KR20220043662A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

(A) 60 to 80% by weight of a base resin comprising a polybutylene terephthalate resin, and (B) a polyethylene terephthalate resin; and (C) 20 to 40% by weight of E-glass, and (D) 7 to 14 aluminum diethyl phosphinate based on 100 parts by weight of the composition including the base resin and the E-glass. parts by weight; (E) 2 to 8 parts by weight of melamine polyphosphate; And (F) relates to a thermoplastic resin composition comprising 0.1 to 0.5 parts by weight of a near-infrared transmitting anthraquinone dye, and a molded article using the same.

Description

Thermoplastic resin composition and molded article using same

It relates to a thermoplastic resin composition and a molded article using the same.

In the production of automobile parts or electric and electronic parts, bonding of the same material or different materials and excellent flame retardancy are required.

In particular, for bonding dissimilar materials, a hot melt method using an adhesive, a vibration welding method using frictional heat between materials, a thermal welding method in which contact with a hot plate is fused and adhered, an IR welding method, a type of non-contact thermal welding, etc. However, these methods have limitations in the application of components having a complex structure, so a laser fusion technique in which a transmitting body through which a near-infrared laser transmits and an absorber that is fused by absorbing a near-infrared laser are paired are widely used.

In this laser fusion technique, near-infrared laser transmittance is very important. On the other hand, polybutylene terephthalate (PBT: polybutylene terephthalate) resin is an engineering plastic having excellent mechanical and electrical properties and physical and chemical properties, and is commonly used in a conventional fusion bonding method.

In general, PBT resin has high industrial productivity due to its rapid crystallization rate and is applied to various fields. Accordingly, there is a demand for the development of a PBT material capable of laser fusion.

However, PBT resin has low transmittance in all wavelength regions due to its fast crystallization rate and crystal size, and when a thin molded product is injected at high temperature, crystallization occurs through rapid cooling in an amorphous state, so sufficient transmittance can be secured. There is no problem. In order to improve the permeability of the PBT resin, an attempt has been made to improve the permeability by adding a resin having a slow crystal growth rate, such as polyethylene terephthalate (PET), to prepare an alloy resin, but the crystallization rate of each resin is different. For this reason, it is difficult to provide optimal transmittance for laser fusion. As an example, there is a limitation in the formation of high permeability only with the alloy resin to which PET is added. There is an attempt to add a resin by blending it, but there is a limit to providing sufficient transmittance.

In addition, impact reinforcing materials and glass fibers can be added to enhance impact resistance and rigidity, but refractive index matching is required, and there is a limitation in actual product mass production because a fine ratio adjustment is required for refractive index matching. The use of it acts as a factor that inhibits the flame retardancy.

In addition, each country has begun to regulate halogen-based flame retardants, and the use of non-halogen flame retardants is important. In order to improve flame retardancy in flame-retardant polyester, a phosphorus-based aromatic flame retardant can be used, but it is accompanied by a decrease in heat resistance and impact strength. In addition, the use of a phosphorus-based flame retardant and a high molecular weight melamine-based flame retardant constituting a metal salt capable of realizing high flame retardancy may act as a factor significantly inhibiting near-infrared (NIR) laser transmittance.

An object of the present invention is to provide a thermoplastic resin composition excellent in both flame retardancy, impact resistance, rigidity and bonding strength, and a molded article using the same, while mitigating a decrease in transmittance to a near-infrared laser.

According to one embodiment, (A) a polybutylene terephthalate resin, and (B) 60 to 80% by weight of a base resin comprising the polyethylene terephthalate resin; and (C) 20 to 40% by weight of E-glass, and (D) aluminum diethyl phosphinate 7 to 100 parts by weight of the composition including the base resin and the E-glass 14 parts by weight; (E) 2 to 8 parts by weight of melamine polyphosphate; And (F) provides a thermoplastic resin composition comprising 0.1 to 0.5 parts by weight of a near-infrared transmitting anthraquinone-based dye.

The (D) aluminum diethyl phosphinate and (E) melamine polyphosphate may be included in a weight ratio of 6:1 to 1:1.

The refractive index measured at 23° C. of the (C) E-glass may be 1.550 or more.

The (C) E-glass may have an average diameter of 5 to 15 μm, and an average length of 1 to 10 mm.

The (C) E-glass may be coated with at least one of a polyurethane resin, an epoxy resin, and a polyamide resin.

The (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin may be included in a weight ratio of 8:1 to 1:1.

The base resin may include the (A) polybutylene terephthalate resin in an amount of 30 to 60 wt%, and the (B) polyethylene terephthalate resin in an amount of 10 to 40 wt%.

The thermoplastic resin composition may have a UL-94 flame retardancy rating of V0 in a molded article having a thickness of 1.5 mm.

The thermoplastic resin composition may have a near-infrared transmittance of 10% or more at a wavelength of 980 nm in a molded article having a thickness of 2 mm.

The thermoplastic resin composition may further include at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, an antistatic agent, a colorant, and an impact modifier can

The additive may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the composition including the base resin and the E-glass.

Meanwhile, a molded article using the thermoplastic resin composition according to an embodiment may be provided.

The thermoplastic resin composition according to one embodiment is excellent in flame retardancy, impact resistance, rigidity, and bonding strength while alleviating a decrease in transmittance to a near-infrared laser, and is suitable for molding automobile parts or electrical and electronic parts, especially products in which different materials are fused. It can be widely applied.

For example, since the thermoplastic resin composition according to one embodiment satisfies the transmittance of a specific range for near-infrared rays, a molded article using the same is a product optimized for a laser fusion process, and flame retardancy, impact resistance, rigidity and bonding strength are all reinforced automobile interior materials, and It can be usefully applied to automobile exterior materials and the like.

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

Also, when a part "includes" a component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

According to one embodiment, (A) a polybutylene terephthalate resin, and (B) a base resin comprising a polyethylene terephthalate resin; (C) E-glass; (D) aluminum diethyl phosphinate; (E) melamine polyphosphate; and (F) a near-infrared transmitting anthraquinone-based dye is provided.

Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

base resin

The base resin included in the thermoplastic resin composition according to the exemplary embodiment may include (A) a polybutylene terephthalate (PBT) resin and (B) a polyethylene terephthalate (PET) resin.

The polybutylene terephthalate (PBT) resin used in the thermoplastic resin composition according to an embodiment is polycondensed through direct esterification or transesterification using butane-1,4-diol and terephthalic acid or dimethyl terephthalate as monomers. As a polymer prepared by , it means a conventional polybutylene terephthalate resin.

The polybutylene terephthalate resin may have a weight average molecular weight in the range of 30,000 to 100,000 g/mol, and excellent mechanical properties may be realized within this range.

The polybutylene terephthalate resin may be mixed with polyethylene terephthalate (PET) resin.

Polyethylene terephthalate (PET) resin used in the thermoplastic resin composition according to one embodiment is a polymer prepared by polycondensation through direct esterification or transesterification using ethylene glycol and terephthalic acid or dimethyl terephthalate as monomers. , for example, a polymer having a repeating unit represented by the following formula (1) may be used.

[Formula 1]

In Formula 1, n represents an integer of 10 or more (eg, 10 to 200), preferably an integer of 95 to 120.

The base resin according to the thermoplastic resin composition of the present invention is a mixture of (A) polybutylene terephthalate resin and (B) polyethylene terephthalate resin, (A) polybutylene terephthalate resin and (B) polyethylene The terephthalate resin may be included in a weight ratio of 8:1 to 1:1. and, for example, may be included in a weight ratio of 6:1 to 1:1.

According to an embodiment of the present invention, within the above-described range, the (A) polybutylene terephthalate resin is included in an amount of 30 to 60% by weight, and the (B) polyethylene terephthalate resin is included in an amount of 10 to 40% by weight. can do.

By maintaining an appropriate crystal rate within this range, it has excellent processability and excellent transmittance and mechanical properties, and it is possible to provide a composition optimized for laser fusion technology by matching the refractive index with E-glass, which will be described later.

According to an embodiment of the present invention, 60 to 80% by weight of the base resin comprising the (A) polybutylene terephthalate resin, and the (B) polyethylene terephthalate resin; And 20 to 40 wt% of the (C) E-glass (E-glass) may be included.

(C) E-glass

The glass fiber included in the thermoplastic resin composition according to an embodiment may be, in particular, E-glass.

Silica, limestone, and borax are the main raw materials for glass fiber, and depending on the composition of the raw material, A-glass (for high alkali), C-glass (for chemical), E-glass (for electric parts), It can be divided into S-glass (for high strength).

In particular, E-glass has a low alkali composition for the purpose of electrical insulation and the like, and generally, a case where the alkali metal content is 2% or less is classified as E-glass.

The E-glass may have calcium aluminoborosilicate as a main component and increase the ratio of components such as MgO, TiO ₂ , and ZnO.

According to an example of the present invention, the E-glass may be coated with at least one of a polyurethane resin, an epoxy resin, and a polyamide resin.

The average diameter of the E-glass used in the present invention may be 5 to 15 μm. By employing such a diameter, the mechanical properties can be more effectively exhibited.

In addition, the average length of the E-glass may be 1 to 10 mm. By employing such a length, the reinforcing effect of the glass fiber is more effectively expressed, and melt-kneading with the base resin and molding of the thermoplastic resin composition become easier.

In addition, the E-glass may have a refractive index of 1.550 or more, specifically 1.560 to 1.600 at 23°C.

In addition, the E-glass may have a circular, oval, or rectangular cross-section.

(D) aluminum diethyl phosphinate

In particular, the phosphorus-based flame retardant included in the thermoplastic resin composition according to the embodiment may be aluminum diethylphosphinate, which is an aluminum-substituted phosphinate compound.

The aluminum diethylphosphinate has excellent flame retardancy and excellent balance of properties, and may be included in an amount of 7 to 14 parts by weight based on 100 parts by weight of the composition including the base resin and the E-glass.

Within this range, the flame retardancy and the balance of physical properties may be further improved.

(E) melamine polyphosphate

The flame retardant synergist included in the thermoplastic resin composition according to one embodiment may be, in particular, melamine polyphosphate.

The melamine polyphosphate may be included together with the above-mentioned aluminum diethyl phosphinate to further increase the flame retardancy, and may serve to prevent deterioration of physical properties by substantially reducing the content of aluminum diethyl phosphinate, which is a flame retardant. .

By including the melamine polyphosphate, melamine sublimes during combustion to absorb energy, and ammonia, a decomposition product, is generated while lowering the temperature of the combustion material, diluting oxygen and the combustion gas of the resin composition to increase the flame retardant effect. there is.

The melamine polyphosphate may be included in an amount of 2 to 8 parts by weight based on 100 parts by weight of the composition including the base resin and the E-glass.

In particular, within the above range, (D) aluminum diethyl phosphinate and (E) melamine polyphosphate may be included in a weight ratio of 6:1 to 1:1, while minimizing deterioration of physical properties within this range and providing excellent Flame retardancy can be exhibited.

(F) Near-infrared transmission anthraquinone dye

In the thermoplastic resin composition of the present invention, a dye can be blended in a molded article having a thickness of 2 mm so that the transmittance of near-infrared rays having a wavelength of 980 nm is 10% or more.

The dye included in the thermoplastic resin composition according to the exemplary embodiment may be, in particular, an anthraquinone-based dye that transmits near-infrared rays.

The near-infrared transmitting anthraquinone-based dye may be used together with other dyes and/or pigments depending on the application purpose.

The blending amount of the near-infrared transmitting anthraquinone-based dye may be 0.1 to 0.5 parts by weight based on 100 parts by weight of the composition including the base resin and the E-glass. By making the compounding quantity of the near-infrared transmitting anthraquinone type dye into the said range, the bleed-out to the surface of the molded article using a thermoplastic resin composition, and the fall of mechanical strength can be suppressed.

(G) other additives

The thermoplastic resin composition according to one embodiment, in addition to the components (A) to (F), in order to balance the respective physical properties under conditions of maintaining excellent both impact resistance and rigidity, or in the end use of the thermoplastic resin composition It may further include one or more additives as required.

Specifically, as the additive, a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, an antistatic agent, a colorant, an impact modifier. It can be used in combination of more than one species.

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the composition including the base resin and the E-glass, However, the present invention is not limited thereto.

For example, it may be included in an amount of 0.1 to 10 parts by weight, or 0.1 to 5 parts by weight.

The thermoplastic resin composition according to the present invention may be prepared by a known method for preparing a thermoplastic resin composition.

For example, the thermoplastic resin composition according to the present invention may be prepared in the form of pellets by mixing the components of the present invention and other additives at the same time and then melt-kneading in an extruder.

The molded article according to an embodiment of the present invention may be prepared from the above-described thermoplastic resin composition.

Since the thermoplastic resin composition has high transmittance to near-infrared rays and has excellent both impact resistance and rigidity, it can be widely applied to various products manufactured by laser fusion technique, and in particular, uses for interior materials, exterior materials, etc. of automobiles, such as electric vehicles can also be usefully applied.

A molded article prepared from the thermoplastic resin composition may have excellent flame retardancy, impact resistance, rigidity and bonding strength without a decrease in near-infrared transmittance.

For example, it may have a UL-94 flame retardancy rating of V0 in a molded article having a thickness of 1.5 mm.

For example, in a molded article having a thickness of 2 mm, the transmittance of near-infrared rays having a wavelength of 980 nm may be 10% or more.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes and are not intended to limit the present invention.

Examples 1 to 4 and Comparative Examples 1 to 5

The thermoplastic resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were prepared according to the component content ratios shown in Table 1 below.

(A), (B) and (C) shown in Table 1 are expressed in weight % based on the total weight of components, (D), (E), (F) and (F'), and not shown in Table 1 Other additives (G-1) and (G-2) are expressed in parts by weight based on 100 parts by weight of the composition.

The components listed in Table 1 were dry-mixed and quantitatively continuously added to the supply part of a twin-screw extruder (L/D=36, Φ=45mm) to melt/knead. Subsequently, the thermoplastic resin composition pelletized through a twin-screw extruder was dried at about 100 ° C. for about 4 hours, and then a specimen for measuring mechanical properties and permeability was obtained using a 6 oz injection molding machine with a cylinder temperature of about 280 ° C and a mold temperature of about 60 ° C. Each was prepared.

division (A)
PBT (B)
PET (C)
E-glass (D)
ADP (E)
MPP (F)
Near-infrared transmission anthraquinone dyes (F')
carbon black Example 1 32.5 32.5 35 10.2 3.8 0.2 - Example 2 32.5 32.5 35 8.4 5.6 0.2 - Example 3 32.5 32.5 35 11.2 2.8 0.2 - Example 4 45.5 19.5 35 10.2 3.8 0.2 - Comparative Example 1 32.5 32.5 35 10.2 3.8 - 0.2 Comparative Example 2 32.5 32.5 35 14.0 - 0.2 - Comparative Example 3 32.5 32.5 35 12.6 1.4 0.2 - Comparative Example 4 32.5 32.5 35 5.8 2.2 0.2 - Comparative Example 5 58.5 6.5 35 10.2 3.8 0.2 -

A description of each configuration shown in Table 1 is as follows.

(A) polybutylene terephthalate resin

A polybutylene terephthalate resin having a refractive index of about 1.550 (manufacturer: SHINKONGhinkong, trade name: Shinite DHK011) was used.

(B) polyethylene terephthalate resin

Polyethylene terephthalate resin (manufacturer: Lotte Chemical, trade name: BCN76) having a refractive index of about 1.575 was used.

(C) E-glass

E-glass having a refractive index of about 1.558, an average diameter of about 13 μm, an average length of about 3 mm, and containing calcium aluminoborosilicate as a main component (manufacturer: Owens-corning, trade name: 183F) was used.

(D) Aluminum diethylphosphinate (ADP)

Kempia's FR-119L was used.

(E) Melamine polyphosphate (MPP: Melamine polyphosphate)

MPP-D from Kempia was used.

(F) Near-infrared transmitting dye

A black dye containing 1,4-bis[(4-methylphenyl)amino]-9,10-anthraquinone was used.

(F') carbon black

Orion engineered carbon's HIBLACK 50L was used.

(G) other additives

Although not shown separately in the above table, the following composition was used as other additives.

(G-1) heat stabilizer

BASF's IRGANOX B-215 was used in an amount of 0.2 parts by weight based on 100 parts by weight of the composition of the base resin and E-glass.

(G-2) lubricant

Mitsui Chemicals' HI-WAX 400P It was used in an amount of 0.1 parts by weight based on 100 parts by weight of the composition of the base resin and E-glass.

Experimental example

The physical properties of each prepared specimen were measured by the following method, and the results are shown in Table 2 below.

(1) Impact resistance (unit: kgf·cm/cm): Notched Izod impact strength was measured for 1/8 inch thick specimens according to ASTM D256.

(2) Stiffness (unit: kgf/cm ² ): The tensile strength was measured at a tensile rate of 50 mm/min according to ASTM D790.

(3) Heat resistance (unit: ℃): According to ASTM D638, heat deflection temperature (HDT: Heat Deflection Temperature) was measured with a load of 18.6 kg/cm ² .

(4) Flame retardancy: In accordance with the UL-94 vertical test (vertical test) regulations, the flame retardancy rating for a 1.5mm thick specimen was measured.

(5) Transmittance (%): Transmittance at 980 nm of a 1.5 mm thick specimen was measured using an Eurivision ETM-10 instrument.

(6) Bonding strength (unit: MPa): After each injection molding of 60 mm × 60 mm × 1.5 mm (width × length × thickness) specimens acting as a laser transmission layer and a laser absorption layer, bonding them through laser fusion The laser fusion bonding strength of the laser transmission layer and the laser absorption layer was measured using a universal testing machine (UTM) at a speed of 5 mm/min.

division impact strength
(kgf cm/cm) The tensile strength
(kgf/cm ² ) HDT
(℃) flame retardant grade permeability
(%) bonding strength
(MPa) Example 1 6.5 1,100 209 V0 12.0 27 Example 2 6.2 1,218 209 V0 11.1 26 Example 3 6.3 1,210 210 V0 15.2 28 Example 4 5.9 1,040 207 V0 10.6 25 Comparative Example 1 6.6 1,110 209 V0 0 - Comparative Example 2 6.4 1,100 183 drip 39.1 31 Comparative Example 3 6.4 1,230 210 drip 21.0 - Comparative Example 4 6.8 1,140 208 drip 13.6 - Comparative Example 5 6.4 1,100 210 V1 10.0 -

From Table 1 and Table 2, E-glass, aluminum diethylphosphinate flame retardant and melamine polyphosphate flame retardant improver, and near-infrared transmission dye in the base resin mixed with PBT resin and PET resin as in Examples 1 to 4 It can be confirmed that, when used together, it is possible to provide a composition optimized for laser fusion technology and a molded article with improved flame retardancy, impact resistance, and bonding strength using the same without lowering near-infrared transmittance compared to Comparative Examples.

In the above, the present invention has been described through preferred embodiments as described above, but the present invention is not limited thereto and various modifications and variations are possible without departing from the concept and scope of the following claims. Those skilled in the art to which the invention pertains will readily understand.

Claims (12)

(A) 60 to 80% by weight of a base resin comprising a polybutylene terephthalate resin, and (B) a polyethylene terephthalate resin; And
(C) 20 to 40% by weight of E-glass,
With respect to 100 parts by weight of the composition comprising the base resin and the E-glass
(D) 7 to 14 parts by weight of aluminum diethyl phosphinate;
(E) 2 to 8 parts by weight of melamine polyphosphate; and
(F) 0.1 to 0.5 parts by weight of a near-infrared transmitting anthraquinone dye
A thermoplastic resin composition comprising a. In claim 1,
The (D) aluminum diethyl phosphinate and the (E) melamine polyphosphate are included in a weight ratio of 6:1 to 1:1, the thermoplastic resin composition. In claim 1,
The (C) the refractive index measured at 23 ℃ of the E-glass is 1.550 or more, the thermoplastic resin composition. In claim 1,
The (C) E-glass has an average diameter of 5 to 15 μm, and an average length of 1 to 10 mm, a thermoplastic resin composition. In claim 1,
The (C) E-glass will be coated with at least one of a polyurethane resin, an epoxy resin, and a polyamide resin, a thermoplastic resin composition. In claim 1,
The (A) polybutylene terephthalate resin and the (B) polyethylene terephthalate resin are included in a weight ratio of 8:1 to 1:1, the thermoplastic resin composition. In claim 1,
The base resin comprises 30 to 60% by weight of the (A) polybutylene terephthalate resin,
Wherein the (B) polyethylene terephthalate resin is included in an amount of 10 to 40% by weight, the thermoplastic resin composition. In claim 1,
The thermoplastic resin composition, which has a UL-94 flame retardancy rating of V0 in a molded article having a thickness of 1.5 mm. In claim 1,
In a molded article having a thickness of 2 mm, the near-infrared transmittance at a wavelength of 980 nm is 10% or more, the thermoplastic resin composition. In claim 1,
A nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, an antistatic agent, a colorant, and an impact modifier. The thermoplastic resin composition further comprising at least one additive selected from the group consisting of. In claim 10,
The additive will be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the composition including the base resin and the E-glass, the thermoplastic resin composition. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 11.