KR101240320B1 - Polycarbonate Resin Composition having Good Flame Retardancy and Transparency - Google Patents

Abstract

The polycarbonate resin composition of the present invention is (B) with respect to 100 parts by weight of the base resin consisting of 50 to 90% by weight of the linear polycarbonate resin (A1) and 10 to 50% by weight of the branched polycarbonate resin (B). 5 to 20 parts by weight of a phosphoric acid ester compound or a mixture thereof; (C) 0.1 to 10 parts by weight of the cyclic phosphazene compound or a mixture thereof; And (D) 0.1 to 10 parts by weight of a phenyl group substituted siloxane copolymer. The polycarbonate resin composition has excellent fluidity and impact resistance, but has high flame retardancy and transparency.

Polycarbonate, phosphate ester compound, cyclic phosphazene compound, phenyl substituted siloxane copolymer, transparency, flame retardant

Description

Polycarbonate Resin Composition having Good Flame Retardancy and Transparency

The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention exhibits excellent transparency, flame retardancy, and high fluidity by applying a phosphate ester flame retardant, a cyclic phosphazene compound, and a phenyl substituted siloxane copolymer to a polycarbonate resin, and exhibits impact resistance, thermal stability, workability, and appearance characteristics. An excellent flame retardant thermoplastic resin composition.

Polycarbonate resin is an engineering plastic having excellent mechanical strength, high heat resistance, transparency, and the like, and is widely used in office automation devices, electric / electronic parts, and automotive materials. Recently, the invention of the resin composition that can meet the following requirements in the commercial use is urgent situation.

1) Resin composition having flame retardance without using halogen flame retardant due to environmental problems

2) It should have excellent melt flowability that enables injection molding of thin products to reduce the weight of products.

3) Transparent to increase design freedom or design

4) Maintaining characteristics such as heat resistance, melt stability, impact resistance, etc. of aromatic polycarbonates inherently

Polycarbonate resin is inherently flammable 　 Melting at high temperatures may cause flammable material. Therefore, in order to safely apply polycarbonate to your field, it must contain additives that delay the flammability of the material or reduce the dripping during combustion. In the case of most anti-dripping agents, the result is a decrease in the transparency of the polycarbonate, and therefore, it is a challenge to impart flame retardancy to the resin composition that maintains transparency.

In order to impart flame retardancy to such a resin composition, the method of mix | blending a halogen type flame retardant is known conventionally. For example, Japanese Patent Laid-Open No. 47-445337 proposes a flame-retardant polycarbonate resin composition containing 1 to 20% by weight of a carbonate oligomer of brominated bisphenol-A based on polycarbonate resin. Publication 24660 proposes a copolymerized polycarbonate resin composition of brominated bisphenol-A and bisphenol-A. In addition, Japanese Patent Application Laid-Open No. 53-50261 proposes a composition which is a mixture of an aromatic polycarbonate resin and an organic alkali metal salt. In this example, diphenyl sulfone- is used as an organic alkali metal salt in 100 parts by weight of the aromatic polycarbonate resin. A flame retardant aromatic polycarbonate resin composition has been proposed in which 0.2 parts by weight of sodium 3-sulfonic acid, 1.5 parts by weight of polycarbonate of bisphenol N-A bromide and 0.1 parts by weight of fluorinated polyolefin resin are mixed as an organic halogenated material. However, halogen-containing compounds have disadvantages such as lowering the thermal stability of the blended resin composition, corroding a molding machine screw, a molding die, and the like, and in recent years, there are problems such as environmental pollution.

As a method of improving the flame retardancy of aromatic polycarbonate without using a bromine-based flame retardant, Japanese Patent Publication No. 47-40445 discloses a method of blending an aromatic polycarbonate with an alkali metal salt or alkaline earth metal salt of perfluoro alkane sulfonic acid. Japanese Patent Application Laid-Open No. 60-38418 discloses a method of blending an organic alkali metal salt or alkaline earth metal salt with polytetrafluoroethylene in an aromatic polycarbonate to prevent dropping during combustion. However, in the aromatic polycarbonate resin composition disclosed in such a publication, the shear rate dependence of the melt viscosity is small, and in the case of forming a particularly thin molded article, it is easy to cause molding defects such as short shot due to lack of fluidity of the molten resin. There was a problem. In addition, blending polytetrafluoroethylene has a problem that transparency is largely lost.

On the other hand, a method of blending a branched aromatic polycarbonate having a branched structure or a linear aromatic polycarbonate having no branched structure in the molecular structure and maintaining a transparency has been attempted to prevent the dropping of the combustion products. For example, Japanese Patent Laid-Open No. 7-258532 discloses that dropping can be prevented without using polytetrafluoroethylene by blending an organic alkali metal salt or an organic alkaline earth metal salt with a branched aromatic polycarbonate. Doing. As the branched polycarbonate resin, only a branched polycarbonate resin synthesized by adding a branching agent represented by 1,1,1-tris (4-hydroxyphenyl) -ethane is disclosed. In the mixed resin composition disclosed in the examples, branched polycarbonate resins are used in a proportion of 30 to 100 parts by weight, and the mixed resin composition has a flame retardancy, but cannot be said to be sufficient for fluidity and transparency.

An object of the present invention is to provide a polycarbonate resin composition excellent in physical properties such as flame retardancy and transparency, mechanical strength, heat resistance, flowability.

Another object of the present invention is to provide a polycarbonate resin composition having high fluidity and impact resistance while maintaining excellent flame retardancy and transparency.

Still another object of the present invention is to provide a polycarbonate resin composition capable of preventing dropping during combustion.

Another object of the present invention is to provide a plastic molded article having excellent flame retardancy and appearance.

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

In order to achieve the above technical problem, the present invention (A) (A1) 100 parts by weight of the base resin consisting of 50 to 90% by weight of linear polycarbonate resin and (A2) 10 to 50% by weight of branched polycarbonate resin; (B) 5 to 20 parts by weight of an oligomeric phosphate ester compound derived from bisphenol-A represented by the following Chemical Formula 1 or a mixture thereof; (C) 0.1 to 10 parts by weight of the cyclic phosphazene compound represented by Formula 2; And (D) provides a polycarbonate resin composition comprising 0.1 to 10 parts by weight of a phenyl group substituted siloxane copolymer represented by the following formula (5).

[Formula 1]

Wherein R ₁ is each independently C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 to 0 representing the number of repeating units It is an integer of 5, and the average value of the mixture m of the oligomeric phosphate ester compound of the said Formula (1) is 0.5 to 2.

[Formula 2]

In the above formula, each R ₂ is independently a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted aryl group, a C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl Substituent selected from an oxy group, an amino group, or a hydroxyl group is shown, n is an integer of 0-10.

[Chemical Formula 5]

Wherein R ₅ is a methyl or phenyl group, R ₆ is a methyl, phenyl, hydroxy, methoxy, phenoxy or vinyl group, and p and q are integers in the range 1 <p + q <500, indicating the number of repeating units to be.

In another embodiment of the present invention, the degree of branching of the (A2) branched polycarbonate resin is 0.05 to 0.8%.

In another embodiment of the present invention, R ₁ of Formula 1 is each a phenyl group or a naphthyl group or methyl, ethyl, propyl, isopropyl butyl, sec-butyl, t-butyl, isobutyl, isoamyl or t-amyl group Substituted phenyl group or naphthyl group.

In another embodiment of the present invention, R ₂ of the cyclic phosphazene compound represented by Formula ₂ is a phenoxy group.

In another embodiment of the present invention, the cyclic phosphazene compound (C) is a cyclic phosphazene compound represented by the following formula (4) of the oligomeric compound of the cyclic phosphazene consisting of a linking group (linking group) having an R ₃ group Mixtures.

[Formula 4]

Wherein R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ aralkyl group, C ₁ -C ₂₀ alkoxy A substituent selected from a group, a C ₆ -C ₂₀ aryloxy group, an amino group or a hydroxy group, x and y are each an integer from 0 or 1 to 10 and R ₃ is C ₆ -C ₃₀ dioxyaryl or C _1- C ₂₀ -alkyl substituted C ₆ -C ₃₀ dioxyaryl group derivative, the average z value in the mixture of the oligomeric compound of the cyclic phosphazene represented by the formula (4) is 0.3≤z≤3 as the number average degree of polymerization.

In another embodiment of the present invention, the dynamic viscosity of the (D) phenyl group substituted siloxane copolymer is 1 to 1000 centistokes (cSt) at 25 ℃.

In another embodiment of the present invention, the (D) phenyl group substituted siloxane copolymer is a poly (methylphenyl) siloxane in which R ₅ and R ₆ are both methyl groups.

In another embodiment of the present invention, the (D) phenyl group substituted siloxane copolymer is poly (diphenyl) siloxane in which both R ₅ and R ₆ are substituted with a phenyl group.

In another embodiment of the present invention, the (D) phenyl group substituted siloxane copolymer is an air of dimethylsiloxane in which both R ₅ and R ₆ are substituted with a methyl group, and diphenylsiloxane in which both R ₅ and R ₆ are substituted with a phenyl group. It is coalescing.

In another embodiment of the present invention, the ratio of the average p and q values of the (D) phenyl group substituted siloxane copolymer is in the range of 9: 1 to 3: 7.

In order to achieve the above another technical problem, it provides a molded article prepared from the thermoplastic resin composition.

The present invention by applying the phosphate ester compound, cyclic phosphazene compound and phenyl substituted siloxane copolymer to the polycarbonate resin, while maintaining excellent flame retardancy and transparency, while providing a polycarbonate resin composition with improved fluidity and impact resistance Have

Hereinafter, the content of the present invention will be described in more detail.

The present invention (A) (A1) 100 parts by weight of the base resin consisting of 50 to 90% by weight of the linear polycarbonate resin and (A2) 10 to 50% by weight of the branched polycarbonate resin; (B) 5 to 20 parts by weight of an oligomeric phosphate ester compound derived from bisphenol-A represented by the following Chemical Formula 1 or a mixture thereof; (C) 0.1 to 10 parts by weight of the cyclic phosphazene compound represented by the following formula (2); And (D) 0.1 to 10 parts by weight of a phenyl group-substituted siloxane copolymer represented by the following Formula 5, providing transparency and flame retardancy of the polycarbonate resin composition.

[Formula 1]

Wherein each R ₁ is independently C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 indicating the number of repeating units It is an integer of 5 to 5, and the average value of the mixture m of the oligomeric phosphate ester compound of Formula 1 is 0.5 to 2.

[Formula 2]

In the above formula, each R ₂ is independently a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted aryl group, a C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl Substituent selected from an oxy group, an amino group, or a hydroxyl group is shown, n is an integer of 0-10.

[Chemical Formula 5]

Wherein R ₅ is a methyl or phenyl group, R ₆ is a methyl, phenyl, hydroxy, methoxy, phenoxy or vinyl group, and p and q are integers in the range 1 <p + q <500 indicating the number of repeating units to be.

(A) Polycarbonate resin

(A1) linear polycarbonate resin

The aromatic linear polycarbonate resin used in the preparation of the resin composition of the present invention can be prepared by reacting diphenols represented by the following formula (3) with phosgene, halogen formate or carbonic acid diester.

(3)

In the formula, A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO _2- .

Specific examples of the diphenol of the general formula (3) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 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-hydroxyphenyl) -propane and the like. In addition, the diphenol compound may be used a compound such as hydroquinone, resorcinol. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Hydroxyphenyl) -cyclohexane and the like, and the most preferred and most industrially used aromatic polycarbonate is prepared from 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A.

Suitable polycarbonates used in the production of the resin composition of the present invention include those having a weight average molecular weight of 10,000 to 200,000, preferably 15,000 to 80,000.

Examples of the polycarbonate used in the production of the resin composition of the present invention include homo polycarbonates and copolycarbonates, and may also be used in the form of a blend of copolycarbonates and homo polycarbonates.

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

(A2) Branched Polycarbonate Resin

The branched polycarbonate used in the preparation of the resin composition of the present invention can be produced by adding a branching agent during polycarbonate polymerization. Branching agents are well known and may include multifunctional organic compounds containing at least three functional groups which may be hydroxyl, carboxyl, carboxylic anhydride, haloformyl and mixtures thereof.

Specific examples include trimellitic acid, trimellitic anhydride, trimellitic acid trichloride, tris-p-hydroxyphenylethane (THPE), 2,6-bis (2'-hydroxy-5-5'-methyl Benzyl) -4-methylphenol, isatin-bisphenol, tris-phenol TC (1,3,5-trias ((p-hydroxyphenyl) isopropyl) benzene)), trias-phenol PA (4 ( 4 (1,1-bis (p-hydroxyphenyl) -ethyl), 4-chloroformyl phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid.

Branching agents may be added at a level of about 0.05 to 2.0 weight percent. Branching agents and methods for preparing branched polycarbonates are described in US Pat. Nos. 3,635,895 and 4,001,184. All or most types of polycarbonate end groups are considered useful in flame retardant polycarbonate compositions.

Preferred branched polycarbonates are based on bisphenol A. Preferably the weight average molecular weight of the polycarbonate is about 5,000 to 100,000, more preferably about 10,000 to 65,000, most preferably 15,000 to 40,000.

The resin composition of the present invention includes both linear and branched polycarbonate resins. Typically 50 to 90% by weight, preferably 60 to 80% by weight linear polycarbonate is present. In addition, the branched polycarbonate includes 10 to 50% by weight, preferably 20 to 40% by weight.

Branched polycarbonates have a branching degree of about 0.05 to about 0.8%, preferably a branching degree of about 0.1 to about 0.6%, and most preferably about 0.2 to about 0.4%. The percentage of branches is determined by the number of branches per 100 repeat units. The final amount of branching in the composition is determined by the ratio of branched resin to linear resin and the level of branching agent in the branched resin.

(B) bisphenol-A derived oligomeric phosphate ester compound

The oligomeric phosphate ester compound derived from bisphenol-A used in the preparation of the resin composition of the present invention is a phosphate ester compound represented by the following formula (1) or a mixture thereof.

[Formula 1]

Wherein R ₁ is each independently C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 to 0 representing the number of repeating units It is an integer of 5, and the average value of the mixture m of the oligomeric phosphate ester compound of the said Formula (1) is 0.5 to 2.

R ₁ in Formula 1 may be a phenyl group or a naphthyl group or a phenyl group or a naphthyl group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. Etc., and a phenyl group in which a phenyl group, a naphthyl group or a methyl, ethyl, isopropyl or t-butyl group is substituted is more preferable.

The compound of formula 1 used in the preparation of the resin composition of the present invention is an oligomeric phosphate ester compound derived from bisphenol-A, and is an oligomeric bisphenol-A derived phosphate ester having an average value of m of 0.5 to 2. In the present invention, two or more phosphate ester compounds having different m values may be used in a mixed form. At the time of preparation in the polymerization process, two or more phosphate ester compounds having different m values are already mixed or used separately. It is also possible to mix and use the manufactured thing.

In the present invention, the bisphenol-A derived oligomeric phosphate ester compound (B) may be used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin (A). When the bisphenol-A derived oligomeric phosphoric acid ester compound is used in less than 5 parts by weight, sufficient flame retardancy may not be obtained, and when used in excess of 20 parts by weight, fluidity and heat resistance may be lowered. Preferably, the bisphenol-A derived oligomeric phosphate ester compound may be used in an amount of 10 to 17 parts by weight based on 100 parts by weight of the polycarbonate (A).

(C) cyclic phosphazene compound

The cyclic phosphazene compound used in the present invention is a phosphazene compound or a mixture thereof represented by the following formula (2).

[Formula 2]

In the above formula, each R ₂ is independently a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted aryl group, a C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl Substituent selected from an oxy group, an amino group, or a hydroxyl group is shown, n is an integer of 0-10.

The alkoxy group or the aryloxy group of the above formula may be substituted with an alkyl group, an aryl group, an amino group, a hydroxyl group, or the like. Preferred R ₂ includes an alkoxy group, an aryloxy group, and more preferably a phenoxy group. .

In addition, in the present invention, as a cyclic phosphazene compound represented by the following formula (4), a mixture of oligomeric compounds of cyclic phosphazene formed by linking with a linking group having a R ₃ group may be mixed.

[Formula 4]

Wherein R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ aralkyl group, C ₁ -C ₂₀ alkoxy A substituent selected from a group, a C ₆ -C ₂₀ aryloxy group, an amino group or a hydroxy group, x and y are each an integer from 0 or 1 to 10 and R ₃ is C ₆ -C ₃₀ dioxyaryl or C _1- C ₂₀ alkyl substituted C ₆ -C ₃₀ dioxyaryl group derivative, the average z value in the mixture of the oligomeric compound of the cyclic phosphazene represented by the formula (4) is 0.3≤z≤3 as the number average degree of polymerization.

The method for preparing the cyclic phosphazene oligomeric compound is not particularly limited and may be prepared by the following method.

The alkyl alcohol (or aryl alcohol) is first reacted with an alkali metal hydroxide such as sodium hydroxide or lithium hydroxide to obtain an alkali metal alkylate (or alkali metal arylate). In the same manner, an alkali metal diphenolate can be obtained by reacting diols having an R ₃ group with an alkali metal hydroxide. The cyclic dichlorophosphazene compound is reacted with a mixture of an alkali metal alkylate (or alkali metal arylate) and an alkali metal diphenolate in an appropriate ratio, and then again with alkali metal alkylate (or alkali metal arylate). The reaction can yield a cyclic phosphazene oligomeric compound.

In the present invention, the phosphazene compound is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, most preferably 1 to 5 parts by weight, based on 100 parts by weight of the base resin consisting of (A).

(D) phenyl group substituted siloxane copolymer

The phenyl group substituted siloxane copolymer (D) which is a component used for manufacture of the resin composition of this invention can be represented by following formula (5).

[Chemical Formula 5]

Wherein R ₅ is a methyl or phenyl group, R ₆ is a methyl, phenyl, hydroxy, methoxy, phenoxy or vinyl group, and p and q are integers in the range 1 <p + q <500, indicating the number of repeating units to be.

The phenyl-substituted siloxane copolymer may be used in a form in which copolymers having different p and q values are mixed, and in this case, the average p: q ratio is preferably in the range of 9: 1 to 3: 7.

As the dynamic viscosity of the phenyl group-substituted siloxane copolymer used in the preparation of the resin composition of the present invention, one having 1 to 1000 centistokes (cSt) may be used at 25 ° C., and it is preferable to use 4 to 500 centistokes (cSt). . When the dynamic viscosity is outside the range of 1 to 1000 centistokes cSt, transparency may be degraded.

Examples of the phenyl group substituted siloxane copolymer include poly (methylphenyl) siloxane in which R ₅ and R ₆ are both methyl groups; Poly (diphenyl) siloxane in which both R ₅ and R ₆ are substituted with a phenyl group; There is a copolymer of dimethylsiloxane in which both R ₅ and R ₆ are substituted with methyl groups and diphenylsiloxane in which both R ₅ and R ₆ are substituted with phenyl groups. Of these, poly (methylphenyl) siloxane polymers are preferred.

It is more preferable that the number of repeating units of the phenyl group substituted siloxane used for producing the resin composition of the present invention accounts for 50% or more, and 80% or more in the total unit structure.

In the present invention, the phenyl group-substituted siloxane copolymer is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base resin comprising (A). In the case of using less than 0.1 part by weight, the effect of improving fluidity, rigidity and flame retardancy is not remarkable, and in the case of using more than 10 parts by weight, transparency is lowered, which is not preferable.

The polycarbonate resin composition of the present invention may further include an additive according to each use. The additives may include antioxidants, impact modifiers, lubricants, mold release agents, nucleating agents, antistatic agents, reinforcing agents, inorganic additives, UV stabilizers, fluorescent brighteners, pigments or dyes, and the like, but are not limited thereto. These can be used individually or in mixture of 2 or more types. The additive may be used in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the base resin.

The polycarbonate resin composition according to the present invention can be produced by a known method. For example, the components of the present invention and other additives may be simultaneously mixed and then melt-extruded in an extruder and produced in the form of pellets.

The polycarbonate resin composition according to the present invention has high flame retardancy and excellent transparency, and can be used for molding various products requiring high appearance. For example, housings and office automation equipment for electrical and electronic products such as TVs, audio, mobile phones, digital cameras, navigation, washing machines computers, monitors, MP3s, video players, CD players, etc., which require excellent transparency, flame retardancy and moldability. Large injection moldings can be widely used in the manufacture.

There is no particular limitation on the method of molding the plastic molded article using the thermoplastic resin composition according to the present invention. For example, an extrusion, injection or casting molding method may be applied. The molding can be easily carried out by those skilled in the art.

The present invention can be better understood by the following examples, and the following examples are only specific examples of the present invention and are not intended to limit or limit the protection scope of the present invention.

Example

example 　 The specification of each component used by the Example and comparative example of this invention is as follows.

(A) Polycarbonate resin

(A1) linear polycarbonate resin

PANLITE L-1250WP of Teijin, Japan was used as bisphenol-A type polycarbonate with a weight average molecular weight of 25,000 g / mol.

(A2) Branched Polycarbonate Resin

As bisphenol-A polycarbonate having a weight average molecular weight of 35,000 g / mol, US PK2870 was used.

(B) bisphenol-A derived oligomeric phosphate ester compound

In Formula 1, the value of m is 0, 3.4 wt%, the value of m is 1, 85.4 wt%, and the value of m is 11.2 wt%, and the average m value is 1.08, R ₁ CR-741 from Daihachi, Japan, which is a mixture of the bisphenol-A derived oligomeric phosphoric acid ester which is this phenyl group, was used.

(C) cyclic phosphazene compound

Rabitle FP-110 from Fushimi Pharmaceutical of Japan was used.

(D) phenyl group substituted siloxane copolymer

TSF-433 polymethylphenylsiloxane oil from GE-Toshiba Silicone Co., Ltd. was used.

Examples 1-3-3 and Comparative Examples 1-7

Each component, antioxidant, and heat stabilizer were added, mixed in a conventional mixer, extruded using a twin screw extruder having L / D = 35 and Φ = 45 mm, and then the extrudate was manufactured in pellet form, followed by injection temperature. Specimens for physical property measurement and flame retardancy evaluation at 260 ~ 280 ℃ were prepared using a 10 oz injection machine. These specimens were measured for 48 hours at 23 ° C. and 50% relative humidity, and then measured for physical properties according to ASTM standards.

How to measure property

Yellow Index: 2.5t colorchip specimen using ASTM D1925 Minolta 3600D CIE Lab. It measured using the color difference meter.

(2) Transparency: Measured by a color computer measuring instrument manufactured by SUGAINSTRUMENT, Japan, and the results are expressed as total light transmittance and HAZE.

Total light transmittance (%) = (sample transmitted light) / specimen irradiation light x 100

HAZE (%) = (dispersed transmitted light) / (total light transmittance) x 100

(3) Flame retardancy: evaluated by 2.1 mm thick specimens in accordance with UL-94.

(4) Melt Flow Index: According to ASTM D1238, the load was evaluated at 250 ° C. with a 10 kgf load.

(5) Total burn time: The total burn time was measured in accordance with UL 94 flame retardance for 2.1 mm thick specimens.

As shown in Table 1, Examples 1 to 2 have a high melt flow index while having a high flame retardancy and excellent transparency, it can be seen that the formability is good. In contrast, in the case where only the linear polycarbonate was used (Comparative Example 4), and the cyclic phosphazene compound (C) and the phenyl-substituted siloxane copolymer (D) were not applied (Comparative Examples 1 and 3), the flame retardancy was V2. Was lowered.

In addition, when the phenyl-substituted siloxane copolymer (D) was used in a composition outside the scope of the present invention (Comparative Example 2), it was confirmed that yellowness, transparency and flame retardance were lowered.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications are considered to be included within the scope of the present invention.

Claims (12)

(A) 100 parts by weight of a basic resin consisting of 50 to 90% by weight of a linear polycarbonate resin (A1) and 10 to 50% by weight of a branched polycarbonate resin; (B) 5 to 20 parts by weight of an oligomeric phosphate ester compound derived from bisphenol-A represented by the following Chemical Formula 1 or a mixture thereof; (C) 0.1 to 10 mixture of a cyclic phosphazene compound represented by the following formula (2) or a cyclic phosphazene compound represented by the following formula (4) connected by a linking group having a R ₃ group Parts by weight; And (D) 0.1 to 10 parts by weight of a phenyl group substituted siloxane copolymer represented by Formula 5 below; A polycarbonate resin composition having excellent transparency and flame retardancy, comprising: [Formula 1]

Wherein each R ₁ is independently C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl or C ₁ -C ₁₀ alkyl substituted C ₆ -C ₂₀ aryl group, m is 0 representing the number of repeating units An integer of 5 to 5, and the average value of the mixture m of the oligomeric phosphate ester compound of Formula 1 is 0.5 to 2) [Formula 2]

Wherein each R ₂ independently represents a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkoxy group , A C ₆ -C ₂₀ aryloxy group, an amino group or a substituent selected from a hydroxy group, n is an integer from 0 to 10) [Formula 4]

Wherein R ₄ is a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkyl substituted C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ aralkyl group, C ₁ -C ₂₀ A substituent selected from an alkoxy group, a C ₆ -C ₂₀ aryloxy group, an amino group or a hydroxy group, x and y are each an integer from 0 or 1 to 10, and R ₃ is C ₆ -C ₃₀ dioxyaryl or C ₁ -C ₂₀ alkyl substituted C ₆ -C ₃₀ dioxyaryl group derivative, the average z value in the mixture of the oligomeric compound of the cyclic phosphazene represented by the formula (4) is 0.3≤z≤3 as the number average degree of polymerization. ) [Chemical Formula 5]

Wherein R ₅ is a methyl or phenyl group, R ₆ is a methyl, phenyl, hydroxy, methoxy, phenoxy, vinyl group, and p and q are in the range of 1 <p + q <500 indicating the number of repeating units. Integer). The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein the degree of branching of the (A2) -branched polycarbonate resin is 0.05 to 0.8%. The phenyl group according to claim 1, wherein R ₁ in Formula 1 is a phenyl group or a naphthyl group, respectively, or a phenyl group substituted with methyl, ethyl, propyl, isopropyl butyl, sec-butyl, t-butyl, isobutyl, isoamyl or t-amyl group Or a naphthyl group, polycarbonate resin composition excellent in transparency and flame retardancy. The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein R ₂ of the cyclic phosphazene compound represented by Formula 2 is a phenoxy group. delete The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein the dynamic viscosity of the (D) phenyl group-substituted siloxane copolymer is 1 to 1000 centistokes (cSt) at 25 ° C. The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein the (D) phenyl group substituted siloxane copolymer is poly (methylphenyl) siloxane in which R ₅ and R ₆ are both methyl groups. The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein the (D) phenyl group substituted siloxane copolymer is poly (diphenyl) siloxane in which both R ₅ and R ₆ are substituted with a phenyl group. The phenyl group-substituted siloxane copolymer according to claim 1, wherein the phenyl-substituted siloxane copolymer (D) is a copolymer of dimethylsiloxane in which both R ₅ and R ₆ are substituted with methyl groups, and diphenyl siloxane in which both R ₅ and R ₆ are substituted with phenyl groups. Polycarbonate resin composition excellent in transparency and flame retardance to be. The polycarbonate resin composition according to claim 1, wherein the ratio of the average p and q values of the (D) phenyl group-substituted siloxane copolymer is in the range of 9: 1 to 3: 7. The resin composition of claim 1, wherein the resin composition further comprises at least one additive selected from the group consisting of antioxidants, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, dyes, pigments, and mixtures thereof. Polycarbonate resin composition excellent in transparency and flame retardancy. The molded article manufactured from the polycarbonate resin composition in any one of Claims 1-4 and 6-11.