阅读说明：本技术 热塑性树脂组合物及由其生产的模制品 (Thermoplastic resin composition and molded article produced therefrom ) 是由 李玟洙 埃里克·阿里芬 李善熺 李凤宰 洪尚铉 于 2019-09-24 设计创作，主要内容包括：本发明的热塑性树脂组合物包含：约100重量份的包括聚酯树脂的热塑性树脂；约50重量份至150重量份的玻璃纤维；以及约1重量份至10重量份的聚醚-酯共聚物,其中基于ISO1133在230℃和2.16kg的条件下测量,聚醚-酯共聚物的熔体体积流动速率(MVR)为约30cm～3/10min至120cm～3/10min。热塑性树脂组合物的抗冲击性、外观特性、金属结合性等优异。(The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a thermoplastic resin comprising a polyester resin; about 50 to 150 parts by weight of glass fiber; and about 1 to 10 parts by weight of a polyether-ester copolymer, wherein the polyether-ester copolymer has a melt volume flow rate (MVR) of about 30cm, measured at 230 ℃ and 2.16kg based on ISO1133 3 10min to 120cm 3 And/10 min. Impact resistance of the thermoplastic resin composition,Excellent appearance characteristics, metal bonding properties, and the like.)

1. A thermoplastic resin composition comprising:

about 100 parts by weight of a thermoplastic resin comprising a polyester resin;

about 50 to about 150 parts by weight of glass fibers; and

from about 1 to about 10 parts by weight of a polyether-ester copolymer,

wherein the polyether-ester copolymer has a melt volume flow rate (MVR) of about 30cm, measured according to ISO1133 at 230 ℃ and 2.16kg³10min to 120cm³/10min。

2. The thermoplastic resin composition of claim 1, wherein said polyester resin comprises at least one of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexanedimethanol terephthalate.

3. The thermoplastic resin composition of claim 1 or 2, wherein the polyester resin comprises about 20 wt% or less of polyethylene terephthalate and about 80 wt% or more of polybutylene terephthalate.

4. The thermoplastic resin composition of any of claims 1-3, wherein the thermoplastic resin comprises about 70 wt% or more of the polyester resin and about 30 wt% or less of polycarbonate resin.

5. The thermoplastic resin composition of any of claims 1-4, wherein said glass fibers have a rectangular cross-section, an aspect ratio (long side length/short side length) of about 1.5 to about 10, and a short side length of about 2 μm to about 10 μm.

6. The thermoplastic resin composition of any of claims 1-5, wherein said polyether-ester copolymer is C-inclusive₄To C₂₀Dicarboxylic acid, C₁To C₁₀A polymer of a reaction mixture of a diol and a poly (oxyalkylene) diol.

7. The thermoplastic resin composition of any of claims 1-6, wherein a weight ratio of the glass fibers and the polyether-ester copolymer is about 10: 1 to about 50: 1.

8. The thermoplastic resin composition of any of claims 1-7, wherein the thermoplastic resin composition has a dart drop height of about 65cm to about 100cm in a DuPont drop test at which cracks develop on a 2.0mm thick sample when 500g of dart is dropped on the sample.

9. The thermoplastic resin composition of any of claims 1-8, wherein the thermoplastic resin composition has a metal adhesion strength of about 35MPa to about 55MPa, measured according to ISO 19095.

10. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 9.

Technical Field

The present invention relates to a thermoplastic resin composition and a molded article prepared therefrom. More particularly, the present invention relates to a thermoplastic resin composition having good properties in terms of impact resistance, appearance characteristics, etc., and a molded article produced therefrom.

Background

As engineering plastics, polyester resins and blends of polyester resins and polycarbonate resins exhibit useful properties, and are applied to various fields including interior and exterior materials of electric/electronic products. However, the polyester resin has problems of low crystallization rate, low mechanical strength and low impact strength.

Therefore, various attempts have been made to improve the mechanical strength and impact strength of polyester resins by adding additives such as inorganic fillers to the polyester resins. For example, polybutylene terephthalate (PBT) resin reinforced with an inorganic filler such as glass fiber is often used as a material for automobile parts or housings of mobile phones. Since such a material has a limitation in improving impact resistance, an impact modifier may be further added thereto to improve impact resistance. However, typical impact modifiers have a problem of deterioration in appearance characteristics due to elution on the surface of products when they are processed at high temperatures.

Therefore, it is required to develop a thermoplastic resin composition having good impact resistance, appearance characteristics and a balance therebetween.

Background of the invention the background of the present invention is disclosed in japanese patent laid-open No. 2012-533645 and the like.

Disclosure of Invention

[ problem ] to provide a method for producing a semiconductor device

An aspect of the present invention is to provide a thermoplastic resin composition having good properties in terms of impact resistance, appearance characteristics, and the like.

Another aspect of the present invention is to provide a thermoplastic resin composition having good metal adhesion and the like.

It is still another aspect of the present invention to provide a molded article formed of the thermoplastic resin composition.

The above aspects and other aspects of the present invention can be achieved by the present invention described below.

[ technical solution ] A

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a thermoplastic resin comprising a polyester resin; about 50 to about 150 parts by weight of glass fibers; and about 1 to about 10 parts by weight of a polyether-ester copolymer, wherein the polyether-ester copolymer has a melt volume flow rate (MVR) of about 30cm, measured according to ISO1133 at 230 ℃ and 2.16kg³10min to 120cm³/10min。

2. In embodiment 1, the polyester resin may include at least one of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, and polycyclohexanedimethanol terephthalate.

3. In embodiment 1 or 2, the polyester resin may include about 20 wt% or less of polyethylene terephthalate and about 80 wt% or more of polybutylene terephthalate.

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

5. In embodiments 1 to 4, the glass fiber may have a rectangular cross section, an aspect ratio (long side length/short side length) of about 1.5 to about 10, and a short side length of about 2 μm to about 10 μm.

6. In embodiments 1 to 5, the polyether-ester copolymer may be a packageContaining C₄To C₂₀Dicarboxylic acid, C₁To C₁₀A polymer of a reaction mixture of a diol and a poly (oxyalkylene) diol.

7. In embodiments 1-6, the weight ratio of glass fibers and polyether-ester copolymer may be from about 10: 1 to about 50: 1.

8. In embodiments 1 to 7, the thermoplastic resin composition may have a dart drop height of about 65cm to about 100cm in the dupont drop test, at which a crack is generated on a 2.0mm thick sample when 500g of the dart is dropped.

9. In embodiments 1 to 8, the thermoplastic resin composition may have a metal adhesion strength of about 35MPa to about 55MPa, measured according to ISO 19095.

10. Another aspect of the invention relates to a molded article. The molded article may be formed of the thermoplastic resin composition described in any one of embodiments 1 to 9.

[ technical effects ] of

The present invention provides a thermoplastic resin composition having good impact resistance, appearance characteristics, and the like, and a molded article produced therefrom.

Detailed Description

[ best mode ] for carrying out the invention

Hereinafter, embodiments of 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) a polyether-ester copolymer.

As used herein to represent a particular numerical range, "a through b" is defined as ". gtoreq.a and ≦ b".

(A) Thermoplastic resin

According to the present invention, the thermoplastic resin includes a polyester resin. For example, the polyester resin may be used alone or in a blend with a polycarbonate resin.

(A1) Polyester resin

The polyester resin according to the present invention may be selected from any polyester resins used in typical thermoplastic resin compositions. For example, the polyester resin may be obtained by polycondensation of a dicarboxylic acid component and a diol component, wherein the dicarboxylic acid component may include: aromatic dicarboxylic acids such as terephthalic acid (TPA), isophthalic acid (IPA), 1, 2-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and the like; and aromatic dicarboxylic acid esters such as dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl 1, 2-naphthalenedicarboxylate, dimethyl 1, 5-naphthalenedicarboxylate, dimethyl 1, 6-naphthalenedicarboxylate, dimethyl 1, 7-naphthalenedicarboxylate, ethylene 1, 8-naphthalenedicarboxylate, dimethyl 2, 3-naphthalenedicarboxylate, dimethyl 2, 6-naphthalenedicarboxylate, dimethyl 2, 7-naphthalenedicarboxylate and the like, and wherein the diol component may include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and cycloalkylene diol.

In some embodiments, the polyester resin may include at least one of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), and polycyclohexanedimethanol terephthalate (PCT).

In some embodiments, the polyester resin may be a polyester resin prepared by mixing about 10 wt% or less of polyethylene terephthalate with about 90 wt% or more of polybutylene terephthalate, for example, a polyester resin prepared by mixing about 1 wt% to about 10 wt% of polyethylene terephthalate with about 90 wt% to about 99 wt% of polybutylene terephthalate. Within this range, the thermoplastic resin composition may exhibit good impact resistance, appearance characteristics, and the like.

In some embodiments, the polyester resin may have an intrinsic viscosity [ η ] of about 0.5dl/g to about 1.5dl/g (e.g., about 0.7dl/g to about 1.3dl/g) as measured at 25 ℃ using ortho-chlorophenol as a solvent. Within this range, the thermoplastic resin composition may exhibit good mechanical properties.

(A2) Polycarbonate resin

The polycarbonate resin according to the embodiment is used to improve impact resistance, appearance characteristics, and the like of the thermoplastic resin composition, and may include polycarbonate resins used in typical thermoplastic resin compositions. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting a diphenol (an aromatic diol compound) with a precursor such as phosgene, a halogen formate or a carbonic diester.

In some embodiments, diphenols may include, for example, 4' -biphenol, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane, and 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, but are not limited thereto. For example, the diphenol may be 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane or 1, 1-bis (4-hydroxyphenyl) cyclohexane, in particular 2, 2-bis (4-hydroxyphenyl) propane, also known as bisphenol a.

In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a polycarbonate resin prepared by: a trivalent or higher polyfunctional compound, specifically, a trivalent or higher phenolic group-containing compound is added in an amount of about 0.05 mol% to about 2 mol% based on the total moles of diphenols used in the polymerization.

In some embodiments, the polycarbonate resin may be a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. Further, the polycarbonate resin may be partially or completely replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of, for example, an ester precursor of a bifunctional carboxylic acid.

In some embodiments, the polycarbonate resin can have a weight average molecular weight (Mw) of from about 20,000g/mol to about 50,000g/mol, for example from about 25,000g/mol to about 40,000g/mol, as measured by Gel Permeation Chromatography (GPC). Within this range, the thermoplastic resin composition may have good impact resistance and flowability (processability).

In some embodiments, the thermoplastic resin (a) may comprise about 70 wt% or more, e.g., about 80 wt% or more, of the polyester resin (a1) and about 30 wt% or less, e.g., about 20 wt% or less, of the polycarbonate resin (a 2). Within this range, the thermoplastic resin composition may exhibit good properties in terms of impact resistance, metal adhesion, appearance characteristics, and the like.

(B) Glass fiber

According to the present invention, the glass fiber is used to improve mechanical properties, such as rigidity and the like, of the thermoplastic resin composition, and may be selected from glass fibers used in typical thermoplastic resin compositions.

In some embodiments, the glass fibers may have a fiber shape, and may have various cross-sectional shapes, such as circular, elliptical, and rectangular. For example, glass fibers having a circular and/or rectangular cross-sectional shape may be preferable in terms of mechanical properties.

In some embodiments, the glass fiber having a circular cross-section may have a cross-sectional diameter of about 5 μm to about 20 μm and a pretreatment length of about 2nm to about 20mm, and the glass fiber having a rectangular cross-section may have an aspect ratio (ratio of a length of a long side to a length of a short side in the cross-section of the glass fiber) of about 1.5 to about 10, a length of a short side of about 2 μm to about 10 μm, and a pretreatment length of about 2mm to about 20 mm. Within this range, the thermoplastic resin composition may have good properties in terms of rigidity and processability.

In some embodiments, the glass fibers may be surface treated with typical surface treatment agents.

In some embodiments, the glass fibers may be present in an amount of about 50 to about 150 parts by weight, such as about 60 to about 120 parts by weight, and particularly about 70 to about 100 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. If the content of the glass fiber is less than about 50 parts by weight with respect to about 100 parts by weight of the thermoplastic resin, the rigidity, impact resistance, etc. of the thermoplastic resin composition may be deteriorated, and if the content of the glass fiber exceeds about 150 parts by weight, the processability, appearance characteristics, metal adhesion, etc. of the thermoplastic resin composition may be deteriorated.

(C) Polyether-ester copolymer

According to the present invention, the polyether-ester copolymer is used to improve impact resistance, appearance characteristics, metal adhesion, etc. of the thermoplastic resin composition, and may be a polyether-ester copolymer comprising C₄To C₂₀Dicarboxylic acid, C₁To C₁₀A polymer of a reaction mixture of a diol and a poly (oxyalkylene) diol.

In some embodiments, the polyether-ester copolymer can have about 30cm, measured according to ISO1133 at 230 ℃ and 2.16kg³10min to 120cm³Per 10min, e.g. about 30cm³10min to 105cm³Melt volume flow Rate (MVR) of 10 min. If the content of the polyether-ester copolymer is not within this range, impact resistance, appearance characteristics, metal adhesion, and the like of the thermoplastic resin composition may be deteriorated.

In some embodiments, the polyether-ester copolymer may be present in an amount of about 1 to about 10 parts by weight, for example about 1.5 to about 8 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. If the content of the polyether-ester copolymer is less than about 1 part by weight with respect to about 100 parts by weight of the thermoplastic resin, impact resistance, etc. of the thermoplastic resin composition may be deteriorated, and if the content of the polyether-ester copolymer exceeds about 10 parts by weight, impact resistance, appearance characteristics, metal adhesion, etc. of the thermoplastic resin composition may be deteriorated.

In some embodiments, the glass fibers and polyether-ester copolymer may be present in a weight ratio of about 10: 1 to about 50: 1, e.g., about 11: 1 to about 47: 1 (B: C) is present. Within this range, the thermoplastic resin composition may have good properties in terms of impact resistance, appearance characteristics, and a balance therebetween.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives used in typical thermoplastic resin compositions. Examples of the additives may include flame retardants, antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof, but are not limited thereto. The additive may be present in the thermoplastic resin composition in an amount of about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, relative to about 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition according to one embodiment of the present invention may be prepared in the form of pellets by mixing the above components and then melt-extruding at about 200 ℃ to about 280 ℃, for example 220 ℃ to about 250 ℃ in a typical twin-screw extruder.

In some embodiments, the thermoplastic resin composition may have a dart drop height of about 65cm to about 100cm, for example about 70cm to about 90cm, in a dupont drop test at which cracks develop on a 2.0mm thick sample when 500g of dart is dropped.

In some embodiments, the thermoplastic resin composition may have a notched izod impact strength of about 10 kgf-cm/cm to about 15 kgf-cm/cm, for example about 10 kgf-cm/cm to about 14 kgf-cm/cm, as measured on a 1/8 "thick sample according to ASTM D256.

In some embodiments, the thermoplastic resin composition may have a metal bond strength of about 35MPa to about 55MPa, for example about 35MPa to about 50MPa, measured according to ISO 19095.

The molded article according to the present invention is formed of the above thermoplastic resin composition. The thermoplastic resin composition may be prepared in the form of pellets. The prepared pellets can be produced into various molded articles (articles) by various molding methods such as injection molding, extrusion, vacuum forming, casting, and the like. These shaping methods are well known to those skilled in the art. The molded article has good impact resistance, chemical resistance and a balance therebetween, and is useful as a housing for electric/electronic products.

[ modes for the invention ]

Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the invention in any way.

Examples

The details of the components used in the examples and comparative examples are as follows.

(A) Thermoplastic resin

(A1) Polybutylene terephthalate (PBT, manufacturer: China Bluestar (R) Co., Ltd.) was used, and its intrinsic viscosity [. eta. ] was 1.3dl/g as measured at 25 ℃ using o-chlorophenol as a solvent.

(A2) Polyethylene terephthalate (PET, manufacturer: SK Chemicals, Ltd.) was used, and its intrinsic viscosity [. eta. ] was 0.8dl/g as measured at 25 ℃ using o-chlorophenol as a solvent.

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

(B) Glass fiber

(B1) Glass fibers having a rectangular cross section, a length of the short side of 7 μm, an aspect ratio of 4, and a pretreatment length of 3mm were used (manufacturer: Nitto Boseki co., Ltd.).

(B2) Glass fibers having a circular cross section, a cross-sectional diameter of 10 μm and a pretreatment length of 3mm were used.

(C) Polyether-ester copolymer

(C1) A polyether-ester copolymer (manufacturer: DSM, product name: Arnitel EE8100) was used, the MVR of which was 100cm, measured according to ISO1133 at 230 ℃ and 2.16kg³/10min。

(C2) A polyether-ester copolymer (manufacturer: DSM, product name: Arnitel EM400) was used, the MVR of which was 33cm, measured according to ISO1133 at 230 ℃ and 2.16kg³/10min。

(C3) A polyether-ester copolymer (manufacturer: DSM, product name: Arnitel EM550) was used, the MVR of which was 9cm, measured according to ISO1133 at 230 ℃ and 2.16kg³/10min。

(D) Impact modifier

An ethylene/methyl acrylate copolymer (manufacturer: DuPont, product name: Elvaloy AC1330) was used.

Examples 1 to 10 and comparative examples 1 to 8

The above components were mixed in the amounts listed in tables 1 to 3, and then extruded at 260 ℃, thereby preparing thermoplastic resin compositions in the form of pellets. Here, extrusion was performed using a twin screw extruder (L/D: 44, phi: 45mm), and the resulting pellets were dried at 80 ℃ for 4 hours or more and then injection-molded using a 6oz. injection molding machine (molding temperature: 230 ℃, mold temperature: 150 ℃) to prepare samples. The prepared samples were evaluated for the following properties, and the results are shown in tables 1 to 3.

Evaluation of Performance

(1) Plate impact resistance (unit: cm): dart drop height was measured according to dupont drop test method using 500g of dart on a 2.0mm thick sample.

(2) Notched Izod impact strength (kgf. cm/cm): notched Izod impact strength was measured according to ASTM D256 on 1/8 "thick samples.

(3) Metal bond Strength (Unit: MPa): after bonding the thermoplastic resin composition samples to the aluminum samples, the bond strength was measured according to ISO 19095. Here, the aluminum sample was subjected to TRI surface treatment of Geo nature co., ltd. to make it easy to adhere to the thermoplastic resin composition sample. The aluminum sample and the thermoplastic resin composition sample had dimensions of 1.2cm × 4cm × 0.3cm, and were adhered to each other over a cross-sectional area of 1.2cm × 0.3cm to measure the adhesive strength.

(4) Appearance evaluation: the generation of white marks was observed by naked eyes on each of the injection-molded samples prepared in examples and comparative examples.

TABLE 1

The weight portions are as follows: parts by weight per 100 parts by weight of the thermoplastic resin (A).

TABLE 2

The weight portions are as follows: parts by weight per 100 parts by weight of the thermoplastic resin (A).

TABLE 3

The weight portions are as follows: parts by weight per 100 parts by weight of the thermoplastic resin (A).

From the above results, it can be seen that the thermoplastic resin composition according to the present invention has good properties in terms of impact resistance, appearance characteristics, metal adhesion, and the like.

In contrast, it can be seen that the thermoplastic resin composition of comparative example 1 prepared using a small amount of glass fiber is deteriorated in impact strength, metal adhesion, etc.; the thermoplastic resin composition of comparative example 2 prepared using an excessive amount of glass fiber was deteriorated in plate impact strength, metal adhesion, and the like; the thermoplastic resin composition of comparative example 3 prepared using a small amount of the polyether-ester copolymer was deteriorated in impact strength and the like; also, the thermoplastic resin composition of comparative example 4 prepared using an excessive amount of the polyether-ester copolymer was deteriorated in metal adhesion and the like. In addition, the thermoplastic resin compositions of comparative examples 5 to 8 prepared using the polyether-ester copolymer (C3) or the ethylene/methyl acrylate copolymer instead of the polyether-ester copolymer (C1) were deteriorated in plate impact strength, metal adhesion, appearance characteristics, and the like.

It is to be understood that various modifications, alterations, adaptations, and equivalent embodiments may occur to one skilled in the art without departing from the spirit and scope of the present invention.