KR20140086374A - Polycarbonate Resin Composition with Good Light-transmittance and Flame Retardancy - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition with excellent optical permeability and flame retardancy comprising: 100 parts by weight of a polycarbonate resin (A); 0.1-2 parts by weight of a silicon based light diffusing agent (B); 0.1-5 parts by weight of an aromatic phosphoric ester based compound (C); 0.01-1 parts by weight of a fluorinated polyolefin resin (D); and 2-8 parts by weight of a porous aluminum silicate compound (E), and exhibits excellent thin film flame retardancy and optical permeability by minimizing fluorinated polyolefin resin content by introducing the porous aluminum silicate compound (E).

Description

[0001] The present invention relates to a polycarbonate resin composition having excellent light transmittance and flame retardancy,

The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition which is excellent in light transmittance and flame retardancy, and is particularly suitable for use as a cover or a bulb of an LED (light emitting diode) illumination device.

Polycarbonate resins are widely used as engineering plastic materials for office automation equipment, electric / electronic products, building materials and the like because they have excellent mechanical strength, heat resistance and transparency. Recently, light emitting diodes (LED, light emitting diodes (LEDs). Due to its excellent energy efficiency and long life span, LEDs are rapidly emerging as a substitute for many existing light sources.

Polycarbonate resin is also used as a bulb or cover material for LED lighting devices. Considering that the LED light source is high temperature, it has excellent mechanical strength, heat resistance and transparency as well as excellent flame retardancy Is required. Particularly, when it is used as a cover material of an LED lighting device such as a bulb of an LED lighting device or an LED straight tube lamp, it is preferable from the viewpoint of light efficiency to use a material having excellent light transmittance and moldability, Which is advantageous for molding.

A conventional method for imparting flame retardancy to a polycarbonate resin composition uses a halogen-based flame retardant and an antimony compound. However, when a halogen-based flame retardant is used, the demand for a resin that does not contain a halogen-based flame retardant has been rapidly expanding due to human harmfulness of gas generated at the time of combustion. As a technique for imparting flame retardancy to a flame retardant without using a halogen flame retardant, a phosphoric acid ester flame retardant is most commonly used at present. However, such a polycarbonate resin composition has a problem that the mechanical properties such as impact strength are deteriorated due to the flame retardant.

Japanese Patent Application Laid-Open No. 2002-088237 discloses a polycarbonate resin composition having flame retardancy and anti-drop effect by using polytetrafluoroethylene (PTFE) as a drip inhibitor. However, when the fluorinated polyolefin-based resin such as PTFE is contained in an excess amount, the flame retardancy and the drop-preventive property can be improved in the thin film molding, but the light transmittance and thermal stability may be deteriorated. Inappropriate.

A flame retardant of phosphorus type or a metal salt may be used instead of PTFE as an anti-drip agent, but when the phosphorus flame retardant is used in an excess amount for flame retardancy, the heat resistance of the polycarbonate resin composition is lowered. As a result, when PTFE is used in an excessive amount in the polycarbonate resin composition, the flame retardancy is good when the thin film is formed, but the light transmittance is deteriorated. The present inventors have found that the flame retardancy at 1.2 mm or less And at the same time, to develop a polycarbonate resin composition of the present invention using a nano-sized hollow-type aluminum silicate compound at the same time as using a minimum of PTFE.

An object of the present invention is to provide a polycarbonate resin composition excellent in light transmittance and thin film flame retardancy.

Another object of the present invention is to provide a polycarbonate resin composition excellent in light transmittance and thin film flame retardancy while maintaining excellent mechanical properties inherent to the polycarbonate resin.

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

The flame retardant polycarbonate resin composition excellent in light transmittance and thin film flame retardancy according to the present invention comprises (A) 100 parts by weight of a polycarbonate resin; (B) 0.1 to 2 parts by weight of a silicone-based light-diffusing agent; (C) 0.1 to 5 parts by weight of an aromatic phosphate ester compound; (D) 0.01 to 1 part by weight of a fluorinated polyolefin-based resin; And (E) 2 to 8 parts by weight of a hollow aluminum silicate compound.

In the present invention, the silicone-based light-diffusing agent (B) comprises 50 to 100% by weight of polyorganosilsesquioxane based on a total amount of 100% by weight, and the polyorganosilsesquioxane is selected from the group consisting of polymethylsilsesquioxane, poly Ethyl silsesquioxane, polypropyl silsesquioxane, polybutyl silsesquioxane, and mixtures thereof.

In the present invention, the aromatic phosphate ester compound (C) is represented by the following formula (2)

(2)

Wherein R 1, R 2, R 4 and R 5 are each independently an aryl group of C 6 to C 20 or an aryl group of C 6 to C 20 substituted with C 1 to C 4 alkyl, and R 3 is a group selected from the group consisting of resorcinol, hydroquinol, bisphenol- A or bisphenol-S, and m is an integer of 0 to 5.

In the present invention, the fluorinated polyolefin resin (D) may be at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetra Fluoroethylene copolymers, and mixtures thereof.

In the present invention, the hollow aluminum silicate compound (E) is a halloysite nanotube (HNT) having a spacing space and a silicate layer. The diameter of the halo-site nanotubes is preferably in the range of 30 to 200 nm.

The polycarbonate resin composition of the present invention can be used as an anticorrosive agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, a compatibilizer, a dye, an inorganic additive, a surfactant, a coupling agent, a plasticizer, an impact modifier, an admixture, An additive selected from the group consisting of a pigment, a flame retardant, a weather stabilizer, a colorant, an ultraviolet screening agent, a filler, a nucleating agent, an adhesion promoter, a pressure sensitive adhesive and a mixture thereof in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the polycarbonate resin (A) .

The molded article using the polycarbonate resin composition of the present invention may have a light transmittance of 55 to 95% measured on 2.0 mm thick specimens according to ASTM D1003.

The molded article using the polycarbonate resin composition of the present invention may have a flame retardancy of not less than V0 measured on 1.2 mm thick specimens in accordance with UL94.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

The present invention relates to a polycarbonate resin composition which is excellent in light transmittance and flame retardancy during thin film formation while maintaining excellent mechanical properties of a polycarbonate resin, and is particularly suitable for use as a cover or a bulb of an LED lighting device And has the effect of the invention provided.

1 is a scanning electron microscope (TEM) photograph of a haloitanium nanotube used in the examples.

 The present invention relates to a polycarbonate resin composition, which is excellent in light transmittance and flame retardancy when forming a thin film, and more particularly to a polycarbonate resin composition suitable for use in a cover or bulb of an LED lighting device.

(A) a polycarbonate resin, (B) a silicone-based light-diffusing agent, (C) an aromatic phosphate ester compound, (D) a fluorinated polyolefin-based resin, and E) hollow aluminum silicate compound.

The present invention relates to a polycarbonate resin composition using a minimum of PTFE and a nano-sized hollow aluminum silicate compound so as to maintain a good light transmittance while maintaining flame retardancy at a film thickness of 1.2 mm or less . Each component will be described in detail below.

(A) Polycarbonate resin

In the present invention, the polycarbonate resin may be prepared by reacting a diphenol represented by the following formula (1) with a compound selected from the group consisting of phosgene, halogen formate, carbonate, and combinations thereof.

[Chemical Formula 1]

In Formula 1, A is a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkylidene group, a substituted or unsubstituted C5 to C10 cycloalkylene group, A substituted or unsubstituted C5 to C10 cycloalkylidene group, CO, S, and SO2, each of R1 and R2 is independently a substituted or unsubstituted C1 to C30 alkyl group, C1-C30 alkyl group, C1-C30 aryl group, and C1-C30 aryl group, and n1 and n2 are each independently an integer of 0 to 4, Substituted with a substituent selected from the group consisting of haloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, and combinations thereof.

The diphenols represented by the above formula (1) may constitute repeating units of a polycarbonate resin by combining two or more kinds thereof. Specific examples of the diphenols include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane (also referred to as bisphenol-A) (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2- 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, and the like. Among the above diphenols, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro- (4-hydroxyphenyl) -cyclohexane can be preferably used. Further, 2,2-bis- (4-hydroxyphenyl) -propane can be more preferably used.

The polycarbonate resin preferably has a weight average molecular weight of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol. Excellent impact strength can be secured in the molecular weight range, and appropriate fluidity can be obtained, and excellent workability can be obtained.

The polycarbonate resin may be a mixture of copolymers prepared from two or more kinds of diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester-carbonate copolymer resin. Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with a diphenol and a carbonate. The polyfunctional aromatic compound is preferably contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester-carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, cyclic ethylene carbonate and the like can be used.

(B) a silicone-based light diffusing agent

The silicone-based light-diffusing agent (B) is a light-diffusing agent composed of inorganic fine particles, and contains polyorganosilsesquioxane as a main component. That is, the polyorganosilsesquioxane may be contained in an amount of 50 to 100% by weight based on the total amount of the silicone-based light-diffusing agent.

Specific examples of the polyorganosilsesquioxane include polymethylsilsesquioxane, polyethylsilsesquioxane, polypropylsilsesquioxane, and polybutylsilsesquioxane. Of these, polymethylsilsesquioxane, It is preferable to use sesquioxane.

In the present invention, the silicon-based light diffusing agent (B) is preferably included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When it is included in the above-mentioned range, the polycarbonate resin composition has excellent light diffusibility, and excellent impact strength of the polycarbonate resin can be maintained.

(C) an aromatic phosphoric ester compound

The aromatic phosphoric acid ester compound (C) for application as the flame retardant of the polycarbonate resin composition of the present invention is a compound represented by the following formula (2).

(2)

Wherein R 1, R 2, R 4 and R 5 are each independently an aryl group of C 6 to C 20 or an aryl group of C 6 to C 20 substituted with C 1 to C 4 alkyl, and R 3 is a group selected from the group consisting of resorcinol, hydroquinol, bisphenol- A or bisphenol-S, and m is an integer of 0 to 5.

i) when m is 0, triphenylphosphine, tricresyl phosphate, cresyldiphenyl phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4-ditertiarybutylphenyl) 2,6-ditertiary butylphenyl) phosphate, and the like,

(ii) when m is 1, resorcinol bis (diphenylphosphate), hydroquinolbis (diphenylphosphate), bisphenol A-diphosphate, bisphenol A-bis (diphenylphosphate), resorcinol bis 6-ditertiary butylphenylphosphate), and hydroquinolbis (2,6-dimethylphenylphosphate).

iii) When m is 2 or more, it is present as a mixture of oligomeric forms and can be applied alone or as a mixture of the above-mentioned compounds.

The aromatic phosphoric acid ester compound may be partially or wholly substituted with other phosphorus flame retardants such as phosphoric acid, phosphonate, phosphinate, and phosphazene.

In the present invention, the aromatic phosphoric ester compound (C) is preferably included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin (A). If the amount is less than 0.1 parts by weight, the flame retardancy of the polycarbonate resin composition is not sufficiently secured, and if it exceeds 5 parts by weight, the mechanical / thermal properties of the polycarbonate resin composition may be deteriorated.

(D) Fluorinated polyolefin resin

The fluorinated polyolefin-based resin (D) used in the polycarbonate thermoplastic resin composition of the present invention is a resin that can be used as a conventional resin, such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetra Fluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, and the like. These may be used independently of each other, or two or more different types may be used in combination.

When a fluorinated polyolefin resin is mixed with other components of the present invention and extruded, a fibrillar network is formed in the resin composition to increase the melt viscosity and increase the shrinkage ratio of the resin composition during combustion, Thereby preventing the dropping phenomenon.

The fluorinated polyolefin-based resin used in the production of the resin composition of the present invention can be produced by using a known polymerization method, for example, at a pressure of 7 to 71 kg / cm 2 and a temperature of 0 to 200 ° C, preferably 20 In an aqueous medium containing a free radical-forming catalyst such as sodium, potassium or ammonium peroxydisulfate under the conditions of atmospheric pressure and at a temperature of from < RTI ID = 0.0 > 100 C < / RTI >

The fluorinated polyolefin-based resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin-based resin in the emulsion state is used, the dispersibility in the whole resin composition is good, but the manufacturing process becomes complicated. Therefore, it is preferable to use it in a powder state if it can be appropriately dispersed in the whole resin composition to form a fibrous network even in a powder state.

The fluorinated polyolefin resin preferably used in the production of the polycarbonate resin composition of the present invention is polytetrafluoroethylene having a particle size of 0.05 to 1,000 탆 and a density of 1.2 to 2.3 g / cm 3.

In the present invention, the fluorinated polyolefin resin (D) is preferably contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate resin (A). If the amount is less than 0.01 part by weight, the polycarbonate resin composition can not be sufficiently prevented from dropping, and if it exceeds 1 part by weight, the light transmittance and mechanical properties of the polycarbonate resin composition may be deteriorated.

(E) Hollow aluminum silicate compound

The present invention relates to a polycarbonate resin composition which minimizes the content of a fluorinated polyolefin-based resin, particularly polytetrafluoroethylene (PTFE), which is used as an anti-drip agent, Type aluminum silicate compound. In the present invention, it is preferable to use a hollow type halloysite nanotube (HNT) as the hollow aluminum silicate compound. The hollow-type haloitanium nanotube can be defined as a nanotube having a spacing space and a silicate layer.

Hollow-form hollow-core nanotubes are made of aluminum, silicon, hydrogen, oxygen, and are made from the weathering of aluminum silicate mineral such as feldspar, and have a relatively small hollow tube with a diameter of about 30 to 200 nanometers (hollow tube) shape.

In the present invention, the hollow aluminosilicate compound (E) is preferably contained in an amount of 2 to 8 parts by weight based on 100 parts by weight of the polycarbonate resin (A). If the amount is less than 2 parts by weight, the effect of the polycarbonate resin composition on the flame retardancy is insufficient and the thermal stability is insufficient. If the amount is more than 8 parts by weight, the light transmittance of the polycarbonate resin composition may be decreased.

(F) Other additives

The polycarbonate resin composition of the present invention may further comprise additives. The additives may be selected from the group consisting of antimicrobial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, plasticizers, impact modifiers, An additive selected from the group consisting of weathering stabilizers, coloring agents, ultraviolet light blocking agents, fillers, nucleating agents, adhesion promoters, pressure-sensitive adhesives and mixtures thereof.

The additive may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the additive is included in the above range, the effect of the additive for each use can be obtained, and the polycarbonate resin composition can obtain excellent mechanical properties and improved surface appearance.

The polycarbonate resin composition according to one embodiment of the present invention can be used to produce pellets by a known method. For example, after mixing the above-mentioned components of the present invention with the additives, they can be melt-extruded in an extruder to produce pellets. In addition, a molded article produced by molding the polycarbonate resin composition of the present invention can be provided. The polycarbonate resin composition can be used as a molded product in a field where flame resistance and light transmittance are importantly important, but it can be used particularly as a bulb or a cover of an LED lighting device.

The present invention will be further illustrated by the following examples, which are to be construed as illustrative examples only and are not intended to limit or limit the scope of protection of the present invention.

Example

The specifications of each component used in Examples and Comparative Examples of the present invention are as follows.

(A) Polycarbonate resin

SC-1190 was used as a low-viscosity polycarbonate resin of Cheil Industries.

(B) a silicone-based light diffusing agent

SL-200M was used as a silicon-based light diffusing agent of Cheil Industries.

(C) an aromatic phosphoric ester compound

CR-741 was used as bisphenol-A diphosphate (BDP) from Daihachi.

(D) Fluorinated polyolefin resin

MM 5935 EF was used as 3T polytetrafluoroethylene (PTFE).

(E) Hollow aluminum silicate compound

Dragonite-XR LBV from Applied Minerals was used as the hollow type haloisot nanotube.

(F) Plate-shaped aluminum silicate compound

Kaolin (product name: Microbrite) was used as a sheet type aluminum silicate compound.

Example  1 to 3 and comparison Example  1 to 5

Each component was charged into a Henschel mixer according to the contents of Table 1, mixed for 10 minutes, and then melted / kneaded in a biaxial melt extruder heated to 240 to 350 ° C to prepare a resin composition in a pellet form Respectively. The thus-obtained pellets were subjected to the preparation of specimens for the evaluation of optical and mechanical properties using a screw extruder heated to 240 to 330 ° C, and their physical properties were evaluated. The results are also shown in Table 1 below.

Property evaluation method

(1) Occurrence of drip: The flame retardancy of 1.2 mm thick specimens according to UL94 was evaluated visually.

Yes: Occurrence, No: Not occur

(2) Self-extinguishing: Self-extinguishing was evaluated visually by evaluating flame retardancy of 1.2 mm thick specimen according to UL94.

Yes: self-extinguished, No: self-extinguishing

(3) Flame retardancy: The flame retardancy of a 1.2 mm thick specimen was evaluated according to UL94.

(4) Light transmittance: A 2.0 mm thick specimen was measured according to ASTM D1003 using a spectrophotometer.

(5) Vickers softening point temperature (VST): The Vickers softening point temperature was measured under a load of 5 kg for a 3.2 mm thick specimen according to ISO 306.

From the results shown in Table 1, it was found that the polycarbonate resin compositions of Examples 1 to 3 according to the composition of the present invention were excellent in heat resistance and excellent in light transmittance and thin film flame retardancy of 1.2 mm in thickness.

On the other hand, in Comparative Example 1 in which an aromatic phosphoric acid ester compound (C), which is a flame retardant, was used in an excessive amount to ensure flame retardancy of a thin film of 1.2 mm in thickness without using the hollow aluminum silicate compound (E), heat resistance and light transmittance And it was confirmed that it fell significantly. Comparative Example 3 in which the hollow-type aluminum silicate compound (E) was used in an excessive amount outside the scope of the present invention showed a decrease in light transmittance. Comparative Example 2 in which the hollow aluminum silicate compound (E) In Comparative Example 4, which was used less, the thin film flame retardancy of 1.2 mm thickness did not achieve V0. On the other hand, in Comparative Example 5 using the plate-shaped aluminum silicate compound (F), it was confirmed that the light transmittance was lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

(A) 100 parts by weight of a polycarbonate resin;
(B) 0.1 to 2 parts by weight of a silicone-based light-diffusing agent;
(C) 0.1 to 5 parts by weight of an aromatic phosphate ester compound;
(D) 0.01 to 1 part by weight of a fluorinated polyolefin-based resin; And
(E) 2 to 8 parts by weight of a hollow aluminum silicate compound;
Wherein the polycarbonate resin composition is excellent in light transmittance and flame retardancy.
The method according to claim 1, wherein the silicon-based light diffusing agent (B) comprises 50 to 100% by weight of polyorganosilsesquioxane based on a total amount of 100% by weight, and the polyorganosilsesquioxane comprises polymethylsilsesquioxane Wherein the polycarbonate resin composition is selected from the group consisting of polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid, polyacrylic acid,
The polycarbonate resin composition according to claim 1, wherein the aromatic phosphoric acid ester compound (C) is represented by the following formula (2):
(2)

Wherein R 1, R 2, R 4 and R 5 are each independently an aryl group of C 6 to C 20 or an aryl group of C 6 to C 20 substituted with C 1 to C 4 alkyl, and R 3 is a group selected from the group consisting of resorcinol, hydroquinol, bisphenol- A or bisphenol-S, and m is an integer of 0 to 5.
The fluorinated polyolefin resin (D) according to claim 1, wherein the fluorinated polyolefin resin (D) is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer , Ethylene / tetrafluoroethylene copolymers, and mixtures thereof. ≪ Desc / Clms Page number 13 >
The polycarbonate resin composition according to claim 1, wherein the hollow aluminum silicate compound (E) is a halloysite nanotube (HNT) having a spacing space and a silicate layer.
6. The polycarbonate resin composition according to claim 5, wherein the haloisot nanotubes have a diameter of 30 to 200 nm.
The antistatic agent according to claim 1, further comprising at least one additive selected from the group consisting of antimicrobial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, plasticizers, impact modifiers, An additive selected from the group consisting of a flame retardant, a weathering stabilizer, a colorant, an ultraviolet light blocking agent, a filler, a nucleating agent, an adhesion promoter, a pressure sensitive adhesive and a mixture thereof, And 0.1 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin composition.
A molded article produced from the polycarbonate resin composition according to any one of claims 1 to 7.
The molded article according to claim 8, wherein a light transmittance of 55 to 95% measured on a specimen of 2.0 mm thickness according to ASTM D1003.
The molded article according to claim 8, wherein the flame retardancy measured on a 1.2 mm thick specimen according to UL94 is V0 or more.

Images