KR20210038005A - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition including: 100 parts by weight of a thermoplastic resin including a polyester resin; 15-65 parts by weight of glass fibers; and 0.5-6 parts by weight of silica aerosol, wherein the silica aerosol is in the form of secondary particles formed by aggregation of primary particles (single particles), the secondary particles have an average particle size (D50) of 30-90 micrometers as determined by a particle size analyzer, and the silica aerosol has a bulk density measured according to ASTM D1895B of 0.01-0.07 g/cm^3. The thermoplastic resin composition has excellent bonding ability to metals and impact resistance.

Description

Thermoplastic resin composition and molded article manufactured therefrom TECHNICAL FIELD [THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent metal bonding properties, impact resistance, and the like, and a molded article manufactured therefrom.

As engineering plastics, blends of polyester resins, polyester resins, and polycarbonate resins, respectively, exhibit useful properties and are applied to various fields including interior and exterior materials of electric and electronic products. However, the polyester resin has a problem in that the crystallization rate is slow, the mechanical strength is low, and the impact resistance is inferior.

In order to solve this problem, many attempts have been made to improve mechanical strength and impact resistance by mixing an additive such as an inorganic filler in a polyester resin. For example, in the case of a polybutylene terephthalate (PBT) material reinforced with an inorganic filler such as glass fiber, it is used as a housing for automobile parts or mobile phones. However, these materials also have limitations in improving impact resistance, and there is a problem of deteriorating metal bonding properties.

Therefore, there is a need to develop a thermoplastic resin composition excellent in metal bonding properties, impact resistance, and balance of properties thereof.

Background technology of the present invention is disclosed in Korean Patent Registration No. 10-0709878 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in metal bonding properties, impact resistance, and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

All of the above and other objects of the present invention can be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes 100 parts by weight of a thermoplastic resin including a polyester resin; 15 to 65 parts by weight of glass fibers; And 0.5 to 6 parts by weight of silica airgel, wherein the silica airgel is a form of secondary particles formed by agglomeration of primary particles (single particles), and an average particle size (D50) of the secondary particles measured by a particle size analyzer is 30 To 90 μm, and characterized in that the bulk density measured according to ASTM D1895B is 0.01 to 0.07 g/cm ³ .

2. In the above 1 embodiment, the polyester resin may include one or more of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene terephthalate.

3. In the above 1 or 2 embodiments, the polyester resin may include one or more of polybutylene terephthalate, polyethylene terephthalate, and polycyclohexylene terephthalate.

4. In the above 1 to 3 embodiments, the thermoplastic resin may include 70% by weight or more of the polyester resin and 30% by weight or less of the polycarbonate resin.

5. In the above embodiments 1 to 4, the silica aerogel may have an average particle size (D50) of the primary particles measured by a particle size analyzer of 10 to 100 nm.

6. In the above 1-5 embodiments, the weight ratio of the glass fiber and the silica airgel may be 5:1 to 60:1.

7. In the above embodiments 1 to 6, the thermoplastic resin composition is a drop height of a 2.0 mm thick specimen measured using a dart weighing 500 g based on a DuPont drop measurement method. May be 35 to 70 cm.

8. In the above 1 to 7 embodiments, the thermoplastic resin composition may have a notched Izod impact strength of 6 to 15 kgf·cm/cm of a 1/8" thick specimen measured according to ASTM D256.

9. In the above embodiments 1 to 8, the thermoplastic resin composition may have a metal bonding strength of 27 to 45 MPa measured according to ISO 19095.

10. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 9.

The present invention has the effect of the present invention to provide a thermoplastic resin composition excellent in metal bonding properties, impact resistance, and the like, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a thermoplastic resin; (B) glass fibers; And (C) silica airgel.

In the present specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) thermoplastic resin

The thermoplastic resin of the present invention contains a polyester resin. For example, polyester resin alone or a blend of polyester resin and polycarbonate resin can be used.

(A1) Polyester resin

As the polyester resin of the present invention, a polyester resin used in a conventional thermoplastic resin composition can be used. For example, the polyester resin is a dicarboxylic acid component, terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid. Acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as carboxylic acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl- 1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate, dimethyl-2,3-na As diol components such as aromatic dicarboxylate such as phthalate, dimethyl-2,6-naphthalate, dimethyl-2,7-naphthalate, etc., ethylene glycol, 1,2-propylene glycol, 1,3-propylene Glycol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, cyclic alkyl It can be obtained by polycondensing a rendiol or the like.

In a specific embodiment, the polyester resin is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), polycyclohexylene terephthalate (PCT). ), combinations thereof, and the like can be used. Preferably, as the polyester resin, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylene terephthalate, combinations thereof, and the like may be used.

In a specific example, the polyester resin of the present invention may have an intrinsic viscosity [η] of 0.5 to 1.5 dl/g, for example, 0.7 to 1.3 dl/g, measured using an o-chlorophenol solvent at 25°C. . Within the above range, the thermoplastic resin composition may have excellent mechanical properties.

(A2) Polycarbonate resin

The polycarbonate resin according to an embodiment of the present invention is capable of improving the impact resistance and appearance characteristics of the thermoplastic resin composition, and a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin prepared by reacting diphenols (aromatic diol compounds) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

In a specific embodiment, the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. may be exemplified, but are not limited thereto. . For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4- Hydroxyphenyl) propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, specifically, bisphenol- 2,2-bis(4-hydroxyphenyl)propane called A can be used.

In specific embodiments, the polycarbonate resin may be used having a branched chain, for example, with respect to the total diphenols used in polymerization, 0.05 to 2 mol% of a trivalent or higher polyfunctional compound, specifically, 3 It is also possible to use a branched polycarbonate resin prepared by adding a compound having a phenol group having a higher or higher phenol.

In a specific embodiment, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor, such as a bifunctional carboxylic acid.

In a specific embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 20,000 to 50,000 g/mol, for example, 25,000 to 40,000 g/mol. Within the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity (processability), and the like.

In a specific embodiment, the thermoplastic resin (A) is the polyester resin (A1) 70% by weight or more, such as 80% by weight or more, and the polycarbonate resin (A2) 30% by weight or less, such as 20% by weight It may include the following. Within the above range, the thermoplastic resin composition may have excellent impact resistance, metal bonding properties, and appearance properties.

(B) fiberglass

The glass fiber of the present invention is capable of improving mechanical properties such as stiffness of the thermoplastic resin composition, impact resistance, and the like, and a glass fiber used in a conventional thermoplastic resin composition may be used.

In embodiments, the glass fibers may be in the form of fibers, and may have cross-sections of various shapes such as a circle, an oval, and a rectangle. For example, it may be desirable in terms of mechanical properties to use fibrous glass fibers of circular and/or rectangular cross-section.

In a specific embodiment, the circular cross-section of the glass fiber may have a cross-sectional diameter of 5 to 20 µm and a length before processing of 2 to 20 mm, and the rectangular cross-section of the glass fiber has an aspect ratio of the cross-section (long diameter of the cross section/short diameter of the cross section) Is 1.5 to 10, the short diameter may be 2 to 10 μm, and the length before processing may be 2 to 20 mm. Within the above range, the stiffness and processability of the thermoplastic resin composition may be improved.

In embodiments, the glass fibers may be treated with a conventional surface treatment agent.

In a specific embodiment, the glass fiber may be included in an amount of 15 to 65 parts by weight, for example, 25 to 55 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the glass fiber is less than 15 parts by weight, based on 100 parts by weight of the thermoplastic resin, there is a concern that the stiffness and impact resistance of the thermoplastic resin composition may decrease, and when it exceeds 65 parts by weight, the processability of the thermoplastic resin composition, There is a fear that the appearance characteristics, metal bonding properties, and the like may be deteriorated.

(C) Silica aerogel

The silica aerogel of the present invention is capable of improving metal bonding properties and impact resistance of a thermoplastic resin composition, and a conventional silica aerogel having a form of secondary particles formed by agglomeration of primary particles (single particles) can be used, The average particle size (D50) of the secondary particles measured by a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) may be 30 to 90 µm, for example, 40 to 70 µm, according to ASTM D1895B. The measured bulk density may be 0.01 to 0.07 g/cm ³ , for example, 0.03 to 0.07 g/cm ³ . When the average particle size of the silica aerogel secondary particles is less than 30 μm, the impact resistance and processability of the thermoplastic resin composition may be deteriorated, and when it exceeds 90 μm, the impact resistance and metal bonding properties of the thermoplastic resin composition may be reduced. There is a risk of deterioration. In addition, when the bulk density of the silica airgel is ^{less than 0.01 g/cm 3} , the processability and metal bonding properties of the thermoplastic resin composition may be deteriorated, and ^{when it exceeds 0.07 g/cm 3} , the impact resistance of the thermoplastic resin composition, etc. There is a possibility that this may decrease.

In a specific embodiment, the silica airgel has an average particle size (D50) of 10 to 100 nm, for example, 20 to 80 nm, of the primary particles measured by a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment). Can be Within the above range, the thermoplastic resin composition may have excellent impact resistance, metal bonding properties, and the like.

In a specific embodiment, the silica airgel may be included in an amount of 0.5 to 6 parts by weight, for example, 0.5 to 5.5 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the content of the silica aerogel is less than 0.5 parts by weight based on 100 parts by weight of the thermoplastic resin, the impact resistance and metal bonding properties of the thermoplastic resin composition may be deteriorated, and when it exceeds 6 parts by weight, the impact resistance of the thermoplastic resin composition There is a risk of deterioration of properties, metal bonding properties, and the like.

In a specific embodiment, the weight ratio (B:C) of the glass fiber and the silica aerogel may be 5:1 to 60:1, for example, 5:1 to 55:1. Within the above range, the thermoplastic resin composition may have excellent impact resistance, metal bonding properties, and the like.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additives include impact modifiers, flame retardants, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the content may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets obtained by mixing the above constituents and melt-extruding at 250 to 300°C, for example, 260 to 290°C using a conventional twin screw extruder.

In a specific example, the thermoplastic resin composition has a crack occurrence drop height of a 2.0 mm thick specimen measured using a 500 g dart based on a DuPont drop measurement method, 35 to 70 cm, for example It may be 35 to 65 cm.

In a specific example, the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256, 6 to 15 kgf·cm/cm, for example, 7 to 14 kgf·cm/cm have.

In a specific embodiment, the thermoplastic resin composition may have a metal bonding strength of 27 to 45 MPa, for example, 27 to 40 MPa, measured according to ISO 19095.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the field to which the present invention belongs. Since the molded article is excellent in metal bonding properties, impact resistance, and balance of properties thereof, it is useful as a material for mobile devices and tablet devices.

Hereinafter, the present invention will be described in more detail through examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) thermoplastic resin

(A1) Polybutylene terephthalate (PBT, manufacturer: Shinkong company, product name: Shinite K006) having an intrinsic viscosity [η] of 1.10 dl/g measured using an o-chlorophenol solvent at 25°C was used.

(A2) Polyethylene terephthalate (PET, manufacturer: SK Chemicals, product name: SKYPET 1100) having an intrinsic viscosity [η] of 0.8 dl/g measured using an o-chlorophenol solvent at 25°C was used.

(A3) Bisphenol-A-based polycarbonate resin (weight average molecular weight: 25,000 g/mol) was used.

(B) fiberglass

Glass fiber (manufacturer: Nittobo, product name: CSG 3PA-830) having a cross-sectional size of 28 µm × 7 µm and a length of 3.0 mm before processing was used.

(C) Silica aerogel

(C1) Silica aerogel (manufacturer) having an average particle size (D50) of 30 nm of the primary particles, an average particle size (D50) of 40 μm of the secondary particles, and a bulk density of 0.05 g/cm ³ : JIOS Aerogel company, product name: JIOS AeroVa) was used.

(C2) Silica aerogel (manufacturer) having an average particle size (D50) of 30 nm of the primary particles, an average particle size (D50) of 20 μm of the secondary particles, and a bulk density of 0.03 g/cm ³ :JIOS Aerogel Co.) was used.

(C3) Silica aerogel (manufacturer) having an average particle size (D50) of 30 nm of the primary particles, an average particle size (D50) of 100 μm of the secondary particles, and a bulk density of 0.08 g/cm ³ :JIOS Aerogel Co.) was used.

Example 1 to 13 and Comparative example 1 to 12

Each of the above constituents was added in an amount as described in Tables 1, 2, 3 and 4 below, and then extruded at 260°C to prepare a pellet. Extrusion was performed using a twin-screw extruder with L/D=44 and diameter of 45 mm, and the produced pellets were dried at 100°C for more than 4 hours, and then injection-molded in a 6 oz injection machine (mold temperature 270°C, mold temperature: 140°C). Specimens were prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2, 3, and 4 below.

How to measure physical properties

(1) Surface impact strength (unit: cm): Based on the DuPont drop measurement method, a drop height of a 2.0 mm-thick specimen with cracks was measured using a 500 g dart.

(2) Notched Izod impact strength (unit: kgf·cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/8" thick specimen was measured.

(3) Metal bonding strength (unit: MPa): According to ISO 19095, after bonding the aluminum-based metal specimen and the thermoplastic resin composition specimen, the bonding strength was measured. Here, as the metal specimen used, a metal specimen with TRI surface treatment of Geo Nation Co., Ltd. was used to facilitate bonding with the resin composition specimen. In addition, the metal and thermoplastic resin composition specimens used were 1.2 cm × 4 cm × 0.3 cm in size, and the bonding strength was measured by attaching a cross section of 1.2 cm × 0.3 cm to each other.

Example One 2 3 4 5 6 (A)
(weight%) (A1) 100 100 100 100 100 100 (A2) - - - - - - (A3) - - - - - - (B) (parts by weight) 25 25 25 40 40 40 (C1) (parts by weight) One 2.5 5 One 2.5 5 (C2) (parts by weight) - - - - - - (C3) (parts by weight) - - - - - - Cotton impact strength (cm) 38 45 36 46 53 44 Notch Izod impact strength (kgf·cm/cm) 8 10 7 10 13 10 Metal bonding strength (MPa) 29 30 27 32 34 31

* Parts by weight: parts by weight based on 100 parts by weight of thermoplastic resin (A)

Example 7 8 9 10 11 12 13 (A)
(weight%) (A1) 100 100 100 85 75 - 80 (A2) - - - - - 100 5 (A3) - - - 15 25 - 15 (B) (parts by weight) 55 55 55 40 40 40 40 (C1) (parts by weight) One 2.5 5 2.5 2.5 2.5 2.5 (C2) (parts by weight) - - - - - - - (C3) (parts by weight) - - - - - - - Cotton impact strength (cm) 47 53 60 41 43 58 51 Notch Izod impact strength (kgf·cm/cm) 11 13 14 9 10 13 12 Metal bonding strength (MPa) 33 34 34 34 37 38 39

* Parts by weight: parts by weight based on 100 parts by weight of thermoplastic resin (A)

Comparative example One 2 3 4 5 6 (A)
(weight%) (A1) 100 100 85 85 100 100 (A2) - - - - - (A3) - - 15 15 - - (B) (parts by weight) 10 70 10 70 40 40 (C1) (parts by weight) 2.5 2.5 2.5 2.5 0.1 6.5 (C2) (parts by weight) - - - - - - (C3) (parts by weight) - - - - - - Cotton impact strength (cm) 30 72 33 74 40 31 Notch Izod impact strength (kgf·cm/cm) 5 16 6 16 9 9 Metal bonding strength (MPa) 24 25 26 26 24 30

* Parts by weight: parts by weight based on 100 parts by weight of thermoplastic resin (A)

Comparative example 7 8 9 10 11 12 (A)
(weight%) (A1) 85 85 100 100 85 85 (A2) - - - - - - (A3) 15 15 - - 15 15 (B) (parts by weight) 40 40 40 40 40 40 (C1) (parts by weight) 0.1 6.5 - - - - (C2) (parts by weight) - - 2.5 - 2.5 - (C3) (parts by weight) - - - 2.5 - 2.5 Cotton impact strength (cm) 37 33 29 42 30 31 Notch Izod impact strength (kgf·cm/cm) 7 6 6 9 6 5 Metal bonding strength (MPa) 23 32 33 23 31 25

* Parts by weight: parts by weight based on 100 parts by weight of thermoplastic resin (A)

From the above results, it can be seen that the thermoplastic resin composition of the present invention has excellent metal bonding properties and impact resistance.

On the other hand, in the case of Comparative Examples 1 and 3 in which a small amount of glass fiber was applied, it can be seen that the metal bonding property and impact resistance were deteriorated, and in the case of Comparative Examples 2 and 4 in which an excessive amount of glass fiber was applied, it was found that the metal bonding property, etc. , In the case of Comparative Examples 5 and 7 in which a small amount of silica aerogel was applied, it can be seen that metal bonding properties were deteriorated, and in Comparative Examples 6 and 8 in which an excessive amount of silica aerogel was applied, metal bonding properties, impact resistance, and the like were deteriorated. In addition, in the case of Comparative Examples 9 and 11 in which the silica airgel (C2) having an average particle size of the secondary particles less than the range of the present invention was applied instead of the silica airgel (C1) of the present invention, it can be seen that the impact resistance and the like were deteriorated. , In the case of Comparative Examples 10 and 12 to which the silica airgel (C3) having an average particle size of the secondary particles exceeding the scope of the present invention was applied, it can be seen that metal bonding properties, or metal bonding properties, and impact resistance were deteriorated.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (10)

100 parts by weight of a thermoplastic resin containing a polyester resin;
15 to 65 parts by weight of glass fibers; And
Including 0.5 to 6 parts by weight of silica airgel,
The silica aerogel is a form of secondary particles formed by agglomeration of primary particles (single particles), and the average particle size (D50) of the secondary particles measured by a particle size analyzer is 30 to 90 µm, measured according to ASTM D1895B. One bulk density (bulk density) of 0.01 to 0.07 g / cm ³ , characterized in that the thermoplastic resin composition.
The thermoplastic resin of claim 1, wherein the polyester resin comprises at least one of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene terephthalate. Composition.
The thermoplastic resin composition according to claim 1, wherein the polyester resin comprises at least one of polybutylene terephthalate, polyethylene deephthalate, and polycyclohexylene terephthalate.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin comprises 70% by weight or more of the polyester resin and 30% by weight or less of a polycarbonate resin.
The thermoplastic resin composition of claim 1, wherein the silica airgel has an average particle size (D50) of 10 to 100 nm of the primary particles measured by a particle size analyzer.
The thermoplastic resin composition of claim 5, wherein a weight ratio of the glass fiber and the silica aerogel is 5:1 to 60:1.
The method of claim 1, wherein the thermoplastic resin composition has a crack occurrence drop height of a 2.0 mm thick specimen measured using a 500 g dart based on a DuPont drop measurement method. A thermoplastic resin composition, characterized in that cm.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of 6 to 15 kgf·cm/cm.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a metal bonding force of 27 to 45 MPa measured according to ISO 19095.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 9.