WO2014092412A1

WO2014092412A1 - Polycarbonate resin composition having excellent light resistance and fire retardancy, and molded product comprising same

Info

Publication number: WO2014092412A1
Application number: PCT/KR2013/011345
Authority: WO
Inventors: 김필호; 이연주; 신승식
Original assignee: 제일모직 주식회사
Priority date: 2012-12-11
Filing date: 2013-12-09
Publication date: 2014-06-19
Also published as: KR20140075517A; KR101534336B1

Abstract

The polycarbonate resin composition according to the present invention comprises: a polycarbonate resin; a graft copolymer containing polyorganosiloxane; an organic siloxane polymer; a phosphorus-based fire retardant; and titanium dioxide. The polycarbonate resin composition does not decrease heat resistance and mechanical properties, does not emit halogen-based poisonous gas, and has excellent light resistance and fire retardancy.

Description

Polycarbonate resin composition excellent in light resistance and flame retardancy and molded article comprising the same

The present invention relates to a polycarbonate resin composition and a molded article comprising the same. More specifically, the present invention relates to a polycarbonate resin composition and a molded article including the same, which are not deteriorated in heat resistance and mechanical properties, do not generate halogen-based harmful gases, and are excellent in light resistance and flame retardancy.

Polycarbonate resins are engineering plastics having excellent mechanical strength, high heat resistance, transparency, and the like. Accordingly, polycarbonate resins are used in various fields such as office automation devices, electrical / electronic parts, building materials, and the like. Resin used as LCD (Liquid Crystalline Display) back light component in electric / electronic parts field requires high light reflectance, light resistance, color fastness, etc., and high fluidity is required by slimming and thinning of products such as TV, monitor, notebook, etc. .

When the polycarbonate resin is used as a back light component of the LCD, in order to minimize and reflect the back light loss, the resin is often colored with a high white color and used as a back-light flame. As such a white pigment for coloring the resin in a high white color, titanium dioxide (TiO ₂ ), which exhibits the highest refractive index in air, is mainly used.

In order to impart flame retardance to such a resin composition, a halogen-based flame retardant and an antimony compound or a phosphorus-based compound have been conventionally used. However, when halogen-based flame retardants are used, the demand for resins that do not contain halogen-based flame retardants is rapidly expanding due to the problem of human health of gases generated during combustion. Phosphoric acid-based flame retardants are representative of phosphorus compounds, but in resin compositions using the same, a so-called "juice" phenomenon may occur in which the flame retardant moves to the surface of the molding during deposition, and the heat resistance of the resin composition is rapidly increased. There is a risk of deterioration.

Without the use of halogen-based flame retardants, phosphorus compounds, etc., the most common technique is to use sulfonic acid metal salts. However, the use of a large amount of titanium dioxide for coloring with high white color is common. If the flame retardancy is lowered, the resin is decomposed at a high temperature and the mechanical properties of the resin composition may be lowered.

U.S. Pat.No. 7,232,854 discloses a flame retardant resin composition composed of polycarbonate, polycarbonate siloxane copolymer and phosphate ester flame retardant. The resin composition may satisfy the flame retardancy, but there is a fear that the heat resistance is lowered.

An object of the present invention is to provide a polycarbonate resin composition which does not deteriorate heat resistance and mechanical properties, does not generate halogen-based harmful gases, and which is excellent in light resistance and flame retardancy.

Another object of the present invention is to provide a thermoplastic polycarbonate resin composition having excellent physical properties such as heat resistance, impact resistance, workability, and appearance.

Still another object of the present invention is to provide a molded article formed from the polycarbonate resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a polycarbonate resin composition. The polycarbonate resin composition is a polycarbonate resin; Polyorganosiloxane containing graft copolymers; Organosiloxane polymers; Phosphorus flame retardants; And titanium dioxide.

In embodiments, based on about 100 parts by weight of the polycarbonate resin, the content of the polyorganosiloxane-containing graft copolymer is about 0.1 to about 5 parts by weight, and the content of the organosiloxane polymer is about 0.1 to about 5 parts by weight. Part, and the content of the phosphorus-based flame retardant is about 1 to about 3 parts by weight, and the content of the titanium dioxide may be about 5 to about 50 parts by weight.

In an embodiment, the polyorganosiloxane-containing graft copolymer comprises polyorganosiloxane particles; Monomer mixtures comprising at least one of a polyfunctional monomer and another copolymerizable monomer; And it may be a graft copolymer polymerized with a vinyl-based monomer.

The polyorganosiloxane particles may have a number average particle diameter of about 0.008 μm to about 0.6 μm.

In embodiments, the organosiloxane polymer may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ₂₁ to R ₂₇ are each independently an alkyl group having 1 to 6 carbon atoms and 6 to 12 carbon atoms. Is an aryl group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms, Ar is an aryl group having 6 to 12 carbon atoms, and m and n are As an integer indicating the number of repeating units, the m + n value is an integer from 1 to 500, and m is 1 or more.

In embodiments, the organosiloxane polymer may comprise at least one of poly (methylphenyl) siloxane, poly (diphenyl) siloxane, dimethylsiloxane-diphenylsiloxane, or copolymers of dimethylsiloxane-methylphenyl siloxane.

In an embodiment, the organosiloxane polymer may have a kinematic viscosity of about 1 to about 1,000 mm ² / S at about 25 ° C.

In embodiments, the phosphorus flame retardant may include at least one of phosphorus, phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, or metal salts thereof.

In an embodiment, the polycarbonate composition may further include about 0.1 to about 5 parts by weight of the fluorinated polyolefin resin, based on about 100 parts by weight of the polycarbonate resin.

The fluorinated polyolefin resin may be polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, or ethylene / tetrafluoroethylene At least one of the copolymers may be included.

In an embodiment, the polycarbonate composition may further include about 1 to about 100 parts by weight of a filler based on about 100 parts by weight of the polycarbonate resin.

The filler may include at least one of carbon fiber, glass fiber, glass beads, glass flakes, carbon black, talc (talc), clay, kaolin, mica, or calcium carbonate.

Another aspect of the invention relates to a molded article. The molded article is formed from the polycarbonate resin composition.

The polycarbonate resin composition according to the present invention is environmentally friendly because no halogen-based gas is generated, and mechanical properties such as heat resistance and impact resistance are not degraded even when phosphorus-based flame retardants are used, and physical properties such as light resistance, flame retardancy, workability, and appearance It is excellent and useful as a material for electric / electronic parts.

Hereinafter, the present invention will be described in detail.

The polycarbonate resin composition according to the present invention comprises (A) polycarbonate resin, (B) polyorganosiloxane-containing graft copolymer, (C) organosiloxane polymer, (D) phosphorus flame retardant, and (E) titanium dioxide Include.

(A) polycarbonate resin

The polycarbonate resin used in the present invention is a thermoplastic polycarbonate resin. As the polycarbonate resin, for example, an aromatic polycarbonate resin prepared by reacting diphenols represented by the following formula (1) with carbonate precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

[Formula 1]

In Formula 1, A is a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted C2-C5 alkylidene group, a substituted or unsubstituted C3-C6 cycloalkylene group , A substituted or unsubstituted cycloalkylidene group having 5 to 6 carbon atoms, CO, S, or SO ₂ , R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or substituted or unsubstituted An aryl group having 6 to 30 ring carbon atoms, n ₁ and n ₂ are each independently an integer of 0 to 4; Here, the term "substituted" means that the hydrogen atom is a halogen group, an alkyl group of 1 to 30 carbon atoms, a haloalkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbon atoms, 1 to It means what was substituted by substituents, such as 20 alkoxy groups and these.

Examples of the diphenols include hydroquinone, resorcinol, 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, and 2,4-bis (4-hydroxyphenyl) -2-methylbutane , 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxy Phenyl) propane and the like, but is not limited thereto. Examples of the diphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, or 1,1-bis (4 -Hydroxyphenyl) cyclohexane can be used, specifically 2,2-bis (4-hydroxyphenyl) propane, also called bisphenol-A, can be used.

The weight average molecular weight (Mw) of the polycarbonate resin may be about 10,000 to about 200,000 g / mol, for example, about 15,000 to about 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a branched chain, for example, from about 0.05 to about 2 mol% of a trivalent or more polyfunctional compound, specifically trivalent, based on the total diphenols used for polymerization. Or it can also manufacture by adding the compound which has more phenol groups.

The polycarbonate resin may be used in the form of a homo polycarbonate resin, copolycarbonate resin or blends thereof.

In addition, the polycarbonate resin may be partially or entirely replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid.

(B) Polyorganosiloxane-containing Graft Copolymer

Polyorganosiloxane-containing graft copolymers used in the present invention include polyorganosiloxane particles (B-1); Monomer mixture (B-2) comprising at least one of a polyfunctional monomer (B-2-a) and another copolymerizable monomer (B-2-b); And a vinyl monomer (B-3); are polymerized. For example, the polyorganosiloxane-containing graft copolymer is a copolymerizable monomer (B-2-b) different from a polyfunctional (polyfunctional) monomer (B-2-a) having two or more polymerizable unsaturated bonds. From about 0.5 to about 10 weight percent of the monomer mixture (B-2) comprising at least one of the following is polymerized in the presence of about 40 to about 90 weight percent of the polyorganosiloxane particles (B-1); To 50% by weight of the vinyl monomer (B-3) can be used to obtain a further polymerization, specifically, a graft air having a structure in which the vinyl monomer is grafted to the core structure of the rubber to form a hard shell Coalescing may be used.

The polyorganosiloxane particles (B-1) may have a number average particle diameter of about 0.008 to about 0.6 μm, for example, about 0.01 to about 0.2 μm, specifically about 0.01 to about 0.15 μm. This can be measured by light scattering or electron microscopy. It is excellent in workability in the said range, and can reduce the flame retardance of a polycarbonate resin composition.

The polyorganosiloxane particles (B-1) are made of a material insoluble in toluene (measured by impregnating about 0.5 g of particles in about 80 mL of toluene at about 23 ° C. for about 24 hours) in order to improve flame retardancy and impact resistance. The content may be about 95 wt% or less, for example about 50 wt% or less, specifically about 20 wt% or less. The polyorganosiloxane particles (B-1) are modified to contain about 5% by weight or less of other copolymers (for example, butyl polyacrylate, butyl-styrene acrylate copolymer, etc.) in addition to particles made of polyorganosiloxane. Polyorganosiloxane particles.

The polyorganosiloxane particles (B-1) may be prepared from cyclosiloxane, and specific examples of the cyclosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane. , Trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like can be exemplified. Silicone rubber can be manufactured by using 1 or more types of hardening | curing agents for these siloxanes, The examples of the hardening | curing agent are trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, a mixture thereof, etc. It can be illustrated.

Examples of the polyfunctional monomer (B-2-a) include allyl methacrylate, triallyl of cyanuric acid, triallyl of isocyanate, diallyl phthalate, ethylene glycol dimethacrylate, and 1,3-butylene dimethacrylic acid Glycol, divinyl benzene, and the like, and examples of the copolymerizable monomer (B-2-b) include aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, and parabutylstyrene, acrylonitrile, and meta. Vinyl cyanide monomers such as chloronitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxy ethyl acrylate, hydroxy butyl acrylate, methyl methacrylate, meta Carboxes such as acrylic acid ester monomers such as ethyl acrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate, acrylic acid and maleic acid There can be mentioned a group containing vinyl monomer, and a mixture thereof.

The monomer mixture (B-2) containing at least one of the above-mentioned multifunctional monomer (B-2-a) and other copolymerizable monomers (B-2-b) is to improve the flame retardant effect and the impact resistance improvement effect. As used, from about 0 to about 100% by weight, for example from about 50 to about 100% by weight, in particular from about 80 to about 100% by weight of the multifunctional monomer (B-2-a) containing at least two polymerizable unsaturated bonds in the molecule About 100 weight percent, and about 0 to about 100 weight percent of the copolymerizable monomer (B-2-b), for example about 0 to about 50 weight percent, specifically about 0 to about 20 weight percent. The impact resistance of the polyorganosiloxane-containing graft copolymer prepared in the above range may be excellent.

The vinyl monomer (B-3) is a mixture of the graft copolymer (B) and the thermoplastic resin (B) when the graft copolymer (B) is blended with the thermoplastic resin (A) in order to improve flame retardancy and impact resistance. It is a component used to ensure compatibility and disperse | distribute a graft copolymer (B) uniformly in a thermoplastic resin (A).

As the vinyl monomer (B-3), those mentioned in the copolymerizable monomer (B-2-b) of the monomer mixture (B-2) may be used, and these may be used alone or in combination of two or more different kinds thereof. Can be.

In addition, the polymer solubility parameter of the vinyl monomer (B-3) is about 9.15 to about 10.15 cal / cm ³ , for example about 9.17 to about 10.10 cal / cm ³ , specifically about 9.20 to about 10.05 cal / cm ³ For example, the polymer of the vinyl monomer (B-3) may include polymethyl methacrylate, butyl polyacrylate, butyl polymethacrylate, polystyrene, polyacrylonitrile, and the like.

The polyorganosiloxane-containing graft copolymer is structurally grafted monomer mixture (B-2) to the polyorganosiloxane particles (B-1), the vinyl monomer (B-3) polyorganosiloxane particles Since it is obtained by grafting to the polymer formed by (B-1) and the monomer mixture (B-2), the content of the free polymer produced by the graft polymerization of the vinyl monomer is low. In order to obtain the excellent flame retardant effect of the polyorganosiloxane-containing graft copolymer, by infiltrating about 1 g of polyorganosiloxane-containing graft copolymer in about 80 ml of acetone at about 23 ℃ for about 48 hours Obtained) may be at least about 80% by weight, for example at least about 85% by weight.

In an embodiment, the content of silicon in the core, ie the rubber part, of the core in the polyorganosiloxane-containing graft copolymer may be about 10 to about 90% by weight. It is possible to obtain the flame retardancy and impact strength required for the product in the above range.

The content of the polyorganosiloxane-containing graft copolymer (B) may be about 0.1 to about 5 parts by weight, for example about 0.5 to about 3 parts by weight, based on about 100 parts by weight of the polycarbonate resin (A). . It may have excellent heat resistance and flame retardancy in the above range, and may be economical.

(C) organosiloxane polymer

The organosiloxane polymer used in the present invention may be represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R ₂₁ to R ₂₇ (R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ ) each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or 1 carbon atom. And an alkenyl group of 6 to 6, Ar is an aryl group, for example, an aryl group having 6 to 12 carbon atoms, m and n are integers indicating the number of repeating units, and the m + n value is an integer ranging from 1 to 500. , m is 1 or more. Preferably, the organosiloxane polymer is a copolymer having different m and n repeating units, and the m: n ratio is preferably in the range of 1: 9 to 7: 3.

Specific examples of the organosiloxane polymer may be phenyl substituted siloxane copolymer represented by the following formula (3).

[Formula 3]

In Formula 3, R ₁₁ , R ₁₂ , R ₂₁ to R ₂₇ , m and n are as defined in Formula 2. For example, R ₁₁ and R ₁₂ may each independently be a methyl group or a phenyl group, and R ₂₁ to R ₂₇ may each independently be a methyl group, a phenyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, or a vinyl group.

When the said phenyl substituted siloxane copolymer is used as said organic siloxane polymer, it is excellent in light resistance. Preferred examples of the organosiloxane polymer (phenyl substituted siloxane copolymer) include poly (methylphenyl) siloxane, poly (diphenyl) siloxane, dimethylsiloxane-diphenylsiloxane copolymer, copolymers of dimethylsiloxane-methylphenylsiloxane, mixtures thereof, and the like. Can be illustrated.

The dynamic viscosity (dynamic viscosity) of the organosiloxane polymer may be about 1 to about 1,000 mm ² / S, for example about 4 to about 500 mm ² / S at about 25 ℃. In the above range may be excellent in the light resistance and impact strength of the polycarbonate resin composition.

The content of the organosiloxane polymer (C) may be about 0.1 to about 5 parts by weight, for example about 0.5 to about 3 parts by weight, based on about 100 parts by weight of the polycarbonate resin (A). It has excellent flame retardancy and colorability in the above range, it is possible to prevent the heat resistance, flame retardancy and impact strength of the polycarbonate resin composition generated when the polyorganosiloxane-containing graft copolymer and the phosphorus-based flame retardant are used at the same time.

In addition, the content ratio ((B) :( C) weight ratio) of the polyorganosiloxane-containing graft copolymer (B) and the organosiloxane polymer (C) is, for example, about 1: about 1 to about 1: 1: About 50, for example about 1: about 1 to about 1: about 20. The flame retardancy may be excellent in the above range.

(D) phosphorus flame retardant

The phosphorus flame retardant used in the present invention is for improving the flame retardancy of the polycarbonate resin composition and the like, and a conventional phosphorus flame retardant may be used.

In embodiments, the phosphorus-based flame retardant may be used, such as phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene and metal salts thereof. May be, but is not necessarily limited thereto. These can be applied individually or in mixture of 2 or more types.

For example, the phosphate may have a form such as a bisphenol-A derivative oligomeric phosphate ester flame retardant, a resorcinol derivative oligomeric phosphate ester flame retardant, and the like. Non-limiting examples of such phosphate ester flame retardants include bisphenol A diphosphate, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, tri (2,6-dimethylphenyl) phosphate, tri (2,4) , 6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dimethylphenyl) phosphate, resorcinol bis (diphenyl) phosphate, resorcinol bis (2,6 -Dimethylphenyl) phosphate, resorcinol bis (2,4-dibutylbutylphenyl) phosphate, hydroquinol bis (2,6-dimethylphenyl) phosphate, hydroquinol bis (2,4-dibutylbutylphenyl) phosphate, etc. Can be illustrated. The phosphate ester flame retardant may be applied alone or in the form of a mixture of two or more thereof.

The content of the phosphorous flame retardant (D) may be about 1 to about 5 parts by weight, for example about 1 to about 3 parts by weight, based on about 100 parts by weight of the polycarbonate resin (A). It may have excellent flame resistance, light resistance and the like in the above range, it is possible to prevent the heat resistance, flame resistance and impact strength of the polycarbonate resin composition generated when the polyorganosiloxane-containing graft copolymer and the phosphorus flame retardant is used at the same time.

(E) titanium dioxide

As titanium dioxide used in the present invention, ordinary titanium dioxide can be used, and a production method, a particle diameter, and the like are not limited.

In embodiments, the titanium dioxide may be titanium dioxide surface-treated with an inorganic surface treatment agent or an organic surface treatment agent.

The inorganic surface treatment agent may be aluminum oxide (alumina, Al ₂ O ₃ ), silicon dioxide (silica, SiO ₂ ), zirconium dioxide (zirconia, ZrO ₂ ), sodium silicate, sodium aluminate, sodium aluminum silicate, zinc oxide, mica And combinations thereof.

Examples of the organic surface treating agent include polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and combinations thereof.

In the surface treatment of the titanium dioxide, the amount of the surface treating agent may be about 0.01 to about 3 parts by weight, for example, about 0.05 to about 2 parts by weight based on 100 parts by weight of titanium dioxide. Light resistance may be excellent in the above range.

Specifically, titanium dioxide coated with less than about 2 parts by weight of aluminum oxide based on about 100 parts by weight of titanium dioxide may be used in the inorganic surface treatment agent. In addition, the titanium dioxide surface-treated with aluminum oxide is inorganic surface treatment agents such as silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and the like. The organic surface treatment agent may be further modified and used.

The content of the titanium dioxide (E) may be about 5 to about 50 parts by weight, for example about 10 to about 30 parts by weight, based on about 100 parts by weight of the polycarbonate resin (A). It may be excellent in light resistance and impact resistance in the above range.

The polycarbonate resin composition according to the present invention may further include (F) fluorinated polyolefin resin and / or (G) filler.

(F) fluorinated polyolefin resin

The fluorinated polyolefin resin used in the present invention forms a fibrous network in the resin when the polycarbonate resin composition of the present invention is molded (extruded), thereby lowering the melt viscosity of the resin during combustion and reducing the shrinkage rate. By increasing it, the dripping phenomenon of resin can be prevented.

Specific examples of the fluorinated polyolefin resin include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetra Fluoroethylene copolymers, mixtures thereof and the like can be exemplified.

The fluorinated polyolefin resin may be prepared using a known polymerization method, for example, a pressure of about 7 to about 71 kg / cm ² and about 0 to about 200 ℃, for example about 20 to about 100 ℃ At the temperature conditions of, it can be prepared in an aqueous medium containing free radical forming catalysts such as sodium, potassium or ammonium peroxydisulfate.

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin resin in the emulsion state is used, the dispersibility in the entire resin composition is good, but there is a disadvantage in that the manufacturing process is complicated. Therefore, even if it is a powder state, if it can disperse | distribute suitably in the whole resin composition and can form a fibrous network, it is preferable to use in powder state.

Preferred examples of the fluorinated polyolefin resin may include polytetrafluoroethylene having a particle size of about 0.05 to about 1,000 μm and a specific gravity of about 1.2 to about 2.3 g / cm ³ .

When using the fluorinated polyolefin resin (F), the content of the fluorinated polyolefin resin (F) is about 0.1 to about 5 parts by weight, for example about 0.5 to about 3 parts by weight, based on about 100 parts by weight of the polyester resin (A). It may be part by weight. Dropping of the resin can be prevented by lowering the resin melt viscosity and increasing the shrinkage in the above range.

(G) filler

Fillers used in the present invention may be added to increase the mechanical properties, heat resistance, dimensional stability and the like of the polycarbonate resin composition.

As the filler, conventional organic and / or inorganic fillers having various particle forms may be used. For example, carbon fiber, glass fiber, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica , Calcium carbonate and mixtures thereof and the like can be exemplified. Specifically, glass fibers, talc and clay may be used, and more specifically, glass fibers may be used.

When the filler (G) is used, the content of the filler (G) may be about 100 parts by weight or less, for example, about 10 parts by weight to about 90 parts by weight based on about 100 parts by weight of the polycarbonate resin (A). In the above range, mechanical properties, heat resistance, dimensional stability, and the like of the resin composition may be increased.

The polycarbonate resin composition according to the present invention, in addition to the constituent components, according to the respective applications, such as UV stabilizers, fluorescent brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additives, colorants such as pigments or dyes It may further include an additive.

The ultraviolet stabilizer serves to suppress the color change and the light reflectance of the resin composition according to the UV irradiation, compounds such as benzotriazole-based, benzophenone-based, triazine-based may be used.

The fluorescent brightener serves to improve the light reflectance of the polycarbonate resin composition, 4- (benzooxazol-2-yl) -4 '-(5-methylbenzooxazol-2-yl) stilbene or Stilbene-bisbenzooxazole derivatives such as 4,4'-bis (benzooxazol-2-yl) stilbene and the like can be used.

The release agent may be a fluorine-containing polymer, silicone oil, a metal salt of stearyl acid, a metal salt of montanic acid, a montanic acid ester wax or a polyethylene wax, and the nucleating agent may be talc or clay.

As the inorganic additive, glass fiber, silica, clay, calcium carbonate, calcium sulfate or glass beads may be used.

The molded article according to the present invention is formed from the polycarbonate resin composition. The molded article can be easily formed (manufactured) by one of ordinary skill in the art.

In an embodiment, the polycarbonate resin composition may be in the form of pellets, chips, or the like by extrusion. In addition, the molded article may be an electric / electronic component (for example, a liquid crystal display LCD backlight component, etc.) formed by molding a polycarbonate resin composition having a pellet, chip, or the like by various molding methods such as injection molding.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

실시예Example

(A) polycarbonate resin, (B) polyorganosiloxane-containing graft copolymer, (C) organosiloxane polymer, (D) phosphorus flame retardant, (E) titanium dioxide, used in Examples and Comparative Examples of the present invention, The specifications of (F) fluorinated polyolefin resin and (G) filler are as follows.

(A) polycarbonate resin

Bisphenol-A polycarbonate (weight average molecular weight (Mw): 25,000 g / mol) was used.

(B) Polyorganosiloxane-containing Graft Copolymer

KANEACE MR-01 from KANEKA CORPORATION was used.

(B ') polydimethylsiloxane rubber mixture (impact enhancer)

Metablene S-2001 from Mitsubishi Rayon chemical was used.

(C) organosiloxane polymer

Polymethylphenyl siloxane oil (GE-Toshiba Silicone, TSF-433) was used.

(D) phosphorus flame retardant

(D1) Bisphenol-A derivative oligomeric phosphate ester flame retardant

CR-741 from Daihachi, Japan was used.

(D2) Resorcinol Derived Oligomeric Phosphate Ester Flame Retardant

PX-220 from Daihachi, Japan, was used.

(E) titanium dioxide

Titanium dioxide (KRONOS Corporation, KRONOSS 2233) was used.

(F) fluorinated polyolefin resin

Teflon (Dupont, TEFLON 800-J) was used.

(G) filler

Glass fiber (NITTOBO, CSF 3PE 936S) was used.

실시예 1 내지 3 및 비교예 1 내지 12Examples 1 to 3 and Comparative Examples 1 to 12

According to the content of Table 1 below, each component was added and melted / kneaded in a twin screw melt extruder heated to 240 to 280 ℃ to prepare a resin composition in the chip state. The chip thus obtained was dried at a temperature of 130 ° C. for at least 5 hours, and then a specimen for measuring flame retardancy and a specimen for evaluation of mechanical properties were prepared using a screw injection machine heated to 240 to 280 ° C.

Table 1

Composition		Example			Comparative example
Composition		One	2	3	One	2	3	4	5	6	7	8	9	10	11	12
(A)		100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
(B)		One	2	One	-	2	-	-	9	One	-	-	2	2	2	-
(B ')		-	-	-	-	-	2	-	-	-	-	-	-	-	-	-
(C)		2	2	One	-	-	2	2	One	9	-	-	2	2	-	2
(D)	(D1)	One	One	One	-	-	-	-	-	-	7	-	-	-	One	One
(D)	(D2)	One	One	One	-	-	-	-	-	-	-	5	-	-	One	One
(E)		20	20	20	20	20	20	20	20	20	20	20	60	-	20	20
(F)		0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
(G)		10	10	10	10	10	10	10	10	10	10	10	10	10	10	10

Unit: weight part

With respect to the specimen obtained in the composition as shown in Table 1, flame retardancy, Vicat softening temperature, impact strength, light resistance was evaluated by the following method and the results are shown in Table 2 below.

Property evaluation method

(1) Flame retardancy: The 1.5 mm and 1.2 mm thick specimens were measured by UL-94 vertical test method.

(2) Vicat softening temperature (VST): measured at 5 kgf load in accordance with ASTM D1525.

(3) Izod impact strength: According to ASTM D256, notches were made on 1/8 thickness Izod specimens and measured.

(4) Flexural modulus: Measured on a 6.4 mm thick specimen in accordance with ASTM D790.

(5) Light resistance: UV light was irradiated onto 3 cm × 10 cm specimens using a UV-Condensation machine of ASTM G53 standard. Minolta 3600D CIE Lab. The yellowness (Yellow Index) of the test piece was measured by a color difference meter.

TABLE 2

		Example			Comparative example
		One	2	3	One	2	3	4	5	6	7	8	9	10	11	12
Flame retardancy	1.5mm	V-0	V-0	V-0	Fail	V-0	Fail	V-1	Fail	Fail	Fail	Fail	V-1	V-0	V-0	Fail
Flame retardancy	1.2 mm	V-1	V-1	V-1	Fail	Fail	Fail	Fail	Fail	Fail	Fail	Fail	Fail	V-1	Fail	Fail
VST (℃)		136	135	138	139	135	134	135	127	128	120	122	136	136	137	136
Izod impact strength (kgfcm / cm)		14	16	15	4	10	11	10	18	14	4	5	4	20	10	12
Flexural modulus (kgf / cm ² )		38,000	37,000	38,000	39,500	38,000	39,000	39,000	33,000	34,000	37,000	36,000	42,000	32,000	35,000	36,000
Light resistance (yellowness)	Before UV irradiation	1.0	1.5	1.1	1.2	1.3	1.9	1.3	3.4	1.2	2.8	1.6	1.2	1.2	1.3	1.3
	After 72 hours of ultraviolet irradiation	22.1	24.3	23.2	28.3	22.7	27.8	27.4	26.5	19.5	26.6	25.9	18.3	34.2	25.2	26.5
	Yellowness difference	21.1	22.8	22.1	27.1	21.4	25.9	26.1	23.1	18.3	23.8	24.3	17.1	33.0	23.0	24.3

From the results of Table 2, it can be seen that the thermoplastic polycarbonate resin compositions of Examples 1 to 3 according to the composition of the present invention are excellent in impact strength, light resistance and flame retardance without reducing heat resistance.

On the contrary, Comparative Examples 1 to 4, which do not follow the composition of the present invention, are inferior in flame retardancy, and Comparative Example 9 is inferior in flame retardancy, flexural modulus and light resistance. In addition, in Comparative Examples 5 and 6, the impact strength was improved, but the flame retardancy was decreased, and in Comparative Examples 7, 8, the flame retardancy and / or the impact strength was lowered. In addition, Comparative Example 10 was confirmed that the light resistance is lowered, Comparative Examples 11 and 12, flame retardancy and impact strength is lowered.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

Polycarbonate resins;

Polyorganosiloxane containing graft copolymers;

Organosiloxane polymers;

Phosphorus flame retardants; And

Titanium dioxide; Polycarbonate resin composition comprising a.
The amount of the polyorganosiloxane containing graft copolymer is about 0.1 to about 5 parts by weight, and the content of the organosiloxane polymer is about 0.1 to about 5 parts by weight of the polycarbonate resin. 5 parts by weight, the content of the phosphorus-based flame retardant is about 1 to about 3 parts by weight, and the content of the titanium dioxide is about 5 to about 50 parts by weight of polycarbonate resin composition.
According to claim 1, wherein the polyorganosiloxane-containing graft copolymer is polyorganosiloxane particles; Monomer mixtures comprising at least one of a polyfunctional monomer and another copolymerizable monomer; And a vinyl monomer; a polycarbonate resin composition characterized in that it is a graft copolymer polymerized.
The polycarbonate resin composition of claim 3, wherein the polyorganosiloxane particles have a number average particle diameter of about 0.008 to about 0.6 mu m.
The polycarbonate resin composition of claim 1, wherein the organosiloxane polymer is a compound represented by Formula 2 below:

[Formula 2]

In Formula 2, R 11 and R 12 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R 21 to R 27 are each independently an alkyl group having 1 to 6 carbon atoms and 6 to 12 carbon atoms. Is an aryl group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms, Ar is an aryl group having 6 to 12 carbon atoms, and m and n are As an integer indicating the number of repeating units, the m + n value is an integer from 1 to 500, and m is 1 or more.
The method of claim 1, wherein the organosiloxane polymer comprises at least one of poly (methylphenyl) siloxane, poly (diphenyl) siloxane, dimethylsiloxane-diphenylsiloxane, or a copolymer of dimethylsiloxane-methylphenyl siloxane. Polycarbonate resin composition.
The polycarbonate resin composition of claim 1, wherein the organosiloxane polymer has a kinematic viscosity of about 1 to about 1,000 mm 2 / S at about 25 ° C.
The polycarbonate resin composition of claim 1, wherein the phosphorus-based flame retardant comprises at least one of phosphorus, phosphonate, phosphinate, phosphine oxide, phosphazene, or metal salts thereof.
The polycarbonate resin composition of claim 1, wherein the polycarbonate composition further comprises about 0.1 to about 5 parts by weight of the fluorinated polyolefin resin based on about 100 parts by weight of the polycarbonate resin.
The method of claim 9, wherein the fluorinated polyolefin resin is polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, or A polycarbonate resin composition comprising at least one of ethylene / tetrafluoroethylene copolymers.
The polycarbonate resin composition of claim 1, wherein the polycarbonate composition further comprises about 1 to about 100 parts by weight of a filler based on about 100 parts by weight of the polycarbonate resin.
The method of claim 11, wherein the filler is poly, characterized in that it comprises at least one of carbon fiber, glass fiber, glass beads, glass flakes, carbon black, talc (talc), clay, kaolin, mica, or calcium carbonate. Carbonate resin composition.
A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 12.