KR101262309B1 - Polycarbonate resin composition with excellent flame retardancy - Google Patents

Abstract

The present invention relates to a flame-retardant polycarbonate resin composition excellent in impact strength and excellent scratch resistance without visible weld lines, 50 to 85% by weight of polycarbonate resin, 5 to 30% by weight of polymethyl methacrylate, transparent ABS It provides a flame-retardant scratch-resistant polycarbonate resin composition comprising 0.1 to 25% by weight of resin, 5 to 20% by weight of aromatic phosphate, 0.01 to 2% by weight of sulfonate-based metal salt which is an organic salt, and 0.05 to 2% by weight of fluorinated olefin. According to the present invention, by applying a transparent ABS to improve the compatibility of polycarbonate and polymethyl methacrylate, it is possible to provide a flame-retardant polycarbonate resin composition excellent in scratch resistance with excellent impact strength and no visible weld line have.

Description

Flame retardant polycarbonate resin composition {POLYCARBONATE RESIN COMPOSITION WITH EXCELLENT FLAME RETARDANCY}

The present invention relates to a polycarbonate resin composition, and more particularly, to polyaromatic polycarbonate resins, polymethyl methacrylate resins having excellent scratch resistance and transparent ABS are applied to show polycarbonate resins having excellent compatibility and scratch resistance. It relates to a composition.

In general, polycarbonate resin is excellent in transparency, impact resistance, heat resistance and electrical properties, and is used in a wide range of applications from automobile parts to electric, electronic and other office equipment, and is applied to large-scale injection moldings that emit a lot of heat. Since it is used in a wide range of applications and electronic products with high calorific value, it is preferable to impart flame retardancy by using a flame retardant to polycarbonate.

Many known brominated and chlorinated flame retardants are harmful to the human body due to the gases produced during combustion, and due to such human hazards, legal constraints are increasing, and impurities or by-products arising from brominated and chlorinated flame retardants are produced and used. This is undesirable because it can corrode related equipment. Therefore, non-halogenated flame retardants including various phosphorus-containing compounds are necessary for improving the flame retardant properties of polycarbonates.

In addition, in order to be used in the display and home appliance housing field in recent years, there is an increasing demand for materials having high gloss and flame retardant properties and materials having improved scratch resistance. However, polycarbonate cannot be used in the field of housings for electronics and electronics, where scratch resistance is required due to the high hardness of the resin.

In order to compensate for the disadvantage that the use of the housing field is limited due to the lack of scratch resistance, a polycarbonate resin composition having excellent flame resistance and scratch resistance through blending with polymethyl methacrylate resin having excellent hardness and scratch resistance Can provide.

Korea Patent 10-091466 is 50 to 85% by weight of polycarbonate resin, 5 to 30% by weight of polymethyl methacrylate, 5 to 20% by weight of aromatic phosphate, 0.01 to 2% by weight of sulfonate-based metal salt of organic salt and fluorinated olefin 0.05 It provides a flame-retardant scratch-resistant polycarbonate resin composition comprising from 2% by weight.

Republic of Korea Patent 10-0817563 (A) (A1) 20 to 80% by weight of a polycarbonate resin; And (A2) 100 parts by weight of a base resin consisting of 20 to 80% by weight of an alkyl (meth) acrylate resin; (B) 1 to 30 parts by weight of a phosphorus compound; And (C) 1 to 30 parts by weight of a halogen compound; It provides a scratch-resistant flame-retardant thermoplastic resin composition comprising a.

Republic of Korea Patent Publication 10-2009-0066204 50 to 90 parts by weight of a polycarbonate resin; 1 to 50 parts by weight of methacrylic copolymer resin having a refractive index of 1.495 to 1.590; And 5 parts by weight to 40 parts by weight of a flame retardant based on 100 parts by weight of the base resin including 0 to 49 parts by weight of the (meth) acrylic resin.

However, the existing thermoplastic resin composition lacks compatibility between polycarbonate and polymethyl methacrylate, and thus, phase separation occurs during manufacture of the product, resulting in a decrease in impact strength and clearly visible weld lines.

The present invention has been made to solve the above problems, by applying a transparent ABS to improve the compatibility of polycarbonate and polymethyl methacrylate, excellent impact strength and scratch resistance without visible weld line It is an object to provide an excellent flame retardant polycarbonate resin composition.

The present invention includes polycarbonate resin, polymethyl methacrylate, transparent ABS resin, aromatic phosphate, sulfonate-based metal salt which is an organic salt, and fluorinated olefin, wherein the transparent ABS resin is polybutadiene rubber latex; Methacrylic acid alkyl esters or acrylic acid alkyl ester compounds; Aromatic vinyl compounds; And a vinyl cyan compound; provides a polycarbonate resin composition comprising a polymer prepared by graft copolymerization.

Here, the polycarbonate resin 50 to 85% by weight, polymethyl methacrylate 5 to 30% by weight, transparent ABS resin 0.1 to 25% by weight, aromatic phosphate 5 to 20% by weight, sulfonate-based metal salt of 0.01 to 2 It is preferred to include by weight, and 0.05 to 2% by weight fluorinated olefin.

And, more preferably, the polycarbonate resin composition contains 1 to 20% by weight of the transparent ABS resin.

In the present invention, the transparent ABS resin is polybutadiene rubber latex 10 to 60% by weight, methacrylic acid alkyl ester or acrylic acid alkyl ester compound 30 to 70% by weight, aromatic vinyl compound 5 to 25% by weight, and vinyl cyan compound 1 to It is a resin produced by graft copolymerization of 10% by weight.

In the present invention, the polycarbonate resin is produced by the reaction of a dihydric phenol compound and phosgene or diester carbonate, characterized in that it does not contain a halogen.

In the present invention, the polymethyl methacrylate is characterized in that at least one member selected from the group consisting of homopolymers of methyl methacrylate, copolymers of methyl methacrylate and acrylate, and mixtures thereof.

In the present invention, the aromatic phosphate is characterized in that at least one member selected from the group consisting of aromatic monophosphate, aromatic diphosphate, and mixtures thereof.

Wherein the aromatic monophosphate is at least one member selected from the group consisting of halogen-free trialkylphosphates, triaryl phosphates, trialkyl-aryl phosphates, and mixtures thereof.

Wherein the trialkyl phosphate is selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate and trioctyl phosphate, and the triaryl phosphate is triphenyl phosphate, tricresyl phosphate, trizayl phosphate and tresyl diphenyl It is selected from the group consisting of phosphates, characterized in that the trialkyl-aryl phosphate is octyldiphenyl phosphate.

In the present invention, the aromatic diphosphate may be one or a mixture of two selected from compounds represented by Formula 1 and Formula 2.

Ar ₁ in Chemical Formula ₁ Ar ₄ to Ar ₄ are each independently an aryl group substituted with a phenyl group or 1 to 3 C ₁ -C ₄ alkyl groups, R is phenyl or bisphenol A, and n is an integer of 4 or 5.

In the present invention, the organic salt sulfonate-based metal salt is potassium diphenylsulfone sulfonate (KSS), potassium perfluorobutyl sulfonate (KPFBS), sodium trichlorobenzene sulfonate, polystyrene sulfonate sodium sulfate and these It may be at least one selected from the group consisting of a mixture of.

In the present invention, the fluorinated olefin is characterized by using a mixture of Teflon, Teflon and styrene-acrylonitrile, or a mixture of Teflon and polymethyl methacrylate.

In the present invention, the polycarbonate resin composition is an impact modifier, lubricant, heat stabilizer, ultraviolet stabilizer, anti-drip agent, pigment, dye, inorganic filler antioxidant, weathering stabilizer, lubricant, silicone preparation, mold release agent, antistatic agent, antibacterial agent, processing aid And it is characterized in that it further comprises at least one member selected from the group consisting of an anti-friction wear.

By applying transparent ABS to improve the compatibility of polycarbonate and polymethyl methacrylate, it is possible to provide a flame-retardant polycarbonate resin composition excellent in impact resistance and excellent scratch resistance without visible weld line.

Since the polycarbonate resin composition of the present invention is flame retardant, has excellent impact strength, impact strength of the weld portion, and scratch resistance, and no weld line is visible, it can be used for exterior housing parts of displays and electrical and electronic products.

Hereinafter, the present invention will be described in detail with reference to examples.

Flame retardant scratch-resistant polycarbonate resin composition according to the present invention is 50 to 85% by weight polycarbonate resin, 5 to 30% by weight polymethyl methacrylate, 0.1 to 25% by weight transparent ABS resin, 5 to 20% by weight aromatic phosphate, organic 0.01 to 2% by weight of sulfonate-based metal salts, and 0.05 to 2% by weight of fluorinated olefins.

Polycarbonate

The polycarbonate resin of this invention can use what was manufactured by making a polycarbonate precursor, such as a dihydric phenol compound and a phosgene or carbonate diester compound, react. Specifically, for example, in the presence of a solvent such as methylene chloride and a known acid acceptor or molecular weight modifier, or if necessary, a branching agent is added to react the divalent phenol with a carbonate precursor such as phosgene, or divalent. It is produced by the transesterification reaction of phenol and carbonate precursors, such as diphenyl carbonate.

In the present invention, it is preferable to use 50 to 85% by weight of the polycarbonate resin, it is difficult to impart flame retardancy when using less than 50% by weight, blending with polymethyl methacrylate when using more than 85% by weight It is not preferable because it is difficult to impart scratch resistance.

Polymethyl methacrylate

Polymethylmethacrylate (PMMA) used in the present invention is a polymer of methyl methacrylate (MMA), and is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and acrylate. .

Polymethyl methacrylate has the disadvantage of insufficient impact resistance, but not only excellent transparency and weather resistance, but also excellent mechanical properties such as tensile strength, elastic modulus, surface gloss, chemical resistance, adhesiveness, and especially the resin itself. It has excellent hardness and scratch resistance, so it is widely used in decorative products, signs, lighting materials, and various building materials.

The use amount of polymethyl methacrylate in the present invention is preferably 5 to 30% by weight, it is not preferable because the use of less than 5% by weight is difficult to impart scratch resistance, when used in excess of 30% by weight to impart flame retardancy And it is not desirable to maintain the impact strength .

Transparency ABS  Suzy

The transparent ABS resin used in the present invention is 10 to 60% by weight polybutadiene rubber latex, 30 to 70% by weight methacrylic acid alkyl ester or acrylic acid alkyl ester compound, 5 to 25% by weight aromatic vinyl compound, and 1 to 1 vinyl cyan compound. It is characterized by applying a resin prepared by graft copolymerization of 10% by weight.

The methacrylic acid alkyl ester and acrylic acid alkyl ester compound have excellent compatibility with polymethyl methacrylate, and the vinyl cyan compound has excellent compatibility with polycarbonate due to the properties of the components of the transparent ABS resin. By improving the compatibility between carbonate and polymethyl methacrylate, the impact strength is improved, the weld line is not visible, and other mechanical properties are also improved.

In addition, polybutadiene latex serves to improve the impact strength of the flame-retardant scratch-resistant polycarbonate resin composition by playing a role of a general impact modifier, but if the content is too high, there is a disadvantage that the scratch resistance is lowered depending on the soft nature of the latex. However, the methacrylic acid alkyl ester and the acrylic acid alkyl ester compound of the transparent ABS have excellent scratch resistance properties, and have a characteristic of minimizing the scratch resistance deterioration phenomenon of the flame retardant scratch resistant polycarbonate resin composition according to the transparent ABS application.

The amount of the transparent ABS used in the present invention is preferably 0.1 to 25% by weight, more preferably 0.5 to 23% by weight, still more preferably 1 to 20% by weight. When using less than 0.1% by weight of the transparent ABS resin is not preferable because it is difficult to improve the compatibility, when used in excess of 25% by weight is excellent in impact strength, but scratch resistance and flame retardancy is not preferable.

Aromatic Phosphate

The aromatic phosphate used as the flame retardant in the present invention may be used alone or in combination of aromatic monophosphate and aromatic diphosphate. The aromatic monophosphate is trialkyl phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, halogen substituted, triphenyl phosphate, tricresyl phosphate, trigyyl phosphate, cresyl diphenyl phosphate, etc. Triaryl phosphate, trialkyl-aryl phosphate such as octyl diphenyl phosphate and the like can be selected and used at least one, among which triaryl phosphate is preferred, especially trifetyl phosphate, tri (4-methylphenyl ) Phosphate and tri (6-dimethylphenyl) phosphate are more preferred.

The aromatic diphosphate is preferably a compound represented by the following general formula (1) and a pentaerythritol diphosphate represented by the following general formula (2).

[Formula 1]

Ar ₁ in Chemical Formula ₁ Ar ₄ to Ar ₄ are each independently an aryl group substituted with a phenyl group or 1 to 3 C ₁ -C ₄ alkyl groups, R is phenyl or bisphenol A, and n is an integer of 4 or 5.

 [Formula 2]

The aromatic monophosphate and the aromatic diphosphate are preferably added in an amount of 5 to 20% by weight alone or in combination. If the amount of the aromatic phosphate that is the flame retardant is less than 5% by weight, there is a problem that the flame retardancy is lowered. When the amount of the aromatic phosphate is less than 5% by weight, the flame retardancy is excellent.

Organic salts Sulfonate  Metal salt

The sulfonate-based metal salt, which is an organic salt used in the present invention, is added as a catalyst for improving the flame retardancy of polycarbonate and polymethyl methacrylate blend.

Polymethyl methacrylate used to improve the scratch resistance of the present invention has a disadvantage in that the monomer is produced by pyrolysis and the char is difficult to form and thus the flame retardancy is lowered. The sulfonate-based metal salt, which is an organic salt used in the present invention, acts as a catalyst for increasing the char formation rate of polycarbonate and polymethyl methacrylate, thereby increasing the char formation rate of the polycarbonate and polymethyl methacrylate blend. There is a feature to be improved.

As the sulfonate metal salt of the present invention, potassium diphenylsulfone sulfonate (KSS), potassium perfluorobutyl sulfonate (KPFBS), sodium trichlorobenzene sulfonate, polystyrene sulfonate sodium sulfate or a mixture thereof can be used. .

The sulfonate metal salt, which is an organic salt of the present invention, preferably uses 0.01 to 2% by weight. If the content of the sulfonate metal salt is less than 0.01% by weight, the flame retardant effect may not be exhibited. If the content of the sulfonate metal salt is more than 2% by weight, the glossiness of the product may decrease, and the long-term physical properties may be reduced.

Fluorinated olefins

In the present invention, fluorinated olefins are added as a flame retardant aid or anti-dripping agent. The fluorinated olefins used in the present invention select those suitable for polycarbonate resins having various properties such as copolymer composition. have.

* The amount of fluorinated olefin used is 0.01 to 3% by weight, preferably 0.05 to 2% by weight. If the amount is less than 0.05% by weight , the effect of preventing dripping is insignificant, and if it exceeds 2% by weight, problems in appearance characteristics may occur during processing.

Additives which may be added to the present invention include conventionally known impact modifiers, lubricants, heat stabilizers, ultraviolet stabilizers, antidrip agents, pigments, dyes, inorganic filler antioxidants, weathering stabilizers, lubricants, silicone preparations, mold release agents, antistatic agents, Antimicrobial agents, processing aids, or anti-friction wear agents may be used alone or in a mixture of two or more kinds within an appropriate content range.

As the method of kneading using the constituent material of the present invention, a method of hot melt kneading using a twin screw extruder after dry blending is known, and the temperature is usually in the range of 220 ° C to 300 ° C. Preferably it is performed in the range of 230 to 270 degreeC. This is because kneading at the above temperature allows each component to maintain its affinity sufficiently physically and chemically. The obtained composition can be applied to molding methods such as injection molding, extrusion, or blow molding, which are generally used in molding thermoplastic resins.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

The measuring method of the physical property in each Example and a comparative example is as follows.

 (1) pencil hardness

Tensile specimens of ASTM D638 were prepared and measured using a pencil hardness tester manufactured by JUNGDO TESTING INSTRUMENT and a pencil manufactured by Mitsubishi. The measured load was 500 g.

Determination of the pencil hardness was judged whether or not scratching occurs with the naked eye.

 (2) Flammability

According to UL-94 it was measured with a 1.6 mm thick specimen.

 (3) Izod impact strength

According to ASTM D256, measurements were made with specimens notched with a thickness of 1/8 ”at room temperature (23 ° C).

(4) weld line

The specimen in which the weld line was generated was injected and judged visually. If a weld line is observed, it is marked with ○, and if it is not observed, it is marked with X.

Basic resins, flame retardants, impact modifiers used in the following Examples and Comparative Examples are as follows.

(A) polycarbonate resin

Caliber 300-10 grade with a melt index of 10 g / 10 min (ASTM D1238, 300 ℃, 1.2 kgf) of LG DOW was used.

(B) polymethyl methacrylate resin

IH830 grade of LG MMA was used.

(C) transparent ABS resin

LG Chemical's TR540 grade was used.

(D) aromatic phosphates

Daihachi Chemical's CR-741 grade was used.

(E) sulfonate metal salts

Potassium diphenylsulfone sulfonate (KSS) was used.

(F) fluorinated olefins

X-flon-G was used.

Example  1-5

The materials of (A) to (E) described above were added to the contents shown in Table 1, melt-kneaded and pelletized at 260 ° C. to obtain a resin composition, and the resin composition was subjected to specimen molding using an injection molding machine. After measuring the physical properties by the prescribed method, the results are shown in Table 1.

Comparative example  1 to 6

After the above-mentioned materials of (A) to (E) were added in the amounts shown in Table 2, melt-kneaded and pelletized at 260 ° C to obtain a resin composition, and the resin composition was subjected to specimen molding using an injection molding machine. After measuring the physical properties by the prescribed method, the results are shown in Table 2.

division Example One 2 3 4 5 article
castle Polycarbonate 83.2 79.2 74.2 69.2 59.2 Polymethyl methacrylate 5 10 10 10 10 LG Chemical-Transparent ABS One One 5 10 20 Acrylic impact modifier - - - - - ABS - - - - - Aromatic phosphates 10 10 10 10 10 Sulfonate metal salts 0.3 0.3 0.3 0.3 0.3 Fluorinated Olefin 0.5 0.5 0.5 0.5 0.5 water
castle Pencil hardness HB HB-F HB-F HB HB Flammability (UL-94) V-0 V-0 V-0 V-0 V-0 Izod impact strength
(Kgfcm / cm) 8.5 8.0 9.8 22 40 Appearance Characteristics (Weldline) X X X X X

division Comparative Example One 2 3 4 5 6 article
castle Polycarbonate 79.2 74.2 74.2 49.2 - 100 Polymethyl methacrylate 10 10 10 10 100 - LG Chemical-Transparent ABS - - - 30 - - Acrylic impact modifier - 5 - - - - ABS - - 5 - - - Aromatic phosphates 10 10 10 10 - - Sulfonate metal salts 0.3 0.3 0.3 0.3 - - Fluorinated Olefin 0.5 0.5 0.5 0.5 - - water
castle Pencil hardness HB-F B-HB B-HB 1B 2 ~ 3H 2B Flammability (UL-94) V-0 V-0 V-0 V-1 HB V-2 Izod impact strength
(Kgfcm / cm) 3.6 5.5 6.2 60 1.5 80 Appearance Characteristics (Weldline) ○ ○ ○ X X X

Referring to Table 1, the change of the composition from Examples 1 to 5 changed the content of the transparent ABS. As a result of the change in the evaluation items, it was found that as the content of the transparent ABS increased, the impact strength increased significantly, and the weld line did not appear clearly, and the scratch resistance was insignificant.

Referring to Table 1 and Table 2, in the measurement results of Example 2 and Comparative Example 1, if the transparent ABS is applied to improve the compatibility of polycarbonate and polymethyl methacrylate, and the transparent ABS, the weld line does not appear and the impact strength It can be seen that is improved.

Referring to Table 1 and Table 2, in the measurement results of Example 2 and Comparative Examples 2, 3, the transparent ABS improves the compatibility of polycarbonate and polymethyl methacrylate to apply the transparent ABS to the acrylic impact modifier or ABS It can be seen that the impact strength is superior and the weld line does not appear than when the impact modifier is applied.

The results of Comparative Example 4 confirmed that the impact strength is greatly increased when the content of the transparent ABS is too high, but the flame resistance and the scratch resistance are lowered.

Claims (12)

Polycarbonate resin, polymethylmethacrylate, transparent ABS resin, aromatic phosphate, sulfonate-based metal salts which are organic salts, and fluorinated olefins,
The transparent ABS resin is polybutadiene rubber latex; Methacrylic acid alkyl esters or acrylic acid alkyl ester compounds; Aromatic vinyl compounds; And a vinyl cyan compound; and a polymer prepared by graft copolymerization. The polycarbonate resin composition of claim 1, wherein the polycarbonate resin composition comprises 1 to 20% by weight of a transparent ABS resin. According to claim 1 or 2, wherein the transparent ABS resin is polybutadiene rubber latex 10 to 60% by weight, methacrylic acid alkyl ester or acrylic acid alkyl ester compound 30 to 70% by weight, aromatic vinyl compound 5 to 25% by weight, And 1 to 10 wt% of a vinyl cyan compound by graft copolymerization. The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate resin is prepared by the reaction of a dihydric phenol compound with phosgene or diester carbonate and does not contain halogen. The method of claim 1 or 2, wherein the polymethyl methacrylate is one or more selected from the group consisting of homopolymers of methyl methacrylate, copolymers of methyl methacrylate and acrylate, and mixtures thereof. A polycarbonate resin composition characterized by the above. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic phosphate is at least one selected from the group consisting of aromatic monophosphate, aromatic diphosphate, and mixtures thereof. 7. The polycarbonate according to claim 6, wherein the aromatic monophosphate is at least one member selected from the group consisting of halogen-free trialkyl phosphates, triaryl phosphates, trialkyl-aryl phosphates, and mixtures thereof. Resin composition. The method of claim 7, wherein the trialkyl phosphate is selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate and trioctyl phosphate, wherein the triaryl phosphate is triphenyl phosphate, tricresyl phosphate, trizayl phosphate And tresyl diphenyl phosphate, wherein the trialkyl-aryl phosphate is octyl diphenyl phosphate. The polycarbonate resin composition according to claim 6, wherein the aromatic diphosphate is one or a mixture selected from compounds represented by the following Chemical Formulas 1 and 2.
[Formula 1]

Ar ₁ in Chemical Formula ₁ Ar ₄ to Ar ₄ are each independently an aryl group substituted with a phenyl group or 1 to 3 C ₁ -C ₄ alkyl groups, R is phenyl or bisphenol A, and n is an integer of 4 or 5.
(2)

The sulfonate-based metal salt according to claim 1 or 2, wherein the organic salt is potassium diphenylsulfone sulfonate (KSS), potassium perfluorobutyl sulfonate (KPFBS), sodium trichlorobenzene sulfonate, polystyrene sulfonic A polycarbonate resin composition, characterized in that it is at least one member selected from the group consisting of acid sodium sulfate and mixtures thereof. The polycarbonate resin composition according to claim 1 or 2, wherein the fluorinated olefin is teflon, a mixture of teflon and styrene-acrylonitrile, or a mixture of teflon and polymethyl methacrylate. The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate resin composition is an impact modifier, a lubricant, a heat stabilizer, an ultraviolet stabilizer, an antidropping agent, a pigment, a dye, an inorganic filler antioxidant, a weather stabilizer, a lubricant, a silicone preparation agent, a mold release agent, an electrification agent. A polycarbonate resin composition further comprising at least one member selected from the group consisting of an inhibitor, an antibacterial agent, a processing aid, and an anti-friction wear agent.