KR20130074366A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to prevent generation of flow mark and weld line, and to have excellent metal texture with improved brightness. CONSTITUTION: A thermoplastic resin composition includes a thermoplastic resin; a plate shaped metal particle, and a plate shaped mica. The content of the plate shaped mica is 0.01-4.9 parts by weight per 100.0 parts by weight of the thermoplastic resin. The content of the plate shaped metal particle is 0.01-4 parts by weight per 100.0 parts by weight of the thermoplastic resin. TiO2 is coated on the surface of the plate shaped mica. The thickness of the metal particle is 1/80-1 of the long diameter thereof. The thickness of the mica is 1/100-1/2 of the long diameter thereof.

Description

Thermoplastic composition {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT USING THE SAME}

It relates to a thermoplastic resin composition.

In recent years, plastic exterior products in which various colors are implemented in electric / electronic parts and automobile parts are becoming popular, and plastic exterior products capable of feeling a more advanced texture are increasingly being launched.

These plastic exterior products mainly exhibit a metal texture on the exterior of the resin by adding metal to the plastic resin.

In order to change the luminance of such metallic materials, pigments such as carbon black and TiO ₂ are generally used.

Such pigments generally have a spherical shape, and when injection molding, there is a problem that spherical pigments are distributed mainly on the plate-shaped metal particles, thereby preventing the metal particles from appearing outward.

In addition, these particles are spherical in shape and mainly distributed inside the injection-molded product due to the injection molding property, thereby causing problems such as flow marks or weld lines that appear in the injection-molded metal material.

One embodiment of the present invention is to provide a thermoplastic resin composition having almost no appearance of flow marks and weld lines and having an excellent metallic texture with improved brightness.

In one embodiment of the present invention, a thermoplastic resin; Plate-shaped metal particles; And it comprises a plate-shaped mica, the content of the plate-shaped mica provides a thermoplastic resin composition is 0.01 to 4.9 parts by weight relative to 100 parts by weight of the thermoplastic resin.

The content of the plate-shaped mica may be 0.01 to 4 parts by weight based on 100 parts by weight of the thermoplastic resin.

The content of the plate-shaped metal particles may be 0.01 to 4 parts by weight based on 100 parts by weight of the thermoplastic resin.

The plate-shaped mica may be coated with TiO ₂ on the surface.

The plate-shaped metal particles may have a ratio of thickness to long diameter of 1/80 to 1.

The plate-shaped mica may have a ratio of thickness to long diameter of 1/100 to 1/2.

The thermoplastic resin may be a polycarbonate resin, a rubber modified vinyl copolymer resin, a polyester resin, a polyalkyl (meth) acrylate resin, a polystyrene resin, a polyolefin resin, or a combination thereof.

The thermoplastic resin may be acrylonitrile-butadiene-styrene graft resin (ABS).

The metal particles may be made of aluminum, copper, gold, or a combination thereof.

The thermoplastic resin composition according to the exemplary embodiment of the present invention hardly generates a flow mark and a weld line on the appearance of the molded article.

In addition, it is possible to achieve excellent metal texture with improved brightness in the appearance of the molded article.

Therefore, the present invention can be applied to a product having a metallic texture on the exterior without a painting process.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, unless otherwise specified, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible. "(Meth) acrylic acid ester" means that both "acrylic acid alkyl ester" and "methacrylic acid alkyl ester" can be used. It means that it is possible.

Unless otherwise specified herein, "average particle diameter" of the plate-shaped particles means "long diameter", "long diameter" means the longest length of a line connecting two points in a closed curve, In this case, the "closed curve" means a curve in which a point on the curve moves in one direction and returns to the starting point.

In one embodiment of the present invention provides a composition and its molded article to provide a metal texture without separate painting (painting), and used a flop index as an indicator of the performance of the molded article. The flop index is an index indicating the surface metal texture, and the luminance (L) of each reflected light at 15 °, 45 °, and 110 ° is usually measured and obtained according to the following definition. L (x˚) means luminance measured at x˚.

The flop index of the non-metallic surface is 0, the flop index of the metal is about 15 to about 17, and the flop index of the metallic coating used for automobile body coating is about 11, The flop index is about 6.5 or more.

In order to realize the metallic texture, the average particle diameter, particle size distribution, surface roughness, and combination of various particles of the metallic particles to be introduced should be well-fitted, and one embodiment of the present invention provides an optimal composition for implementing such physical properties and molded articles thereof. do.

According to one embodiment of the present invention, a thermoplastic resin; Plate-shaped metal particles; And it comprises a plate-shaped mica, the content of the plate-shaped mica provides a thermoplastic resin composition is 0.01 to 4 parts by weight relative to 100 parts by weight of the thermoplastic resin.

The metal particles and mica may be plate-shaped.

The thermoplastic resin composition hardly generates a flow mark and a weld line during injection, thereby manufacturing a molded article having an excellent metal texture.

Therefore, the present invention may be usefully applied to molded articles having excellent appearance, in particular, plastic exterior products such as electric and electronic parts and automobile parts without a separate coating process. Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

Thermoplastic resin

The thermoplastic resin known as the thermoplastic resin can be used without limitation, and for example, polycarbonate resin, rubber modified vinyl-based graft copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin Resin or a combination thereof can be used. The thermoplastic resin may impart basic physical properties such as impact resistance, heat resistance, bending characteristics, and tensile properties.

The polycarbonate resin may be prepared by reacting a diphenol with phosgene, a halogen formate, a carbonic ester, or a combination thereof.

Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Of these, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- Cyclohexane may be used, and more preferably 2,2-bis (4-hydroxyphenyl) propane may be used.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, specifically 15,000 to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.

Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.

The rubber-modified vinyl-based graft copolymer resin is a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the rubbery polymer.

The rubbery polymer may be at least one selected from the group consisting of butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (Meth) acrylate rubber composite or a combination thereof.

Wherein the vinyl polymer comprises 50 to 95% by weight of a first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And 5 to 50% by weight of a second vinyl monomer of an unsaturated nitrile monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof.

As the aromatic vinyl monomer, styrene, C1 to C10 alkyl-substituted styrene, halogen-substituted styrene, or a combination thereof may be used. Specific examples of the alkyl-substituted styrene include o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and -methylstyrene.

As the acrylic monomer, alkyl (meth) acrylate, (meth) acrylic acid ester, or a combination thereof may be used. Wherein said alkyl means C1 to C10 alkyl. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Methacrylate may be used. Specific examples of the (meth) acrylic acid esters include (meth) acrylates.

As the heterocyclic monomers, maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof may be used.

As the unsaturated nitrile monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or a combination thereof may be used.

The rubber particle size of the rubber-modified vinyl graft copolymer may be 0.05 to 4 μm in order to improve impact resistance and surface properties of the molded product. When the rubber particle size is 0.05 to 4 μm, the impact strength is excellent. Can be secured.

The rubber modified vinyl graft copolymer may be used alone or in the form of a mixture of two or more thereof.

Specific examples of the rubber-modified vinyl graft copolymers include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of butadiene rubber, acrylic rubber or styrene / butadiene rubber. have.

Specific examples of the rubber-modified vinyl-based graft copolymer include graft-copolymerized methyl (meth) acrylate with butadiene rubber, acrylic rubber or styrene / butadiene rubber.

More specific examples of the rubber-modified graft copolymers include acrylonitrile-butadiene-styrene graft copolymers.

The method for producing the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used, For example, the aforementioned aromatic vinyl monomer may be added in the presence of a rubbery polymer and emulsion polymerization or bulk polymerization may be carried out using a polymerization initiator.

The polyester resin may be an aromatic polyester resin, which is obtained by condensation polymerization of a terephthalic acid or terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms by melt polymerization. Wherein said alkyl means C1 to C10 alkyl.

Specific examples of the aromatic polyester resin include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexanedimethylene terephthalate resin, or a part of these resins Among them, a polyethylene terephthalate resin, a polytrimethylene terephthalate resin, a polybutylene terephthalate resin and an amorphous polyethylene terephthalate resin can be used. And more preferably, polybutylene terephthalate resin and polyethylene terephthalate resin can be used.

The polybutylene terephthalate resin is a polymer polycondensed by direct esterification or transesterification of a 1,4-butanediol monomer and a terephthalic acid or dimethyl terephthalate monomer.

In order to increase the impact strength of the polybutylene terephthalate resin, the polybutylene terephthalate resin may be selected from polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or aliphatic poly. It may be used in the form of a modified polybutylene terephthalate resin copolymerized with an amide or blended with an impact improving component.

The polybutylene terephthalate resin may have an intrinsic viscosity [η] of 0.35 kPa to 1.5 kPa / g as measured by 25 ° C. of o-chlorophenol, and specifically, may be 0.5 kPa to 1.3 kPa / g. When the intrinsic viscosity of the polybutylene terephthalate resin is within the above range, the mechanical strength, the moldability, and the like are excellent.

The polyalkyl (meth) acrylate resin can be obtained by polymerizing a starting monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization and emulsion polymerization.

The alkyl (meth) acrylate has an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (Meth) acrylate etc. are mentioned.

At this time, the alkyl (meth) acrylate may be included in more than 50% by weight relative to the total amount of polyalkyl (meth) acrylate.

The polyalkyl (meth) acrylate may have a weight average molecular weight in the range of 10,000 to 200,000 g / mol, specifically, may have a range of 15,000 to 150,000 g / mol. When the weight average molecular weight of the polyalkyl (meth) acrylate is within the above range, the hydrolysis resistance, scratch resistance and processability are excellent.

As the polystyrene resin, for example, rubber-modified polystyrene resin (HIPS) reinforced with impact strength may be used.

The polyolefin resin may be a polyethylene resin (PE), a polypropylene resin (PP), a resin in a copolymerized form thereof, or the like.

The thermoplastic resin may be used in the form of an alloy mixed with two or more kinds, and examples thereof include polycarbonate, acrylonitrile-butadiene-styrene graft resin (ABS), and styrene-acrylonitrile copolymer resin (SAN). mixture; Or when using a mixture of polycarbonate, acrylate-styrene-acrylonitrile graft resin (ASA) and styrene-acrylonitrile copolymer resin (SAN).

Metal particles

The thermoplastic resin may include metal particles to impart a metal texture to the molded article. More specifically, the metal particles may be plate-shaped metal particles.

The metal particles may have a ratio of short diameter to long diameter of 1/80 to 1. In the case of using the above-described metal particles, the change of orientation of the metal particles with respect to the flow rate during injection can be suppressed to the maximum by the effect of the long diameter and the supporting action between the particles.

This makes it possible to provide a material having no flow mark, no weather line, and excellent metal feeling.

The metal particles may have a long diameter of 48 to 5000, and the metal particles may have an average particle diameter of 8 to 100. The range of the long diameter may be selected according to required properties, and the longer the long diameter may suppress the change in orientation within the composition range.

In addition, the average particle diameter of the metal particles may be selected according to the characteristics of the molded article required, and is not limited to the above range.

In addition, the content of the metal particles may include 0.01 to 4 parts by weight based on 100 parts by weight of the thermoplastic resin. More specifically, it may be 0.1 to 2 parts by weight, 0.2 to 1 parts by weight or 0.3 to 0.8 parts by weight based on 100 parts by weight of the thermoplastic resin.

When satisfying the above range, it is possible to satisfy the required metal feeling. However, if the content of the metal particles is less than the above range may not express a sufficient metal texture, if more than the above range may have a problem that can lead to a decrease in the physical properties of the base resin.

The plate-shaped metal particles may be a kind of sparkling particles having a flat surface that reflects light. At this time, the flat surface means a flat surface to the extent that the particles glisten with the naked eye, and means, for example, the surface of the plate glass, or the metal surface finished by polishing.

The plate-shaped metal particles may be made of a material containing aluminum, copper, gold, or a combination thereof, preferably made of aluminum.

Plate-shaped Mica

Mica according to an embodiment of the present invention may be a plate-shaped mica. For this reason, it may be more efficient to express a metal feeling due to the plate-shaped metal particles on the surface of the molded article.

The content of the plate-shaped mica may be 0.01 to 4.9 parts by weight, more specifically 0.01 to 4 parts by weight, 0.1 to 4 parts by weight, 0.2 to 3.5 parts by weight or 0.3 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin. have.

When the content of the mica is 5 parts by weight or more, the impact strength decrease of the molded article is serious.

The plate-shaped mica may be coated with TiO ₂ on the surface. The coating may be of island type.

The plate-shaped mica may have a ratio of thickness to long diameter of 1/100 to 1/2. It is effective to improve the luminance of the metal particles only when the above range is satisfied.

The mica may have an average particle diameter of 10 to 200 μm, a thickness of 0.5 to 10 μm, and a cross sectional area of 80 to 32,000 μm ² . When the mica particles have an average particle diameter, thickness, and cross-sectional area in the above range, a molded article having excellent metal texture can be obtained with little generation of flow marks and weld lines.

Other additives

The thermoplastic resin composition may include an antibacterial agent, a heat stabilizer, an antioxidant, a release agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, a admixture, a colorant, a stabilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, a weatherproof agent, a ultraviolet absorber, a sunscreen, It may further include an additive of a nucleating agent, an adhesion aid, an adhesive, or a combination thereof.

The antioxidant may be a phenol, phosphite, thioether or amine antioxidant, the release agent is a fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid Metal salts, montanic acid ester waxes or polyethylene waxes may be used. Further, benzophenone type or amine type endurance agent can be used as the weathering agent, and a dye or pigment can be used as the coloring agent. Titanium dioxide (TiO ₂ ) or carbon black can be used as the ultraviolet ray blocking agent. As the nucleating agent, talc or clay may be used.

The additive may be suitably included within a range that does not impair the physical properties of the thermoplastic resin composition, specifically, may be included in 40 parts by weight or less based on 100 parts by weight of the thermoplastic resin composition, more specifically 0.1 to 30% by weight. It can be included as a wealth.

The above-mentioned thermoplastic resin composition can be manufactured by a well-known method of manufacturing resin composition. For example, the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

According to another embodiment, a molded article manufactured by molding the aforementioned thermoplastic resin composition is provided. That is, a molded article can be manufactured by various processes, such as injection molding, blow molding, extrusion molding, and thermoforming, using the said thermoplastic resin composition. In particular, there is little flow mark and weld line generation and can be usefully applied to molded articles having a metallic texture appearance, in particular, plastic exterior products such as electric and electronic parts and automobile parts.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Example

A thermoplastic resin composition was prepared as shown in Table 1 below.

Item Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 (A) thermoplastic
Suzy
(Parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100
100 (B)
Amorphous plate-shaped metal particles (B-1)
(Parts by weight) 0.5 0.5 0.5 0.5 0.5 - - 0.5 0.5 0.5 - - 0.5 (B-2)
(Parts by weight) - - - - - 0.5 0.5 - - - 0.5 0.5 - (c) mica 0.3 0.5 One 2 3 One 3 - - - - - 5 TiO ₂ - - - - - - - 0.1 0.3 One One 3 -

Description of each component used in Table 1 is as follows.

(A) a thermoplastic resin

Graft ABS resin consisting of 25% by weight of acrylonitrile and 75% by weight of styrene in 30 parts by weight of butadiene rubber

(B) amorphous Plate  Metal particles

B-1) Silberline, amorphous plate-shaped aluminum particles with a long diameter of 14 µm and a thickness of 0.2 µm

B-2) Amorphous plate-shaped aluminum particles with a long diameter of 8 µm and a thickness of 0.1 µm, Yamato Metal

(C) Plate-shaped  Synthetic mica having a long diameter of 30 μm and a thickness of 5 μm, Merk

Example  1 to 7 and Comparative example  1 to 6

After preparing the thermoplastic resin composition according to each of Examples 1 to 7 and Comparative Examples 1 to 6 with the composition shown in Table 1 using the above-mentioned components, the temperature range of 180 to 240 ℃ in a conventional twin screw extruder After extruding, the extrudate was prepared in pellet form.

After drying the pellets prepared according to Examples 1 to 7 and Comparative Examples 1 to 6 for 4 hours at 80 ℃, using an injection molding machine having an injection capacity of 6 Oz, cylinder temperature 210 to 250 ℃, mold temperature 80 To 120 ° C., the molding cycle was set to 30 seconds, and the ASTM dumbbell test specimen was injection molded to prepare a physical specimen.

Physical property measurement results of the prepared specimens are shown in Table 2 below.

Item Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 6 Metal texture
(FI) 6 6 7 8 8 11 12 6 5 4 9 7 8 Luminance (L) 71 72 74 76 78 73 76 68 72 74 73 77 79 Impact strength 22 22 21 20 19 22 20 22 22 21 21 20 17

The physical property measurement standard of Table 2 is as follows.

Metal texture and luminance

The flop index was measured using a measuring instrument (manufacturer: X-rite, model name: MA98) to measure metal texture and luminance. Using the ASTM E2539-08 method, the flip-flop effect, which is the texture of aluminum particles, was evaluated by combining the angles of -15, 15, 25, 45, 75, and 110 degrees. Are listed in Table 2 above.

Impact strength

In accordance with ASTM D256, a standard measurement method, the impact strength (mechanical strength evaluation) of the specimens was measured.

Through the above Table 2, the thermoplastic resin compositions of Examples 1 to 7 were excellent in the metal texture, excellent in terms of flow mark and weld line reduction, and also excellent in impact strength.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

Thermoplastic resin;
Plate-shaped metal particles; And
Including mica of the plate,
The content of the plate-shaped mica is 0.01 to 4.9 parts by weight based on 100 parts by weight of the thermoplastic resin.
The method of claim 1,
The content of the plate-shaped mica is 0.01 to 4 parts by weight based on 100 parts by weight of the thermoplastic resin.
The method of claim 1,
The content of the plate-shaped metal particles is from 0.01 to 4 parts by weight based on 100 parts by weight of the thermoplastic resin.
The method of claim 1,
The plate-shaped mica is a thermoplastic resin composition is coated with TiO ₂ on the surface.
The method of claim 1,
The plate-shaped metal particles are a thermoplastic resin composition having a ratio of the thickness to the long diameter of 1/80 to 1.
The method of claim 1,
The plate-shaped mica is a thermoplastic resin composition of 1/100 to 1/2 the ratio of the thickness to the long diameter.
The method of claim 1,
The thermoplastic resin is a polycarbonate resin, rubber modified vinyl copolymer resin, polyester resin, polyalkyl (meth) acrylate resin, polystyrene resin, polyolefin resin or a combination thereof.
The method of claim 1,
The thermoplastic resin is an acrylonitrile-butadiene-styrene graft resin (ABS).
The method of claim 1,
The metal particle is a thermoplastic resin composition of aluminum, copper, gold or a combination thereof.