KR20160069129A - Polycarbonate flame retardant resin composition and molded product - Google Patents

Abstract

The present invention relates to a polycarbonate styrene-based alloy flame-retardant resin composition and a molded product, and more particularly, to a polycarbonate styrene-based alloy flame-retardant resin composition in which a polycarbonate resin includes a styrene-based copolymer, an impact modifier, a colorant, and an aromatic phosphate-based flame retardant, wherein a hydrolysis characteristic which is poor due to a colorant is improved by using a hydrolysis adjuvant and a specific impact modifier together and a mechanical property and flame retardancy are maintained, thereby being applicable to automotive and an electrical and electronic product, and to a molded product prepared thereby.

Description

[0001] POLYCARBONATE FLAME RETARDANT RESIN COMPOSITION AND MOLDED PRODUCT [0002]

More particularly, the present invention relates to a polycarbonate-styrene-based alloyed flame retardant resin composition and a molded article, and more particularly to a polycarbonate-styrene-based alloyed flame retardant resin composition and a molded article which contain a styrene-based copolymer, an impact modifier, a colorant and an aromatic phosphate- Styrene-based alloy flame retardant resin composition capable of improving the hydrolysis characteristics, which is poor by incorporating runt, into a combination of a hydrolysis reinforcing agent and a specific impact modifier, and a molded article obtained therefrom.

Polycarbonate resins are amorphous and thermoplastic plastics and have excellent mechanical and thermal properties. Polycarbonate (PC) has excellent impact resistance and heat resistance, and is widely used as an inner and outer material throughout the industry. However, the flame retardancy is not perfect and the hydrolysis resistance is weak due to the coloring agent.

Conventional polycarbonate compounds are excellent in heat resistance and impact resistance, but have poor hydrolytic properties due to colorant and have poor flame retardancy due to PC, ABS and impact modifier. For example, the housing use of electrical and electronic products requires a high level of flame retardancy.

Therefore, the colorant used for color implementation required by various industrial materials is inevitably vulnerable to high-temperature high-humidity hydrolysis, and it is necessary to improve the related technology (related prior art information: Korean Patent Publication No. 2011-0136967) .

In order to solve the problems of the prior art described above, the present invention relates to a flame-retardant resin composition comprising a polycarbonate resin, a styrene-based copolymer, an impact modifier, a colorant and an aromatic phosphate-based flame retardant, Styrene-based alloy flame retardant resin composition capable of improving the properties of the flame retardant by using a hydrolysis reinforcing agent and a specific impact reinforcing agent, and a molded article obtained therefrom.

In order to achieve the above object,

A polycarbonate-styrene-based alloy composition comprising a polycarbonate resin, a styrenic copolymer, an impact modifier, a colorant, and an aromatic phosphate-based flame retardant,

Titanium dioxide, wherein the impact modifier comprises 30 to 60 parts by weight of a methyl (meth) acrylate monomer relative to 100 parts by weight of the conjugated diene rubber polymer; And 10 to 30 parts by weight of a styrene monomer is subjected to emulsion polymerization using a sulfonate emulsifier

A polycarbonate-styrene-based alloy fire retardant resin composition is provided.

The present invention also provides a molded article obtained by injection molding the above-mentioned composition.

According to the present invention, it is possible to improve the hydrolysis property, which has become poor by incorporating a conventional colorant, into the combination of the hydrolysis enhancer and the specific impact modifier, maintain the mechanical properties and flame retardancy, There is provided an effect of providing a polycarbonate-styrene-based alloy fire retardant resin composition and a molded article obtained therefrom.

Hereinafter, the present invention will be described in detail.

The polycarbonate-styrene-based alloyed flame retardant resin composition of the present invention is a polycarbonate-styrene-based alloy composition comprising a polycarbonate resin, a styrenic copolymer, an impact modifier, a colorant, and an aromatic phosphate- Titanium dioxide, wherein the impact modifier comprises 30 to 60 parts by weight of a methyl (meth) acrylate monomer relative to 100 parts by weight of the conjugated diene rubber polymer; And 10 to 30 parts by weight of a styrene monomer is subjected to emulsion polymerization using a sulfonate emulsifier (impact resistant heat resistance grade).

The polycarbonate resin may be a resin having MI (230 DEG C, 3.8 kg load) of 10-22 g / 10 min as measured by ASTM D1238 in consideration of thermal stability and workability of the composition, The lower the flowability of the final product may be a problem, and the flame retardancy and physical properties may not be satisfied when the upper limit is exceeded.

The polycarbonate resin is contained in an amount of 60 to 80% by weight or 70 to 75% by weight of 100% by weight of the total composition, and the flame retardancy can be maximized within this range.

The styrenic copolymer may be, for example, a rubber-modified styrene-acrylonitrile copolymer. Specific examples thereof include 30 to 60 parts by weight of a styrene monomer relative to 100 parts by weight of a conjugated diene-based rubbery polymer; And 10 to 30 parts by weight of an acrylonitrile monomer.

The styrenic copolymer may be contained in an amount of 1 to 10% by weight, or 3 to 7% by weight, based on 100% by weight of the composition, and the polycarbonate resin and the polycarbonate resin may be optimally formed within the range.

As the sulfonate emulsifier, conventionally used emulsifiers may be used.

The impact modifier may be, for example, an impact modifier or an MBS impact modifier having a heat resistant impact modulus, and it is preferable to use an MBS impact modifier having a heat resistant impact modulus.

The impact modifier is included, for example, in the range of 5 to 10 weight% of 100 weight% of the composition, and within this range it is possible to provide optimized impact strength while improving the hydrolysis characteristics reduced by the colorant in the composition.

Examples of the aromatic phosphate-based flame retardant include resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) - piperazine. ≪ / RTI >

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

[Chemical Formula 1]

로 표시되는 화합물일 수 있다.

. ≪ / RTI >

The aromatic phosphate-based flame retardant is, for example, contained in the range of 3 to 15% by weight, or 8 to 13% by weight of 100% by weight of the composition, satisfies the flow without adversely affecting other properties within the range, You can provide a rating.

The colorant includes, for example, 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight per 100 parts by weight of the total composition, such as OG-20 and RD-23 (Lanxess) The mechanical properties and the flame retardancy can be improved without reducing the hydrolysis within the range.

The titanium dioxide can serve as a hydrolysis enhancer, and can include, for example, 90-98 wt% of TiO2, 0-4 wt% of silica and 4 wt% or less of alumina.

Generally, there are various types of titanium dioxide, and specific types can be classified into differences in aluminum amount, presence or absence of silica, degree of silica inclusion, and presence or absence of surface coating with siloxane.

The titanium dioxide of the present invention has been modified to meet the requirements of high processing temperature and heat stability, and titanium dioxide coated on the surface thereof can be used.

Refers to the exposure of the surface of the peritone area to a small amount of silica and aluminum, unless otherwise specified by the term "surface coating"

Specific examples of the titanium dioxide include a product name of Kronos 2233 (product of surface treatment with aluminum, silicon, and polysiloxane compound of TiO2 of not less than TiO2) manufactured by Kronos, or a product of WooShin Pigment named Pigment White 06 have.

The titanium dioxide is contained in the range of 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total composition. Within this range, the titanium dioxide can exhibit hydrolysis resistance, and further, chemical resistance and the like without affecting the mechanical properties and flame retardancy Can be effectively performed as a reinforcing agent for improving the strength of the steel sheet.

The composition may further contain styrene-acrylonitrile-based block copolymer in an amount of 1 to 10% by weight, or 5 to 10% by weight, based on 100% by weight of the composition, .

The composition may further comprise a UV stabilizer. Examples of the UV stabilizer include a benzothiazole UV absorber or a HALS UV absorber. Specific examples thereof include 2- (2'-Hydroxy-5'-t-octylphenyl) benzotriazole, Cyasorb UV-541: 2 - 2'-Hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, product name Tinuvin- 326), 2- (2'-Hydroxy-3,5-di-tert-butylphenyl) -5-chloro-benzotriazole, product name Tinuvin-327) (2'-hydroxy-3 ', 5'-di (1,1-imethylbenzyl) phenyl] -2H-benzotriazole, product name Tinuvin-234) -hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, product name Tinuvin-320), and Methylene bis [3- (2-benzotriazoleyl) -360).

The UV stabilizer can be included, for example, in the range of 0.01 to 3 wt%, or 0.05 to 1.5 wt%, based on 100 wt% of the composition, and the effect of the UV stabilizer can be maximized within this range.

The composition may optionally contain a plasticizer, a heat stabilizer, an inorganic filler, a releasing agent, a dispersant, a dripping inhibitor and a weather stabilizer And at least one additive selected from the group consisting of:

According to the present invention, a molded article obtained by injection molding the composition can be provided. The molded product may be, for example, a housing of an electric or electronic car having durability such as mechanical strength, flame retardancy, hydrolysis resistance, coloring property, and the like.

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 specifications of each component used in the following examples and comparative examples are as follows:

Polycarbonate (PC): A polycarbonate resin having MI (300 DEG C, 1.2 kg load) of 15 g / 10 min as measured by ASTM D1238

* Styrenic copolymer (ABS): 30 to 60 parts by weight of a styrene monomer relative to 100 parts by weight of a conjugated diene-based rubbery polymer; And 10 to 30 parts by weight of an acrylonitrile monomer.

* Impact reinforcement: 30 to 60 parts by weight of a methyl (meth) acrylate monomer relative to 100 parts by weight of a conjugated diene rubber polymer; And 10 to 30 parts by weight of a styrene monomer were emulsion-polymerized with a sulfonate emulsifier. Heat-resistant impact-resistant methyl methacrylate / butadiene / styrene resin (LG Chemical EM505).

* SAN: a block copolymer (SAN95HCl manufactured by LG Chemical Co., Ltd.) containing 73% by weight of styrene monomer and 27% by weight of acrylonitrile,

Flame retardant : An aromatic diphosphate compound represented by the following formula (1)

[Chemical Formula 1]

* UV stabilizer: 2- (2'-Hydroxy-5'-t-octylphenyl) -benzotriazole, product name Cyasorb UV-541.

* Colorant : Merk Company Name M.Dohmen, Lanxess Pigment.

* Titanium Dioxide 1: Siloxane containing silica is surface coated with peroxide

* Titanium Dioxide 2: Siloxane with internal silica is not surface coated

* Silica-free: Silica : Titanium dioxide containing only aluminum and aluminum that does not contain silica.

* ZnS: Used instead of TiO2 as a whitening material.

[Examples 1 to 4, Comparative Examples 1 and 2]

The compositions of Examples 1 to 4 and Comparative Examples 1 and 2 in the following table were well mixed with a lubricant in a super mixer according to the ingredients and content shown in Table 1 below and were fed into a twin-screw extruder And melt-kneaded at a temperature range of 230-250 ° C to perform extrusion processing. After final pelletization, it was dried at 80 ° C for 4 hours or more, left at room temperature for 1 day, and then injected with ASTM specimen using ENGEL.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 PC 72.52 77.59 74.54 72.52 72.52 72.52 ABS 5.07 5.07 5.07 5.07 5.07 5.07 Impact modifier 5.07 5.07 5.07 5.07 5.07 5.07 SAN 5.07 - 5.07 5.07 5.07 5.07 Flame retardant 12.17 12.17 10.14 12.17 12.17 12.17 UV stabilizer 0.10 0.10 0.11 0.10 0.10 0.10 Colorant * 0.2 0.2 0.2 0.2 0.2 0.2 Titanium Dioxide 1 * 0.13 0.13 0.13 Titanium Dioxide 2 * 0.13 Without silica * 0.13 ZnS 0.13

100 parts by weight total of PC + ABS + impact modifier + SAN + flame retardant + UV stabilizer.

The prepared specimens were measured for physical properties according to the following measurement methods and the results are summarized in Table 2.

≪ Evaluation of physical properties &

Tensile Strength (TS, kg / mm2): Measuring the ability of a material to withstand axial load, the dumbbell specimen (specimen thickness 3.2 mm, 23 ℃) was measured by ASTM D638 method using Instron tensile strength The load at the cutting point was measured by pulling at a rate of 2 inches / min, and the load (kg) at the cut was divided by the product of the specimen thickness (cm) and the width (cm).

* Tensile elongation (TE): The tensile elongation (TE) was measured in 3.2 mm thickness of specimen according to ASTM D638 method such as tensile strength evaluation method. Refers to the ratio of strain to initial dimension.

Flexural Strength (kg / cm 2): Measured by ASTM D790 method at 10 mm / min and specimen 3.2 mm thick.

Izod Impact Strength (kg.cm/cm): Measured by ASTM D256 method at 23 ° C and 3.2 mm specimen thickness.

Heat distortion temperature (HDT, ° C): measured under the load of 4.6 kg / cm2 according to the ASTM D648 method.

* Flame retardancy: The flame retardancy grade was measured at a thickness of 1.5 mm by the UL94 vertical method.

* Colorability: Excellent (O) and poor (X) were evaluated according to desired color rendering degree. (O) is not only a visual observation but also an objective numerical value. When the color meter is used, it means that the DELTA E value is close to zero as compared with the standard. The defective (X) DELTA E means the degree to which the value of E is at least 1 as compared to the standard.

* Moisture resistance test : The manufactured pellets were allowed to stand in a 90 ° C 85% RH chamber for 7 days, and the MI was measured according to ASTM D1238 (250 ° C, 2.16 kg) and converted to a percentage of the initial MI value. For reference, the deviation is within the normal range of 50% based on 150%.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 TS (kgf / cm2) 651 664 639 642 640 637 TE (%) 119 223 121 99 92 97 Flexural Strength (kgf / cm2) 1079 1041 1068 1077 1072 1091 Impact strength (kg.cm/cm) 69 57 69 67 68 62 Heat distortion temperature 100 101 106 101 101 99 Flammability V-0 V-0 V-2 V-0 V-0 V-0 Coloring (desired color implementation) 0 0 0 0 0 X Degree of hydrolysis, MI change rate (98 ° C, 80% test after 7 days) 85% 82% 87% 150% 640% 94%

As shown in Table 2, in Examples 1 to 4 including polycarbonate resin, styrene-based copolymer, MBS-based impact modifier, colorant and aromatic phosphate-based flame retardant, titanium dioxide and a specific impact modifier, tensile strength, The mechanical strength, heat distortion temperature, flame retardancy grade, etc., of color intensity, which is a measure of hydrolysis resistance, is also constituted by the coloring performance while maintaining the mechanical strength such as bending strength and impact strength, Hydrolytic properties.

Further, in Example 2 in which the SAN was not included, the flexural strength and the impact strength were slightly reduced, but the remaining mechanical properties, thermal deformation temperature, flame retardancy rating, colorability and hydrolysis resistance were all excellent.

On the other hand, in the case of Comparative Example 1 containing a peroxide and containing a silica-free peroxide, the tensile elongation and hydrolysis resistance were remarkably poor,

It was confirmed that the tensile elongation and the heat distortion temperature were somewhat poor in Comparative Example 2 in which ZnS was replaced by ZnS instead of titanium dioxide.

<Reference example>

The same experiment as in Example 4 was repeated except that the impact modifier in Example 4 was replaced with the following impact modifier-1.

* Impact reinforcement-1: 30 to 60 parts by weight of a methyl (meth) acrylate monomer relative to 100 parts by weight of a conjugated diene rubber polymer; And an impact-resistant methyl methacrylate / butadiene / styrene resin (LG Chem EM500) obtained by emulsion polymerization of 10 to 30 parts by weight of a styrene monomer using a sulfonate emulsifier.

As a result, the tensile strength was 634 kgf / cm 2, the tensile elongation was 76%, the flexural strength was 1078 kgf / cm 2, the impact strength was 65 kg.cm/cm, the heat distortion temperature was 100 ° C, , MI change rate 790%, and the tensile strength, tensile elongation and hydrolysis resistance were remarkably poorer than in Example 4.

&Lt; Additional Comparative Example 1 &

The same experiment as in Example 1 was repeated except that the impact modifier was used in an amount of 2 wt% in Example 1 and PC was increased to that amount.

As a result, the tensile strength was 606 kgf / cm 2, the tensile elongation was 103%, the flexural strength was 1052 kgf / cm 2, the impact strength was 69.3 kg.cm/cm, the thermal deformation temperature was 99 ° C, The degree of hydrolysis and the rate of MI change of 190% were confirmed to be lower than those of Example 1.

&Lt; Additional Comparative Example 2 >

The same experiment as in Example 1 was repeated except that the colorant was used in an excessive amount of 7 to 8 parts by weight in Example 1.

As a result, the tensile strength was found to be 640 kgf / cm 2, the tensile elongation 65%, the flexural strength 1072 kgf / cm 2, the impact strength 68 kg.cm/cm, the thermal deformation temperature 98 ° C, the flame retardancy grade VI, And the MI change rate was 109%.

&Lt; Additional Comparative Example 3 >

The same experiment as in Example 1 was repeated except that the titanium dioxide 1 in Example 1 was used in an excess amount of 9 to 10 parts by weight.

As a result, the tensile strength was 680 kgf / cm 2, the tensile elongation was 65%, the flexural strength was 988 kgf / cm 2, the impact strength was 9.0 kg.cm/cm, the thermal deformation temperature was 97 ° C, The degree of hydrolysis and the change rate of MI were 250%, which confirmed that the hydrolysis effect and impact were lowered compared to Example 1. [

Claims (16)

A polycarbonate-styrene-based alloy composition comprising a polycarbonate resin, a styrenic copolymer, an impact modifier, a colorant, and an aromatic phosphate-based flame retardant,
Titanium dioxide, wherein the impact modifier comprises 30 to 60 parts by weight of a methyl (meth) acrylate monomer relative to 100 parts by weight of the conjugated diene rubber polymer; And 10 to 30 parts by weight of a styrene monomer is subjected to emulsion polymerization using a sulfonate emulsifier
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the polycarbonate resin is a resin having an MI (230 DEG C, 3.8 kg load) of 10 to 22 g / 10 min as measured according to ASTM D1238
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the polycarbonate resin is in the range of 60 to 80% by weight of 100% by weight of the composition
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the styrenic copolymer comprises 30 to 60 parts by weight of a styrene monomer relative to 100 parts by weight of the conjugated diene-based rubbery polymer; And 10 to 30 parts by weight of an acrylonitrile monomer.
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the styrenic copolymer is in the range of 1 to 10 wt% of 100 wt% of the composition
Polycarbonate-Styrene-based Earloy Flame Retardant Resin Composition The method according to claim 1,
Wherein the impact modifier is in the range of 5 to 10 wt% of 100 wt% of the composition
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
The aromatic phosphate based flame retardant is selected from the group consisting of resorcinol bis (diphenylphosphate), bisphenol A bis (diphenylphosphate), and N, N'-bis [di- (2,6-xylyl) &Lt; / RTI &gt;
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the aromatic phosphate-based flame retardant is in the range of 3 to 15 wt% of 100 wt% of the composition
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Characterized in that the colorant is contained in a range of 0.01 to 5 parts by weight based on 100 parts by weight of the total composition
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the titanium dioxide comprises 90-98 wt% of TiO2, 0-4 wt% of silica, and 4 wt% or less of alumina
Polycarbonate-styrene-based alloy fire retardant resin composition. 11. The method of claim 10,
Characterized in that the silica is surface-coated per locally
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
Wherein the titanium dioxide is in the range of 0.05 to 5 parts by weight based on 100 parts by weight of the total composition
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
The composition comprises 1 to 10% by weight of a styrene-acrylonitrile-based block copolymer in 100% by weight of the composition, Further comprising within the range &lt; RTI ID = 0.0 &gt;
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
(2'-Hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2'-Hydroxy-5'- methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-Hydroxy-3 ', 5'-ditert.butylphenyl) -5- (2'-hydroxy-3 ', 5'-di (1,1-imethylbenzyl) phenyl] -2H-benzotriazole, 2- , 5'-di-t-butylphenyl) benzotriazole, and methylene bis [3- (2-benzotriazoleyl) -2-hydroxy-5-tert- To &lt; RTI ID = 0.0 &gt; 3% &lt; / RTI &
Polycarbonate-styrene-based alloy fire retardant resin composition. The method according to claim 1,
The composition may further contain additives such as plasticizers, heat stabilizers, inorganic fillers, release agents, dispersants, anti- And at least one additive selected from the group consisting of
Polycarbonate-styrene-based alloy fire retardant resin composition. A molded article obtained by injection molding the composition of any one of claims 1 to 15.