KR101435084B1 - Polycarbonate resin composition - Google Patents

Abstract

The present invention relates to a flame retardant scratch-resistant polyolefin resin composition comprising (A) a polycarbonate resin, (B) polymethyl methacrylate, (C) a transparent ABS resin, (D) an aromatic phosphate, and (E) a silicone- Carbonate resin composition.

Description

[0001] The present invention relates to a polycarbonate resin composition,

The present invention relates to a flame retardant polycarbonate resin composition excellent in scratch resistance.

Generally, polycarbonate resins are excellent in transparency, impact resistance, heat resistance and electrical properties, and are used in a wide range of applications ranging from automobile parts to electric and electronic equipment and other office equipment, and are applied to large-sized injection molding materials that emit a lot of heat. It is preferable to use a flame retardant to impart flame retardancy to the polycarbonate because it is used for electronic products having a wide range of applications and a large heating value. Many of the known brominated and chlorinated flame retardants are harmful to the human body due to the harmful gas generated during the combustion, and legal restrictions are increasing due to human hazards, and impurities or byproducts generated from the brominated and chlorinated flame retardants are used for the manufacture and use of polycarbonate It is undesirable because it can corrode related equipment. Therefore, a non-halogenated flame retardant containing various phosphorus-containing compounds is needed for improving the flame retardancy of the polycarbonate. In recent years, there is an increasing demand for materials having high gloss and flame retardancy and materials having improved scratch resistance in order to be used in the field of display and household appliance housings. However, polycarbonate can not be used in the field of electric / electronic housing where scratch resistance is required because the self hardness of the resin is not high.

In order to compensate for the disadvantage that the use of the polycarbonate resin is limited to the housing field due to the lack of scratch resistance, the polycarbonate resin composition having excellent flame retardance and scratch resistance through blending with a polymethyl methacrylate resin having excellent hardness and scratch resistance . However, polycarbonate and polymethylmethacrylate are not compatible with each other, resulting in phase separation during production of the product, resulting in a decrease in impact strength and a marked visible weld line. This phenomenon can be solved by applying transparent ABS resin.

However, although the scratch resistant material thus prepared exhibits excellent properties when evaluated by pencil hardness, which is an evaluation standard of scratch, there is a problem that many scratches are generated in actual use when applied to actual products.

1. Published Japanese Patent Application No. 10-2011-0060127 (published on June 8, 2011); 2. Open Patent Publication No. 10-2005-0067674 (published on July 5, 2005);

The present invention is to provide a polycarbonate resin composition including a silicone-based slip agent, exhibiting a low coefficient of friction with an excellent hardness and a reduced occurrence of fine scratches.

(A) 50 to 85% by weight of a polycarbonate resin, (B) 5 to 30% by weight of polymethylmethacrylate, (C) 1 to 20% by weight of a transparent ABS, (D) And (E) 0.1 to 10% by weight of a silicone-based slip agent.

The present invention also provides a polycarbonate resin composition wherein the polycarbonate resin is a polymer produced by the reaction of a divalent phenol compound with a phosgene or a carbonic acid diester, and preferably a polymer not containing a halogen.

The present invention also provides a polycarbonate resin composition wherein the polymethylmethacrylate is selected from a homopolymer of methylmethacrylate, a copolymer of methylmethacrylate and acrylate, or a mixture thereof.

The present invention also relates to a transparent ABS resin comprising 10 to 60% by weight of a polybutadiene rubber latex, 30 to 70% by weight of a methacrylic acid alkyl ester or acrylic acid alkyl ester compound, 5 to 25% by weight of an aromatic vinyl compound, To 10% by weight of a polycarbonate resin composition.

Further, the present invention provides a polycarbonate resin composition wherein the aromatic phosphate is selected from an aromatic monophosphate, an aromatic diphosphate or a mixture thereof.

The present invention also provides a polycarbonate resin composition, wherein the silicon-based slip agent comprises a siloxane-based polymer or an organic modified siloxane-based polymer.

The present invention also provides a polycarbonate resin composition further comprising at least one component selected from the group consisting of an impact modifier, a lubricant, a heat stabilizer, a UV stabilizer, an antistatic agent, a pigment, a dye and an inorganic filler.

Hereinafter, a polycarbonate resin composition according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, there is provided a resin composition comprising (A) a polycarbonate resin, (B) polymethylmethacrylate, (C) a transparent ABS resin, (D) an aromatic phosphate, and (E) a silicone- A thermoplastic polycarbonate resin composition is provided. As a result of experiments conducted by the inventors of the present invention, the polycarbonate resin composition is excellent in flame retardancy, excellent in slip characteristics, low in friction coefficient, and improved in scratch resistance.

Each component of the composition according to the above embodiment will be described in detail.

The polycarbonate resin (A) can be prepared by reacting a polycarbonate precursor such as a phosgene or a carbonate ester compound with a divalent phenol. Concretely, the polycarbonate resin (A) may be a resin which does not contain a halogen. For example, the polycarbonate resin (A) may be used in the presence of a solvent such as methylene chloride and a known acid acceptor or molecular weight regulator, A compound prepared by the reaction of a dihydric phenol with a carbonate precursor such as phosgene can be used. Or those prepared by transesterification of divalent phenol with carbonate precursor such as diphenol and diphenyl carbonate instead of phenol and phosgene.

According to the above-described embodiment, the polycarbonate resin (A) is preferably used in an amount of 50 to 85% by weight based on the total weight of the composition. If it is used in an amount less than 50% by weight, it is difficult to impart flame retardancy. When it is used in an amount exceeding 85% by weight, it is difficult to impart scratch resistance by blending with polymethyl methacrylate.

Polymethyl methacrylate (PMMA) (B) is a polymer of methyl methacrylate (MMA), which is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and acrylate . Polymethyl methacrylate has a disadvantage of insufficient impact resistance, but is excellent in transparency and weather resistance, and has excellent physical properties such as mechanical strength such as tensile strength and elastic modulus, surface gloss, chemical resistance and adhesiveness. Especially, since the resin has excellent hardness and excellent scratch resistance, it is widely used for decorative articles, signboards, lighting materials, and various building materials.

According to the above-described embodiment, the amount of the polymethyl methacrylate (B) is preferably 5 to 30% by weight based on the total weight of the composition. When it is used in an amount of less than 5% by weight, it is not preferable because it is difficult to impart scratch resistance. When it is used in an amount exceeding 30% by weight, it is difficult to impart flame retardancy and maintain the impact strength.

The transparent ABS resin (C) contains 10 to 60% by weight of a polybutadiene rubber latex, 30 to 70% by weight of an alkyl methacrylate ester or an alkyl acrylate ester compound, 5 to 25% by weight of an aromatic vinyl compound, and 1 to 10% By graft copolymerization.

The transparent ABS resin is excellent in compatibility with polymethyl methacrylate due to the nature of its constituent components. The methacrylic acid alkyl ester or acrylic acid alkyl ester compound, which is a component of the transparent ABS resin, and the vinyl cyan compound are compounds excellent in compatibility with polymethyl methacrylate. As a result, transparent ABS resin improves the compatibility between polycarbonate and polymethylmethacrylate, thereby improving the impact strength and preventing the weld line from being seen. Also, the polybutadiene rubber latex serves as a general impact modifier, thereby improving the impact strength of the polycarbonate resin composition. However, if the content of the polybutadiene rubber latex is too large, there is a disadvantage that the scratch resistance is deteriorated according to the soft nature of the latex. However, the methacrylic acid alkyl ester or the acrylic acid alkyl ester compound, which is another component of the transparent ABS, It is possible to complement the scratch resistance of the transparent ABS resin. As a result, the polycarbonate resin composition containing a transparent ABS resin can improve the compatibility of polycarbonate with polymethyl methacrylate and obtain scratch resistance.

According to the above-described embodiment, the amount of the transparent ABS (C) having the above-described constitution is preferably 1 to 20% by weight based on the total weight of the composition. If it is used in an amount less than 1%, it is difficult to improve compatibility, and when it is used in an amount of 20% or more, the impact strength is excellent but the scratch resistance and flame retardancy are reduced.

The aromatic phosphate (D) is for imparting flame retardancy to the polycarbonate resin composition. The aromatic phosphate (D) may be used either alone or in combination with an aromatic monophosphate or an aromatic diphosphate.

The aromatic monophosphate includes trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and trioctyl phosphate, which are not substituted with halogen; Triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, triazylyl phosphate, and cresyldiphenyl phosphate; And trialkyl-aryl phosphate such as octyldiphenyl phosphate. Among them, triarylphosphate is preferable, and triphenylphosphate, tri (4-methylphenyl) phosphate, tri Dimethylphenyl) phosphate is more preferable.

The aromatic diphosphate is preferably a compound represented by the following formula (1) or a pentaerythrityl diphosphate represented by the following formula (2), and the compounds selected from the above compounds may be used alone or in combination.

[Chemical Formula 1]

Wherein Ar ₁ -Ar ₄ is a C ₆ -C ₁₀ aryl group, for example, a phenyl group, substituted or unsubstituted with 1 to 3 C ₁ -C ₄ alkyl groups, R is phenyl or bisphenol A, and n is 4 or 5.)

(2)

According to the above-described embodiment, it is preferable that the aromatic monophosphate or aromatic diphosphate is added alone or in admixture in an amount of 5 to 20% by weight based on the total weight of the composition. When the amount of the aromatic phosphate which is a flame retardant is less than 5% by weight, the flame retardancy is deteriorated. When the amount of the aromatic phosphate is more than 20% by weight, the flame retardancy is excellent but the processability is deteriorated and other properties such as impact strength are deteriorated.

As the slip agent (E), a silicon-based material can be used. As the silicone slip agent, a siloxane-based polymer or a siloxane-based polymer to which an organic group having a functional group bonded thereto is used may be used. One kind of the siloxane-based polymer may be used or a mixture of two or more kinds may be used. As the siloxane-based polymer, an alkyl-bonded polydialkylsiloxane having 1 to 10 carbon atoms such as polydimethylsiloxane may be used. Examples of the organic modified siloxane polymer include a siloxane polymer having an alkyl group, an aryl group, an allyl group, an alkenyl group, an amino group, a halogenated alkyl group, an epoxy group, a carboxyl group, a hydroxyl group, an alkoxy group or a methylhydrogen group This substituted polymer may be used. More specifically, as the organic modified siloxane-based polymer, a polymer having a functional group of the following formula (4) or a functional group of the following formula (5) substituted at the terminal position (X position) of the polydimethylsiloxane of the following formula , And a polymer substituted with a functional group represented by the general formula (5) may be more preferably used. In addition, the silicone slip agent may be either an oil type or a gum type.

(3)

(In the above formula, X may be represented by the following formula (4) or (5), and n is an integer of 1 or more, specifically an integer of 1 to 1000.

[Chemical Formula 4]

[Chemical Formula 5]

(Wherein o and p are each an integer of 1 or more, preferably an integer of 1 to 1000)

According to the above-described embodiment, the content of the silicone slip agent is preferably 0.1 to 10% by weight based on the total weight of the composition. If it is used in an amount of 0.1% by weight or less, the effect of decreasing the friction coefficient is not exhibited, and when it is 10% by weight or more, flame retardancy is deteriorated.

According to one embodiment of the present invention, the polycarbonate resin composition may contain additives such as impact modifiers, lubricants, heat stabilizers, ultraviolet stabilizers, anti-drop agents, pigments, dyes and inorganic fillers, anti-shock agents, antioxidants, , A releasing agent, an antistatic agent, an antibacterial agent, a processing aid, and the like in an appropriate amount.

As a known method of kneading the constituent materials according to the above-described embodiments, a method of heat-melt kneading using a twin-screw extruder after dry blending can be applied. At this time, the temperature is usually in the range of 220 ° C to 300 ° C, preferably 230 ° C to 270 ° C. This is because when the components are kneaded in the above-mentioned temperature range, the constituent components can maintain sufficient affinity for both physically and chemically.

The composition obtained by the above-mentioned kneading can be applied by a molding method such as an injection molding method, an extrusion molding method or a blow molding method generally used for molding a thermoplastic resin.

The polycarbonate resin composition according to the present invention is excellent in compatibility between the constituent components and is excellent in flame retardancy and scratch resistance of the composition, and can be suitably used for displays and external housing parts of electric and electronic products.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

The measurement methods of physical properties in each of the examples and comparative examples are as follows.

(1) Pencil Hardness

ASTM D638 tensile specimen was prepared and measured using a pencil hardness tester of JUNGDO TESTING INSTRUMENT Co., Ltd. and a pencil of Mitsubishi Co., and a load of 500 g was measured.

The hardness of the pencil was judged by scratching with the naked eye.

(2) Coefficient of Friction

The coefficient of friction was measured using a friction coefficient meter manufactured by Toyuseiki.

(3) appearance discoloration

The dE of the specimen was measured using Gretagmacbeth coloreye to determine appearance discoloration.

The respective components used in the following Examples and Comparative Examples are as follows.

(A) Polycarbonate resin

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

(B) Polymethyl methacrylate resin

IH830 grade of LG MMA was used.

(C) Clear ABS resin

A TR540 grade from LG Chemical was used.

(D) an aromatic phosphate

CR-741 grade of Daihachi Chemical was used.

(E) Slip agent

Polydimethylsiloxane (Dow Corning, DC 200F) was used as the siloxane-based polymer, and H-Si-6440P from Evonik was used as the organic modified siloxane-based polymer.

Examples 1 to 6 and Comparative Examples 1 to 3

The above-mentioned materials (A) to (E) were charged in the same amounts as in Table 1, melted and kneaded at 260 占 폚 and pelletized to obtain a resin composition. The obtained resin composition was subjected to specimen molding using an injection molding machine, and physical properties were measured by a prescribed method. The results are shown in Table 1.

Example Comparative Example One 2 3 4 5 One 2 3 4 Furtherance
(weight%) Polycarbonate 74 76.9 72 67 69 85 - 100 77 Polymethyl methacrylate 10 10 10 10 10 - 100 - 10 Transparent ABS 3 3 3 3 3 - - - 3 ABS - - - - - 5 - - - Aromatic phosphate 10 10 10 10 10 10 - - 10 The siloxane-based polymer (DC 200F) 3 - - - 3 - - - - The organic modified siloxane polymer (H-Si-6440P - 0.1 5 10 5 - - - - Properties Pencil hardness F F F F F 2B 2H 2B F Coefficient of friction 0.37 0.40 0.20 0.17 0.15 0.5 0.47 0.48 0.45

Referring to Table 1, the compositions of Examples 1 to 5 exhibit excellent pencil hardness and coefficient of friction. However, as the content of the siloxane polymer or the organic modified siloxane polymer as the slip agent increases, the friction coefficient tends to decrease Was confirmed.

In contrast, Comparative Examples 1 and 3, which did not use polymethylmethacrylate, transparent ABS and slip agent, showed poor pencil hardness and high friction coefficient compared with the Examples. In addition, in Comparative Example 2 using polymethylmethacrylate instead of polycarbonate, it was confirmed that the friction coefficient was also high. In Comparative Example 4 in which the silicone slip agent was not added, the pencil hardness was the same as in Example , And the coefficient of friction was relatively high.

Claims (13)

(A) 50 to 85% by weight of a polycarbonate resin;
(B) 5 to 30% by weight of polymethylmethacrylate;
(C) 1 to 20% by weight of a transparent ABS resin;
(D) 5 to 20% by weight of aromatic phosphate; And
(E) 0.1 to 10% by weight of a silicone-based slip agent,
Lt; / RTI >
Wherein the silicon-based slip agent comprises an organic modified siloxane polymer having a functional group of the following formula (4) or (5) bonded to the terminal position of the polydimethylsiloxane of the following formula (3)
(3)

(Wherein X is represented by the following general formula (4) or (5), and n is an integer of 1 or more.)
[Chemical Formula 4]

[Chemical Formula 5]

(Wherein, o and p are each an integer of 1 or more).
The method according to claim 1,
Wherein the polycarbonate resin (A) is a polymer of a divalent phenol compound and a phosgene or carbonic acid diester.
3. The method of claim 2,
The polycarbonate resin (A) does not contain a halogen-containing flame-retardant scratch polycarbonate composition.
The method according to claim 1,
The polymethyl methacrylate (B) is a homopolymer of methyl methacrylate, a copolymer of methyl methacrylate and acrylate, or a mixture thereof.
The method according to claim 1,
Wherein the transparent ABS resin comprises 10 to 60% by weight of a polybutadiene rubber latex; 30 to 70% by weight of a methacrylic acid alkyl ester or an acrylic acid alkyl ester compound; From 5 to 25% by weight of an aromatic vinyl compound; And 1 to 10% by weight of a vinyl cyan compound, wherein the polycarbonate resin composition is a graft copolymer.
The method according to claim 1,
Wherein the aromatic phosphate is selected from the group consisting of aromatic monophosphate, aromatic diphosphate, and mixtures thereof.
The method according to claim 6,
Wherein the aromatic monophosphate is at least one selected from the group consisting of trialkylphosphate, triarylphosphate and trialkyl-arylphosphate in which halogen is not substituted.
8. 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 selected from the group consisting of triphenyl phosphate, tricresyl phosphate, triazyl phosphate and tresyl diphenyl phosphate,
Wherein the trialkyl-aryl phosphate is octyldiphenyl phosphate.
The method according to claim 6,
A flame retardant scratch polycarbonate resin composition comprising at least one compound selected from the group consisting of compounds represented by the following general formula (1) or (2):
[Chemical Formula 1]

Wherein Ar ₁ -Ar ₄ is a C ₆ -C ₁₀ aryl group substituted with 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)

delete delete delete The method according to claim 1,
The flame retardant scratch polycarbonate resin composition further comprising at least one additive selected from the group consisting of an impact modifier, an impact modifier, a lubricant, a heat stabilizer, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye, and an inorganic filler.