 100 parts by weight of the composition may be not less than 0.6 parts by weight, not less than 0.7 parts by weight, not less than 0.8 parts by weight, not less than 0.9 parts by weight, or not less than 1 part by weight, 4 parts by weight or less, 3.5 parts by weight or less, or 3 parts by weight or less. When the content of the mica particles in a total of 100 parts by weight of the composition is 0.5 parts by weight or less, it may be difficult to realize a desired level of appearance of metal texture and surface gloss (shine). If the content of the mica particles is more than 5 parts by weight , Mechanical properties such as tensile strength, flexural strength and elongation are poor, and dispersibility and workability may be poor.

(3) Additives for dispersing

The thermoplastic elastomer resin composition of the present invention may further include an additive for dispersion in order to further improve the dispersibility of the mica particles.

 The dispersing additive that can be used in the present invention includes a polymer resin containing an amine group and a phosphoric acid group; Polymeric resin containing an amine group and a peptidic acid group; Or a mixture thereof. The polymer resin is not particularly limited as long as it contains an amine group and a phosphoric acid group at the same time or contains both an amine group and a peptide acid group. Preferably, the main chain of the polymer resin is a polyacrylate, a polyurethane, , And more preferably polyacrylate.

According to one embodiment of the present invention, the dispersing additive may be selected from a polyacrylate resin containing an amine group and a peptide acid group, a polyacrylate resin containing an amine group and a phosphoric acid group, or a mixture thereof have.

Examples of the dispersant for use in the present invention include BYK 4102P (a polyacrylate resin containing an amine group and a peptide acid group as a functional group), BYK 3955P (an amine group as a functional group, A polyacrylate resin containing a phosphoric acid group and having an average of not more than 2 functional groups) or BYK D2200 (a polyacrylate resin containing an amine group and a phosphoric acid group as functional functional groups and having an average of 2 functional functional groups Etc.).

In the present invention, when a polymer resin which simultaneously contains an amine group and a phosphoric acid group or a polymer resin which simultaneously contains an amine group and a peptide acid group is used as an additive for dispersing the mica particles, existing additives for dispersing organic or inorganic fillers It is possible to exhibit significantly superior appearance characteristics and dispersibility.

According to one embodiment of the present invention, the content of the dispersing additive is 0.1 part by weight to less than 3 parts by weight (for example, 0.2 to 2.9 parts by weight) based on 100 parts by weight of the total amount of the thermoplastic elastomer resin composition of the present invention Preferably 0.2 to 2.5 parts by weight, more preferably 0.3 to 2 parts by weight. When the content of the dispersing additive in the total 100 parts by weight of the composition is 0.1 parts by weight or less, the effect of improving the dispersibility of the mica particles by the use of the dispersing additive may be insignificant. When the content of the dispersing additive is 3 parts by weight or more , Appearance and mechanical properties may be poor.

(4) Other additives

The thermoplastic elastomer resin composition of the present invention may further comprise, in addition to the above-mentioned components, one or more other additives usually added to the thermoplastic resin composition for injection molding or extrusion molding. The other additives may be selected from the group consisting of a light stabilizer, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, a colorant, or a combination of two or more thereof.

Examples of the light stabilizer include 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxy-benzophenone, 2- (2'- Bis (1-methyl-1-phenylethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin- ) -5-hexyloxy-phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis - (2H-benzotriazol-2-yl)) - 4- (1,1,3,3-tetramethylbutyl) phenol or a mixture of two or more thereof.

As the thermal stabilizer, a bisphenol A epoxy resin, a monocarbodiimide, a polycarbodiimide, or a mixture of two or more thereof may be used, but is not limited thereto.

Examples of the antioxidant include tris (nonylphenyl) phosphite, (2,4,6-tri-tert-butylphenyl) (2-butyl- (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4- Organic phosphorus antioxidants such as spite or distearyl pentaerythritol diphosphite; (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or octadecyl-3- (3,5- Phenyl) propionate, etc .; a thioester antioxidant such as pentaerythritol tetrakis (3-dodecylthiopropionate), or a mixture of two or more of them may be used, It does not.

The nucleating agent may include, but is not limited to, talc, silicate, ionomer, sodium 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate or a mixture of two or more thereof.

The lubricant may be a long chain ester of pentaerythritol, stearyl stearate, or a mixture of two or more thereof, but is not limited thereto.

As the colorant, pigments, dyes, carbon black or a combination thereof can be used. The kind of pigment, dye and carbon black is not particularly limited, and commercially available products can be used.

The content of the other additives is not particularly limited and may be an amount that can be used to add additional functions to the extent that the desired physical properties of the thermoplastic elastomer resin composition of the present invention are not impaired.

According to one embodiment of the present invention, the content of the other additives may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic elastomer resin composition of the present invention May be 1 to 5 parts by weight. When the content of the other additives is less than 0.1 part by weight, the effect of improving the various functions due to the use of other additives may be insignificant. When the content of the other additives is more than 10 parts by weight, the appearance and mechanical properties are poor .

The thermoplastic elastomer resin composition of the present invention can be used as a non-coated metallic material because it can impart metallic texture and surface gloss through mica particles contained in the composition without additional coating process.

Therefore, according to another aspect of the present invention, there is provided a molded article comprising the thermoplastic elastomer resin composition of the present invention.

The molded article can be produced by extruding or injection molding the thermoplastic elastomer resin composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  1 to 10 and Comparative Example  1 to 7

The thermoplastic elastomer resin compositions of Examples 1 to 10 and the thermoplastic elastomer resin compositions of Comparative Examples 1 to 7 were prepared by mixing the thermoplastic elastomer resin, mica particles and additives in the amounts shown in Tables 1 and 2 below.

Thereafter, extrusion was performed on each of the prepared thermoplastic elastomer resin compositions using a 32 pie twin screw extruder while maintaining the extrusion temperature within the range of 230 to 250 ° C and maintaining the extruder rotating speed within the range of 200 rpm to 250 rpm, Injection specimens were manufactured using an injection machine (mold force: 100 to 200 tons) under the same temperature conditions.

Injection specimens for the measurement of surface gloss, dispersibility and workability were prepared from square specimens of 100mm × 100mm size. Injection specimens for the measurement of mechanical properties were prepared for tensile strength, flexural strength and tensile elongation, An injection specimen conforming to each ASTM standard was prepared.

[Property evaluation]

(1) Surface glossiness

The Flop index was measured using a CM-M6 Spectrophotometer from Minolta. Specifically, the luminance of the reflected light was measured at an angle of 15 °, 45 °, and 110 ° with respect to the normal portion (Normal) of the injection specimen produced through the thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7, And a flop index was calculated by substituting the following equation (1).

[Equation 1]

L ^* of the reflected light measured at an angle of _{15 [deg.]} = 15 [

The luminance of the reflected light measured at an angle of L ^* _{45 °} = 45 °

The luminance of the reflected light measured at an angle of L ^* _{110 °} = 110 °

The flop index of the surface of the object without metal texture is 0, the flop index of the actual metal surface is 15 to 17, the flop index of the surface coated with the coating composition used in the automobile body coating is 12 to 14, The surface index of the surface that can feel the texture is 6 or more. The higher the flop index value, the better the surface gloss.

(2) Dispersibility

The dispersibility of the mica particles of the injection specimen prepared through the thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 was measured using a CM-M6 Spectrophotometer manufactured by Minolta. The lower the dispersibility, the higher the dispersibility of the mica particles.

(3) Processability

The thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were used to prepare injection specimens in consideration of the generation of gas during extrusion, the swell phenomenon and the constant introduction of raw materials, Were evaluated in five steps as described below.

- Very good: no extrusion problem at all

- Excellent: In the case of extrusion, the above-mentioned problem exists in minute but there is no problem in production

- Normal: In the case of extrusion, the above-mentioned problem exists but there is no problem in production

- Defective: The above-mentioned problem exists at the time of extrusion, especially when the swell phenomenon is serious and there is a problem in production

- Extremely defective: In case of extreme gas production, swell phenomenon,

(4) Tensile strength

Tensile strengths of the injection specimens prepared through the thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were measured according to ASTM D638.

(5) Flexural strength

Flexural strengths of the injection specimens prepared through the thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were measured according to ASTM D760.

(6) Elongation

Tensile elongation (%) was measured according to ASTM D638 for the injection specimens prepared through the thermoplastic elastomer resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7.

[Component description]

28GL80A: Thermoplastic polyester elastomer (Samyang, containing plasticizer, hardness 80A or less)

SYMIC A001: mica material (ECKART) having an average particle size of 7 탆 (center d50 basis)

SYMIC C001: mica material (ECKART) having an average particle diameter of 25 mu m (center d50 basis)

SYMIC E001: mica material (ECKART) having an average particle diameter of 75 mu m (center d50 basis)

S1303D: Mica material (BASF) having an average particle size of 19 占 퐉 (center d50 basis)

S1303V: Mica material (BASF) having an average particle diameter of 10 mu m (center d50 basis)

MagnaPearl 3000: mica material (BASF) having an average particle diameter of 80 mu m (center d50 basis)

MagnaPearl 4000: mica material (BASF) having an average particle size of 150 mu m (center d50 basis)

Song 1010: Hydroxyphenyl-based antioxidant

PEP 36: Phosphite heat stabilizer

UV 5411: benzotriazole light stabilizer

BK-A: colorant

BYK 4102P: Additive for dispersion (polyacrylate resin containing amine group and peptide acid group)

As shown in Table 1, in Examples 1 to 10, the appearance characteristics including surface gloss and workability at the surface of the injection specimen during injection molding of the composition were improved by improving the dispersibility of the mica particles in the thermoplastic elastomer resin composition And the mechanical properties (tensile strength, flexural strength, and elongation) were hardly lowered.

However, as shown in Table 2, in the case of Comparative Examples 1 and 2, the surface gloss was very low, and the metal texture could not be visually recognized. In Comparative Examples 3 and 4, the processability in extrusion molding and / or injection molding was very poor, and the dispersibility was poor and the mechanical properties were also deteriorated. In Comparative Example 5, the surface gloss was low, and in Comparative Example 6, the dispersibility and the mechanical properties were greatly deteriorated and the workability in extrusion molding and / or injection molding was poor. In the case of Comparative Example 7, the processability in extrusion molding and / or injection molding was very poor, the dispersibility was poor, and the deterioration of mechanical properties was seriously deteriorated, making it difficult to apply it as an actual product.

Claims (8)

Thermoplastic elastomer resin; And mica particles, wherein the mica particles have an average particle diameter of 10 to 100 m on the basis of d50, and the content of the mica particles is 0.5 to 5 parts by weight based on 100 parts by weight of the composition. Parts by weight of the thermoplastic elastomer resin composition. The thermoplastic elastomer resin composition according to claim 1, wherein the thermoplastic elastomer resin is selected from a thermoplastic polyester elastomer, a thermoplastic styrene-butadiene elastomer, a thermoplastic polyurethane or a combination thereof. The thermoplastic elastomer resin composition according to claim 1, further comprising a dispersing additive. The thermoplastic elastomer resin composition according to claim 3, wherein the dispersing additive is a polymer resin containing an amine group and a phosphoric acid group, a polymer resin containing an amine group and a peptide acid group, or a mixture thereof. The thermoplastic elastomer resin composition according to claim 4, wherein the main chain of the polymer resin of the additive for dispersion is polyacrylate, polyurethane, polyester or polyether. The thermoplastic elastomer composition according to claim 3, wherein the dispersing additive is selected from a polyacrylate resin containing an amine group and a peptide acid group, a polyacrylate resin containing an amine group and a phosphoric acid group, or a mixture thereof . The thermoplastic elastomeric resin composition according to claim 1, further comprising at least one additive selected from the group consisting of a light stabilizer, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, a colorant, or a combination of two or more thereof. A molded article comprising the thermoplastic elastomer resin composition according to any one of claims 1 to 7.