KR101776990B1 - Glass fiber reinforced thermoplastic flame retardant resin alloy composition and injection molding - Google Patents

Abstract

The present invention relates to a glass fiber-reinforced thermoplastic flame retardant resin composition and a molded article thereof. According to the present invention, the moldability is improved by improving the flowability, the impact strength is improved without reducing the heat resistance and the flame retardancy, There is an effect of providing a glass fiber-reinforced thermoplastic flame retardant resin composition and a molded article obtained therefrom, which can be widely used in the fields of electronics, industrial materials and automobile interior parts, in particular, satisfying the required performance as a housing for electrical and electronic products.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass fiber reinforced thermoplastic flame retardant resin composition,

More particularly, the present invention relates to a glass fiber-reinforced thermoplastic flame retardant resin composition and a molded article thereof, and more particularly to a glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene- By incorporating a small amount of a rhenitrile-butadiene-styrene copolymer and using a lubricant, it is possible to solve the problem of heat resistance or flame retardancy reduction caused by blending of acrylonitrile-butadiene-styrene polymer in the past, And which can provide a molded article which can improve flame retardancy and impact strength together, and a molded article obtained therefrom. BACKGROUND OF THE INVENTION [0002] The present invention relates to a glass fiber reinforced thermoplastic flame retardant resin composition.

Recently, in the field of automobiles, metal and crosslinked rubber parts have been replaced by plastic parts due to the demand for lighter weight and eco-friendliness. Thus, utilization of thermoplastic resin which has low specific gravity, good workability and can be recycled is increasing. The polycarbonate resin (PC), which is a representative thermoplastic resin, has excellent mechanical and thermal properties, and has high transparency and impact resistance. Therefore, it can be used for optical applications such as lenses and compact disks, OA materials for mobile phones, notebooks and printers, And the like.

However, such a PC resin is disadvantageous in that molding is difficult due to high melt viscosity and low fluidity. In addition, there is a limit to the application of a product requiring a low temperature impact strength because the notch impact strength at low temperature is rapidly lowered.

In order to compensate for the drawbacks of such PC resins, various thermoplastic resins and blends with elastomers have been used. Among these resins, acrylonitrile-butadiene-styrene resin (ABS) is one of the most widely used resins.

However, since the heat resistance is reduced or the flame retardancy is adversely affected by the blending of ABS, there is a problem that there is a limit to the resin content that can be blended.

Therefore, it is necessary to study a method of strengthening the impact resistance of the ABS resin in the blending of the ABS resin in order to strengthen the impact strength of the polycarbonate resin, especially the glass fiber reinforced polycarbonate resin.

The present invention provides a glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer as a base resin. The glass fiber-reinforced thermoplastic flame retardant resin composition according to claim 1, By incorporating a small amount of acrylonitrile-butadiene-styrene copolymer and using a lubricant, the problem of heat resistance or flame retardancy reduction caused by blending of acrylonitrile-butadiene-styrene polymer conventionally is solved and flowability is improved, To provide a glass fiber-reinforced thermoplastic flame retardant resin composition and a molded article obtained therefrom, which can provide a molded article which can improve flame retardancy and impact strength together.

In order to achieve the above object, the present invention provides a glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer as a base resin, wherein the acrylonitrile-butadiene- 5 parts by weight or less based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant, and pentaerythritol tetrastearate and polyethylene wax Based on the total weight of the glass fiber reinforced thermoplastic flame retardant resin composition.

Further, the present invention provides a molded article comprising the above glass fiber-reinforced thermoplastic flame retardant resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to improve the moldability by improving the flowability and to improve the impact strength without reducing the heat resistance and the flame retardancy, and thus it can be widely used in the fields of electric and electronic materials, industrial materials and automobile interior parts. There is an effect of providing a glass fiber-reinforced thermoplastic flame retardant resin composition satisfying the required performance and a molded article obtained therefrom.

Hereinafter, the present invention will be described in detail.

The glass fiber-reinforced thermoplastic flame retardant resin composition of the present invention is a glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer as a base resin. The acrylonitrile-butadiene- 5 parts by weight or less based on 100 parts by weight of the total amount of the polycarbonate resin, the glass fiber and the flame retardant, and the pentaerythritol tetrastearate and the polyethylene wax And at least one lubricant selected from the group consisting of

The lubricant may be, for example, 0.15 to 2 parts by weight , or 0.5 to 1.5 parts by weight, based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant And within this range, it is possible to improve the fluidity and to improve the moldability, while improving the impact strength even when a small amount of the ABS copolymer is added.

Specific examples of the lubricant include 0.01 to 1.5 parts by weight, or 0.3 to 1.0 part by weight of pentaerythritol tetrastearate, and 0.05 to 0.5 parts by weight of polyethylene wax, based on 100 parts by weight of the total of the polycarbonate resin, glass fiber and flame retardant , Or 0.2 to 0.8 parts by weight.

In the present invention, the pentaerythritol tetrastearate has a releasing property with respect to a metal surface and can reduce frictional heat that may occur during processing. The polyethylene wax has a polarity and penetrates into the inner polymer So that the chains can slide well and induce intermolecular flow, so that the combined use of these two species can maximize the effect.

As the polycarbonate resin, for example, 61.2 parts by weight or more, or 61.3 to 75 parts by weight, in 100 parts by weight of the total of the polycarbonate resin, glass fiber and flame retardant, , And it is preferable to form an acrylonitrile-butadiene-styrene copolymer and an alloy within this range, and stiffness in the alloy composition can be maintained.

Specific examples of the polycarbonate resin include a resin having a melt index of 10 or more g / 10 minutes (300 DEG C, 1.2 kg) or 10 to 15 g / 10 minutes (300 DEG C, 1.2 kg) measured by ASTM D1238 standard .

The polycarbonate resin may have a weight average molecular weight of 30,000 to 80,000 g / mol, and preferably 40,000 to 70,000 g / mol. In the weight-average molecular weight range, there is an advantage in that it has excellent chemical resistance, mechanical properties, molding processability and impact resistance.

Examples of the acrylonitrile-butadiene-styrene copolymer include 50 to 70 wt% of diene rubber having an average diameter of 0.1 to 2 mu m, or 0.5 to 1.5 mu m, 20 to 40 wt% of styrene monomer, and acrylonitrile monomer 5 By weight to 10% by weight. It is possible to prevent the impact strength of the thermoplastic silicone resin composition of the present invention from lowering in the above average diameter range.

The acrylonitrile-butadiene-styrene copolymer may be used in an amount of 5 parts by weight or less, or 3 to 5 parts by weight, based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant , Which is preferable for forming a polycarbonate resin and an alloy within this range. In addition, it is possible to provide a shock reinforcing synergistic effect as much as the content lowered and lowered than in the prior art.

As the glass fiber, for example, 22.8 parts by weight or less, or 15 to 22.7 parts by weight, in the total amount of 100 parts by weight of the polycarbonate resin, glass fiber, , And the effect of injecting the glass fiber as a filler within this range can be maximized.

Specific examples of the glass fiber include a glass fiber having a length (L) of 1-5 mm or 2-4 mm, a width (D) of 10-20 탆, or 10-15 탆, an aspect ratio (L / D) of 200-300, , Or within the range of 215-245.

As another example, the glass fiber may be a cylindrical type having a silane-based surface treatment.

As another example, the glass fiber may be a cylindrical type surface-treated with 0.5 to 2% by weight or 0.5 to 1.5% by weight of epoxy silane based on 100% by weight of glass fiber.

Examples of the flame retardant include resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) phosphoryl] -piperazine It is preferable in view of the flame retardancy and the formability of the flame retardant.

The aromatic phosphate-based flame retardant is, for example,

[Chemical Formula 1]

로 표시되는 화합물일 수 있다.

. ≪ / RTI >

The flame retardant is included, for example, in an amount of 16 parts by weight or less, or 12 to 16 parts by weight, based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant. In this range, , The flame retardant effect of the V0 grade can be sufficiently exhibited, and the heat resistance reduction effect can be reduced as a result.

The above-mentioned alloy composition may further comprise a styrene-acrylonitrile block copolymer.

For example, the styrene-acrylonitrile block copolymer may be prepared by dissolving a certain amount of rubber in a mixed solution of a certain proportion of an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, a third monomer and a solvent, Method, and specific examples thereof may be bulk polymerization of 60 to 80 wt% of styrene monomer and 20 to 40 wt% of acrylonitrile monomer.

For example, the styrene-acrylonitrile block copolymer may have a weight average molecular weight of 50,000 to 180,000 g / mol, or 120,000 to 150,000 g / mol.

The styrene-acrylonitrile block copolymer is contained in an amount of 1 to 12.5 parts by weight, 3 to 7 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the sum of the polycarbonate resin, glass fiber and flame retardant , And the effect of reinforcing the mechanical properties including the surface rigidity within this range can be also provided.

The alloy composition may further comprise a diene-methyl methacrylate core / shell copolymer.

The diene-methyl methacrylate core / shell copolymer may be, for example, a core / shell graft copolymer in which a methyl methacrylate compound is grafted to a diene rubber, %, And the methyl methacrylate compound may be contained in an amount of 5 to 40 wt%, respectively.

The methyl methacrylate compound may be used by mixing a vinyl aromatic hydrocarbon compound and / or a vinyl cyanide compound.

Specific examples include a methyl methacrylate-butadiene-styrene copolymer having a diene rubber content of 0.1 to 0.5 μm in average diameter of 58 to 70 wt%, styrene monomer of 28 to 40 wt%, and methyl methacrylate monomer of 0.1 to 2 wt% Lt; / RTI >

It is possible to prevent the impact strength of the thermoplastic silicone resin composition of the present invention from lowering in the above average diameter range.

The diene-methyl methacrylate core / shell copolymer is contained in an amount of 3 to 7 parts by weight, or 4 to 6.5 parts by weight based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant, It is also possible to provide an impact reinforcing effect within a range.

The composition may contain one or more additives selected from a plasticizer, a heat stabilizer, a light stabilizer, an inorganic filler, a releasing agent, and a dispersant within a range not adversely affecting the physical properties of the invention.

The alloy composition of the present invention is excellent in mechanical properties such as rigidity, impact resistance and heat resistance, and thus can be widely used in the fields of electric, electronic, industrial and automotive interior parts. Especially, .

The method of kneading the resin composition is not limited to those used in the art, but it is possible to apply a method of dry blending the components and additives of the present invention, followed by heating and melt kneading. The temperature is usually in the range of 230 to 270 캜, Kneading can be performed so that each component can physically and chemically maintain sufficient affinity in the range of 240 to 260 캜.

According to the present invention, it is possible to provide a molded article comprising the above glass fiber-reinforced thermoplastic flame retardant resin composition.

The molded article can be widely used in the fields of electrical and electronic, industrial materials and automobile interior parts, and in particular, it can be an electric and electronic housing.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[Example]

The materials used in the following examples and comparative examples are as follows:

Polycarbonate (PC): Polycarbonate resin having MI (300 캜, 1.2 kg load) of 10 g / 10 min as measured by ASTM D1238.

Acrylonitrile-butadiene-styrene copolymer (ABS): a core / shell graft copolymer comprising 50 to 70 wt% of a conjugated diene rubber polymer, 20 to 40 wt% of a styrene monomer and 5 to 10 wt% of an acrylonitrile monomer Acrylonitrile / butadiene / styrene resin.

Styrene-acrylonitrile block copolymer (SAN): 60 to 80% by weight of styrene monomer and 20 to 40% by weight of acrylonitrile monomer (Mw 140,000 g / mol).

Flame retardant : an aromatic phosphate-based compound represented by the following formula (1).

[Chemical Formula 1]

Impact reinforcing agent : a methyl methacrylate-butadiene-styrene copolymer comprising 58 to 70% by weight of a diene rubber having an average particle diameter of 0.1 to 0.5 占 퐉, 28 to 40% by weight of styrene and 0.1 to 2% by weight of methyl methacrylate.

Glass fiber: glass fiber having a diameter of 13 탆 and a length of 4 mm (aspect ratio (L / D) of 300) was used as a fiber filler, and on the 100% by weight of the fibrous filler, aminopropyltriepoxysilane 0.6 Weight% applied material.

Lubricant-1: pentaerythritol tetrastearate having a melting point of 48 to 68 캜, an acid value of 0 to 1.5 mg KOH / g, and a hydroxyl value of 25 mg KOH / g.

Lubricant-2: polyethylene wax (product name LC102N from Lione chemtec).

[Example 1-2, Comparative Example 1-4]

For the preparation of the alloy composition of the present invention, pellets were prepared by melt mixing / kneading in a twin-screw extruder at 250 캜 according to the contents and components shown in Table 1 below.

Classification (parts by weight) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PC +
Flame retardant +
Glass fiber *
(Weight ratio) 100 (61.4:
15.9: 22.7) 100
(61.4: 15.9: 22.7) 100 (61.1:
16.0: 22.9) 100 (60.5:
16.2: 23.3) 100 (58.3:
17.9: 23.8) 100 (58.2:
16.5: 25.3) ABS ** 4.5 3 5.1 4.7 7.1 7.6 SAN ** 2.3 2.3 3.4 5.8 6 12.5 Impact reinforcement ** 5.7 5.7 5.7 5.8 6 6.25 Loot-1 ** 0.57 0.57 - - - - Loot-2 ** 0.45 0.45 - - - -

** The content is based on 100 parts by weight of *.

Experimental Example

The pellets prepared from the alloy compositions of Examples 1 to 2 and Comparative Examples 1 to 4 were molded into test specimens for measurement of physical properties using an injection molding machine. The evaluation of physical properties was carried out as follows, and the results are shown in Table 2 below.

The specific physical properties are measured as follows.

How to measure property

IZOD Impact Strength: Measured at 23 ° C in accordance with ASTM D256 (Specimen Thickness 1/8 ", 23 ° C), the unit of which is Kgf.cm/cm.

* Melt Index (MI): Measured according to ASTM D1238 (250 ° C, 5.0 kg), the unit being g / 10 min.

* Heat distortion temperature (HDT, ° C): Measured according to ASTM D648 standard (18.5 kgf.cm2 load).

* Tensile Strength (TS) and Tensile Elongation (TE): Measured at 50 mm / min according to ASTM D638 (specimen thickness 3.2 mm, 23 캜), the units being kgf / cm 2 and%.

Flexural Strength (FS) and Flexural Modulus (FD): Measured at 10 mm / min according to ASTM D790 (specimen thickness 6.4 mm, 23 캜), the units being kgf / cm 2 and%.

* Flammability Rating (UL94V): When the flame is applied in the vertical direction of a plastic product according to the UL94 method, the combustion pattern of the product and the degree of flame propagation around the product are evaluated.

1. Burning time of t1 and burning pattern of specimen after pouring flame of 20 mm length into specimen for 10 seconds, 2. Burning time of specimen after tilting for 10 seconds again after completion of first flushing, t2 and fire 3. Determine glowing time t3 and record the combustion pattern. 3. Calculate the combustion time and the combustion pattern of t1 t2 t3 (whether or not the ignition is ignited by dripping, whether it is burned to the clamp, etc.).

(V-0, V-1, V-2)

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 IZOD (23 < 0 > C) 9.5 8 7.5 7 7 6.9 MI (g / 10 min) 20 21 17 17 19 18 HDT (° C) 90 91 91 90 86 88 TS 1115 1150 1119 1120 1160 1010 TE 2.2 2.2 2 2 2.2 2.4 FS 1621 1650 1510 1540 1600 1560 FD 3.77 3.97 2.89 2.95 2.79 3.21 Flammability rating V-0 @ 1.5T V-0 @ 1.5T V-0 @ 1.5T V-0 @ 1.5T V-1 @ 1.5T V-1 @ 1.5T

As shown in Table 2, the glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer as a base resin, which contains a small amount of the acrylonitrile-butadiene- In Examples 1 and 2, it was confirmed that impact strength, flow index, flexural strength, flexural modulus and the like were improved in Comparative Examples 1 to 4 in which no lubricant was used.

Particularly, in Examples 1, 2 and Comparative Examples 1 to 4, as the ABS resin content increases, the impact strength and the flow index are inversely proportional to each other.

Experiments for additional Examples 1 and 2 were presented below as experimental examples relating to the use of lubricants.

<Additional Experimental Example 1-4>

The above components were melt-mixed / kneaded in a twin-screw extruder at 250 ° C according to the content ratios shown in Table 3 below, and pellets were prepared. The properties were measured in the same manner as in Example 1, and the results are summarized in Table 4.

Classification (parts by weight) Additional Experimental Example 1 Further Experimental Example 2 Further Experimental Example 3 Further Experimental Example 3 PC +
Flame retardant +
Glass fiber *
(Weight ratio) 100 (61.4:
15.9: 22.7) 100 (61.4:
15.9: 22.7) 100 (61.4:
15.9: 22.7) 100 (61.4:
15.9: 22.7) ABS ** 4.5 4.5 4.5 4.5 SAN ** 2.3 2.3 2.3 2.3 Impact reinforcement ** 5.7 5.7 5.7 5.7 Loot-1 ** 0.5 - 2 - Loot-2 ** - 0.6 - 2

division Additional Experimental Example 1 Further Experimental Example 2 Further Experimental Example 3 Further Experimental Example 4 IZOD (23 &lt; 0 &gt; C) 9.5 9.0 9 9.8 MI (g / 10 min) 18 20 20 22 HDT (° C) 90 90 90 90 TS 1115 1110 1110 1110 TE 2.2 2.2 2.3 2.2 FS 1600 1595 1605 1600 FD 3.50 3.70 3.65 3.5 Flammability rating V-0 @ 1.5T V-0 @ 1.5T V-0 @ 1.5T V-0 @ 1.5T

As shown in Table 3, the additional Experimental Examples 1 and 2, in which the lubricant was used within the appropriate amount range, were able to maintain the mechanical properties thereof without changing the physical properties, Do.

Accordingly, through the Tables 2 and 4, it can be seen that when the optimum composition ratio combination of the present invention is followed as in Examples 1 to 2 and Additional Experiments 1 and 2, even though a small amount of the acrylonitrile-butadiene- , Impact resistance, heat resistance, and other mechanical properties, and further, the heat resistance and the flame retardancy are not reduced.

Claims (17)

A glass fiber-reinforced thermoplastic flame retardant resin composition comprising a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer as a base resin,
Wherein the acrylonitrile-butadiene-styrene copolymer is contained in an amount of 5 parts by weight or less based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant, 0.01 to 1.5 parts by weight of pentaerythritol tetrastearate as a lubricant, And 0.05 to 0.5 parts by weight of a polyethylene wax, wherein the impact modifier comprises 58 to 70% by weight of a diene rubber having an average particle diameter of 0.1 to 0.5 μm, 28 to 40% by weight of styrene and 0.1 to 2% by weight of methyl methacrylate And 3 to 7 parts by weight of a methacrylate-butadiene-styrene copolymer
Glass fiber reinforced thermoplastic flame retardant resin composition. delete delete The method according to claim 1,
Wherein the polycarbonate resin is at least 61.2 parts by weight based on 100 parts by weight of the total of the polycarbonate resin, glass fiber and flame retarder
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the polycarbonate resin has a melt index of 10 or more g / 10 min (300 DEG C, 1.2 kg)
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the acrylonitrile-butadiene-styrene copolymer has a diene rubber content of 0.1 to 2 mu m in average diameter of 50 to 70 wt%, 20 to 40 wt% of styrene monomer, and 5 to 10 wt% of acrylonitrile monomer doing
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the glass fiber is 22.8 parts by weight or less in 100 parts by weight of the total of the polycarbonate resin, glass fiber and flame retardant
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the glass fiber is a cylindrical type surface treated with a silane having a length of 1-5 mm, a width of 10-20 탆 and an aspect ratio of 200-300
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
The flame retardant is selected from the group consisting of resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) Based flame retardant selected from the group consisting of
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the flame retardant is not more than 16 parts by weight in 100 parts by weight of the total of the polycarbonate resin, glass fiber and flame retardant
Glass fiber reinforced thermoplastic flame retardant resin composition. The method according to claim 1,
Characterized in that said alloy composition further comprises a styrene-acrylonitrile block copolymer
Glass fiber reinforced thermoplastic flame retardant resin composition. 12. The method of claim 11,
Wherein the styrene-acrylonitrile block copolymer is contained in the range of 1 to 12.5 parts by weight based on 100 parts by weight of the total amount of the polycarbonate resin, glass fiber and flame retardant.
Glass fiber reinforced thermoplastic flame retardant resin composition. delete delete The method according to claim 1,
Wherein the composition comprises at least one additive selected from a plasticizer, a heat stabilizer, a light stabilizer, an inorganic filler, a releasing agent, and a dispersing agent
Glass fiber reinforced thermoplastic flame retardant resin composition. 15. A molded article comprising the glass fiber-reinforced thermoplastic flame retardant resin composition according to any one of claims 1, 4, 12, and 15. 17. The method of claim 16,
Wherein the molded article is an electric and electronic housing.