KR102231625B1 - Polycarbonate resin composition and molded articles thereof - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molded article comprising the same. More specifically, it relates to a polycarbonate resin composition exhibiting good processability, excellent flame retardancy and weather resistance, and a molded article manufactured therefrom.

Description

Polycarbonate resin composition and article containing the same TECHNICAL FIELD [POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLES THEREOF}

The present invention relates to a polycarbonate resin composition and a molded article thereof. More specifically, it relates to a polycarbonate resin composition having good processability and excellent flame retardancy and weather resistance, and a molded article manufactured therefrom.

Polycarbonate resins are manufactured by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have excellent impact strength, numerical stability, heat resistance and transparency, and exterior materials of electrical and electronic products, automobile parts, construction materials, and optical parts. And so on.

In particular, recently, various electrical and electronic product materials have been made lighter and thinner, and a higher level of flame retardancy is required for polycarbonate resins to be applied thereto.

In particular, in order to increase the flame retardancy of polycarbonate, studies using Br-based or Cl-based flame retardants have been conducted in the past, but the use of the flame retardant using the flame retardant has been strengthened day by day due to toxicity and environmental problems caused by the generation of harmful gases. In particular, export products to Europe are heavily regulated, and it is expected that overall regulations will be applied to interior and exterior products of small items in the future.

Accordingly, research on a material that can replace the flame retardant is in progress, and an example may be a sulfonic acid-based metal salt. Examples of such sulfonic acid-based metal salts include potassium perfluorobutanesulfonate (KFBS) and potassium diphenyl sulfonate (KSS). U.S. Patent No. 3,775,367 describes that by using such a metal salt in a polycarbonate resin, it is possible to maintain excellent flame retardancy, heat resistance, and impact strength of UL-94 V0 class. From U.S. Patent No. 3,775,367, even when a molded article having a thin thickness of about 4 mm is manufactured by using such a metal salt in a small amount of 0.5% by weight or more based on the total weight of the composition, it is possible to achieve UL-94 V0 level of flame retardancy. Can be seen. However, in the case of manufacturing a molded article having a thinner thickness, the content of the metal salt must be increased in order to obtain the desired flame retardancy, but there is a problem in that the excessive metal salt causes decomposition of the polycarbonate resin, resulting in lower flame retardancy.

A technique of using a silicone compound as another method for obtaining flame retardancy and heat resistance by using a flame retardant other than a Br-based or Cl-based flame retardant has been reported (WO 99/028387). However, even in this case, it is difficult to produce excellent flame retardancy at a thickness of about 2 mm, and when the content of the flame retardant is increased in order to improve flame retardancy, there is a problem in that heat resistance is deteriorated.

In addition, a low molecular weight decomposition product during combustion accelerates the decomposition of the resin, causing a sharp drop in the viscosity of the resin, resulting in a dripping phenomenon in which the flame falls down, and a dripping inhibitor is added to prevent this. However, it is not easy for the conventional anti-drip agent to lower the transparency of the resin composition to maintain the transparency while satisfying the anti-drip properties.

U.S. Pat. No. 3,775,367 WO 99/028387

Accordingly, the present invention is to provide a polycarbonate resin composition exhibiting excellent processability, flame retardancy and weather resistance.

In addition, the present invention is to provide a molded article comprising the polycarbonate resin composition.

In order to solve the above problems, the present invention provides a polycarbonate resin composition comprising the following:

(a) a linear polycarbonate resin comprising a first repeating unit represented by the following formula (1);

(b) a branched polycarbonate resin comprising a first repeating unit represented by the following formula (1);

Based on 100 parts by weight of the linear polycarbonate resin and the branched polycarbonate resin,

(c) 0.04 to 0.6 parts by weight of an organic sulfonate-based metal salt;

(d) 0.05 to 1.0 parts by weight of a dioxybenzoin-based epoxy compound;

(e) 1.5 to 5.0 parts by weight of phenylmethyl silicone oil having a kinematic viscosity at 25° C. of 5 to 60 mm 2 /second; And

(f) 0.1 to 0.5 parts by weight of an ultraviolet absorber:

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

The present invention also provides a molded article comprising the polycarbonate resin composition.

The polycarbonate resin composition and the molded article thereof according to the present invention may exhibit excellent processability, flame retardancy, and weather resistance.

Accordingly, the polycarbonate resin composition and the molded article thereof of the present invention are suitable for blow molding and injection molding processes, and can be suitably used as materials for electric and electronic parts, lighting equipment parts, and the like.

The present invention will be described in detail below and exemplify specific embodiments, as various modifications can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a polycarbonate resin composition and a molded article thereof according to specific embodiments of the present invention will be described in more detail.

Prior to that, the terminology used herein is for reference only to specific embodiments and is not intended to limit the invention. In addition, the singular forms used herein also include plural forms unless the phrases clearly represent the opposite meaning.

Polycarbonate resin composition

Polycarbonate resin composition according to an embodiment of the invention,

(a) a linear polycarbonate resin comprising a first repeating unit represented by the following formula (1);

(b) a branched polycarbonate resin comprising a first repeating unit represented by the following formula (1);

Based on 100 parts by weight of the linear polycarbonate resin and the branched polycarbonate resin,

(c) 0.04 to 0.6 parts by weight of an organic sulfonate-based metal salt;

(d) 0.05 to 1.0 parts by weight of a dioxybenzoin-based epoxy compound;

(e) 1.5 to 5.0 parts by weight of phenylmethyl silicone oil having a kinematic viscosity at 25° C. of 5 to 60 mm 2 /second; And

(f) 0.1 to 0.5 parts by weight of an ultraviolet absorber is included:

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

The polycarbonate resin composition according to an embodiment of the present invention includes the linear polycarbonate resin and the branched polycarbonate resin at the same time. The branched polycarbonate resin includes a first repeating unit as a basic main chain, and has a structure in which a plurality of the first repeating units are connected to a branched second repeating unit according to a branching agent included during polymerization. It has a structure with reinforced entanglement. Accordingly, it may have excellent melt strength compared to the case where the linear polycarbonate resin is used alone, and thus, it is possible to exhibit more excellent workability during blow molding.

In addition, the polycarbonate resin composition according to the present invention includes an organic sulfonate-based metal salt, a dioxybenzoin-based epoxy compound, and a phenylmethylsilicone oil as a non-halogen-based flame retardant, together with the linear polycarbonate resin and the branched polycarbonate resin. , The polycarbonate resin composition may exhibit UL-94 VO grade flame retardancy and at the same time exhibit excellent weather resistance.

Therefore, the polycarbonate resin composition of the present invention containing the linear polycarbonate resin and the branched polycarbonate resin in a predetermined weight ratio and simultaneously containing three non-halogen-based flame retardants has excellent processability and flame retardancy due to their interaction. And weather resistance.

Accordingly, the polycarbonate resin composition according to an embodiment of the present invention is not limited thereto, but may be particularly usefully used as a material for electric and electronic parts, lighting equipment parts, and the like that require the above characteristics.

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

(a) linear polycarbonate resin

The'linear polycarbonate resin' according to the present invention is a resin containing a polycarbonate-based first repeating unit represented by Chemical Formula 1, and is distinguished from a branched polycarbonate resin in that it does not contain a branched repeating unit to be described later. do.

Specifically, the repeating unit represented by Formula 1 is formed by reacting an aromatic diol compound and a carbonate precursor.

In Formula 1, preferably, R ₁ to R ₄ are each independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is a straight or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

The repeating unit represented by Formula 1 may be derived from an aromatic diol compound represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, R ₁ to R ₄ and Z are as defined in Formula 1.

As a non-limiting example, the repeating unit represented by Formula 1 is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyl) Phenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4- Hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4 -Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and at least one aromatic diol compound selected from the group consisting of a,ω-bis[3-(ο-hydroxyphenyl)propyl]polydimethylsiloxane It can be derived from

The meaning of "derived from an aromatic diol compound" means that the hydroxy group of the aromatic diol compound represented by Formula 1-1 reacts with a carbonate precursor to form a repeating unit represented by Formula 1.

As a non-limiting example, when bisphenol A, which is an aromatic diol compound, and triphosgene, which is a carbonate precursor, are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-2:

[Formula 1-2]

.

.

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, At least one selected from the group consisting of bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used. Preferably, triphosgene or phosgene may be used.

The linear polycarbonate resin may have a weight average molecular weight (Mw) of 1,000 to 100,000 g/mol, preferably 10,000 to 60,000 g/mol, and more preferably 15,000 to 50,000 g/mol. More preferably, the weight average molecular weight (Mw) is 17,000 g/mol or more, 18,000 g/mol or more, or 20,000 g/mol or more. In addition, the weight average molecular weight is 43,000 g/mol or less, 42,000 g/mol or less, or 41,000 g/mol or less. At this time, the weight average molecular weight is a value converted to a standard polycarbonate (PC Standard) measured using a gel permeation chromatograph (GPC).

In addition, the linear polycarbonate resin is melted at 2 g/10 minutes to 50 g/10 minutes, or 3 g/10 minutes to 40 g/10 minutes according to ASTM D1238 (300° C. and 1.2 kg load; measured for 10 minutes) Having an index (MI) may be preferable in terms of stable expression of physical properties of the entire resin composition.

In addition, the linear polycarbonate resin may be included in 50 to 80% by weight, or 50 to 70% by weight, or 55 to 65% by weight, based on the total weight of the linear polycarbonate resin and the branched polycarbonate resin.

If the content of the linear polycarbonate resin is too small, there may be a problem in that processability is deteriorated. Conversely, if the content of the linear polycarbonate resin is too large, there may be a problem in preventing dripping.

Meanwhile, the above-described linear polycarbonate resin can be directly prepared by using the aromatic diol compound and carbonate precursor represented by Formula 1-1 as starting materials according to a known polymerization method of a general aromatic polycarbonate resin.

As the polymerization method, an interfacial polymerization method may be used as an example, and in this case, a polymerization reaction is possible at normal pressure and a low temperature, and molecular weight control is easy. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, pre-polymerization followed by introducing a coupling agent and then polymerizing again, and in this case, a high molecular weight polycarbonate may be obtained.

The materials used for the interfacial polymerization are not particularly limited as long as they can be used for polymerization of polycarbonate, and the amount of the material used for the interfacial polymerization may be adjusted as necessary.

As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine may be used.

The organic solvent is not particularly limited as long as it is a solvent commonly used for polymerization of polycarbonate, and halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used as an example.

In addition, the interfacial polymerization is a reaction such as triethylamine, tetra-n-butylammonium bromide, and tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds, etc. Additional accelerators can be used.

The reaction temperature of the interfacial polymerization is preferably 0 to 40°C, and the reaction time is preferably 10 minutes to 5 hours. In addition, during the interfacial polymerization reaction, the pH is preferably maintained at 9 or more or 11 or more.

In addition, the interfacial polymerization may be performed by further including a molecular weight modifier. The molecular weight modifier may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization.

Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol, and triacontylphenol, preferably p-tert-butylphenol, and in this case, the molecular weight control effect is large.

The molecular weight modifier is, for example, 0.01 parts by weight or more, 0,1 parts by weight or more, or 1 part by weight or more, and includes 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound. And a desired molecular weight can be obtained within this range.

(b) branched polycarbonate resin

The'branched polycarbonate resin' according to the present invention refers to a branched polycarbonate resin including a polycarbonate-based first repeating unit represented by Formula 1 above. More specifically, a copolycarbonate resin further comprising a trivalent or tetravalent branched second repeating unit connecting a plurality of the first repeating units to each other in addition to the polycarbonate-based first repeating unit represented by Formula 1 it means.

The description of the first repeating unit is as described above.

In addition, the trivalent or tetravalent second repeating unit is a repeating unit formed by graft polymerization in a branched manner with respect to the main chain by a branching agent added during polymerization of the aromatic diol compound represented by Formula 1-1 and the carbonate precursor. it means.

Specifically, the trivalent or tetravalent second repeating unit is a branching agent which is a phenol derivative compound having 3 or 4 hydroxyl groups, for example, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,3,5-tris-(2-hydroxyethyl) cyanuric acid, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptane-2,2,2-bis [4,4'-(dihydroxyphenyl)cyclohexyl]propane, 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,4-bis-(4', 4 ''-Dihydroxytriphenylmethyl)-benzene, 2',3',4'-trihydroxyacetophenone, 2,3,4-trihydroxybenzoic acid, 2,3,4,-trihydroxybenzo Phenone, 2,4,4'-trihydroxybenzophenone, 2',4',6'-trihydroxy-3-(4-hydroxyphenyl)propiophenone, pentahydroxyflavone, 3,4, 5-trihydroxyphenylethylamine, 3,4-trihydroxyphenylethyl alcohol, 2,4,5-trihydroxypyrimidine, tetrahydroxy-1,4-quinone hydrate, 2,2',4, It may be derived from one or more branching agents selected from the group consisting of 4'-tetrahydroxybenzophenone and 1,2,5,8-tetrahydroxyanthraquinone.

The meaning of'derived from a branching agent' means that 3 or 4 hydroxy groups of the branching agent are reacted with a carbonate precursor and are graft-polymerized with a plurality of repeating units represented by Formula 1 to be trivalent or 4 Is meant to form a second repeating unit.

This second repeating unit may be represented by the following formula (2):

[Formula 2]

In Formula 2, R ₁ to R ₄ and Z are as defined in Formula 1, and Q is a trivalent or tetravalent phenol derivative compound derived from a branching agent.

As a non-limiting example, when polymerized using bisphenol A as an aromatic diol compound, triphosgene as a carbonate precursor, and 1,1,1,-tris (4'-hydroxyphenyl) ethane (THPE) as the branching agent, the above formula The repeating unit of 2 may be represented by the following formula 2-1:

[Formula 2-1]

The branched polycarbonate resin may include 98 to 99.999 mol% of the first repeating unit and 0.001 to 2 mol% of the second repeating unit. Alternatively, 98 to 99.99 mol% of the first repeating unit and 0.01 to 2 mol% of the second repeating unit may be included. Alternatively, it may include 98 to 99.9 mol% of the first repeating unit and 0.1 to 2 mol% of the second repeating unit. When the content of the second repeating unit is excessively decreased, it may be difficult to sufficiently improve the elongational viscosity properties due to the branched structure. On the other hand, when the content of the second repeating unit is too high, a large amount of gel may be formed and physical properties may deteriorate.

The branched polycarbonate resin may have a weight average molecular weight of 10,000 to 100,000 g/mol, preferably 20,000 to 50,000 g/mol. More preferably, the weight average molecular weight (Mw) is 10,000 g/mol or more, 21,000 g/mol or more, 22,000 g/mol or more, 23,000 g/mol or more, 24,000 g/mol or more, 25,000 g/mol or more, 26,000 g/mol or more, 27,000 g/mol or more, or 28,000 g/mol or more. In addition, the weight average molecular weight is 100,000 g/mol or less, 50,000 g/mol or less, 45,000 g/mol or less, 42,000 g/mol or less, or 40,000 g/mol or less. At this time, the weight average molecular weight is a value converted to a standard polycarbonate (PC Standard) measured using a gel permeation chromatograph (GPC).

In addition, the branched polycarbonate resin is 1 g/10 minutes to 50 g/10 minutes, or 1.5 g/10 minutes to 40 g/10 minutes according to ASTM D1238 (300° C. and 1.2 kg load; measured for 10 minutes) Having a melt index (MI) may be desirable in terms of stable expression of physical properties of the entire resin composition.

In addition, the branched polycarbonate resin may be included in an amount of 20 to 50% by weight, or 30 to 50% by weight, or 35 to 45% by weight, based on the total weight of the linear polycarbonate resin and the branched polycarbonate resin.

If the content of the branched polycarbonate resin is too small, there may be a problem in the dripping prevention effect, and on the contrary, if the content of the branched polycarbonate resin is too large, there may be a problem in that processability is deteriorated.

On the other hand, the above-described branched polycarbonate resin can be directly prepared according to a known polymerization method of a general aromatic polycarbonate resin using the aromatic diol compound represented by Formula 1-1, a carbonate precursor, and a branching agent as starting materials. . As the polymerization method, an interfacial polymerization method may be used as an example, and the description of the interfacial polymerization is referred to above.

(c) organic Sulfonate Metal salt

On the other hand, polycarbonate is relatively superior in mechanical properties, electrical properties, and weather resistance compared to other types of resins, but its flame retardancy is poor, and thus flame retardancy is required to be improved in order to be applied to various fields requiring flame retardancy. Accordingly, in the present invention, in addition to the above-described polycarbonate resin, an organic sulfonate-based metal salt, a dioxybenzoin-based epoxy compound and phenylmethyl silicone oil to be described later may be further included to improve flame retardancy.

Here, the'organic sulfonate-based metal salt' refers to a salt compound of an organic sulfonate ion and a metal ion, and contributes to improvement of the flame retardancy of the polycarbonate resin composition by increasing the char formation rate of the polycarbonate.

The organic sulfonate-based metal salt may be an organic sulfonate alkali metal salt or an organic sulfonate alkaline earth metal salt.

For example, the organic sulfonate-based metal salt is sodium trifluoromethyl sulfonate, sodium perfluoroethyl sulfonate, sodium perfluorobutyl sulfonate, sodium perfluoroheptyl sulfonate, sodium perfluorooctyl sulfonate. Sodium trichlorobenzene sulfonate, sodium polystyrene sulfonate, potassium perfluorobutyl sulfonate, potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, potassium diphenylsulfone sulfonate, calcium perfluoromethane Sulfonate, rubidium perfluorobutyl sulfonate, rubidium perfluorohexyl sulfonate, cesium trifluoromethyl sulfonate, cesium perfluoroethyl sulfonate, cesium perfluorohexyl sulfonate and cesium perfluorooctyl sulfonate It may be one or more compounds selected from the group consisting of.

Preferably, as an organic sulfonate-based metal salt, potassium perfluorobutyl sulfonate, potassium diphenyl sulfone sulfonate, or a mixture thereof may be used.

In addition, the organic sulfonate-based metal salt is 0.04 parts by weight or more, or 0.08 parts by weight or more, and 0.6 parts by weight or less, or 0.3 parts by weight, based on 100 parts by weight of the sum of the linear polycarbonate resin and the branched polycarbonate resin. It may be included below.

If the content of the organic sulfonate-based metal salt is too small, there may be a problem of deteriorating flame retardancy, and on the contrary, if the content of the organic sulfonate-based metal salt is too large, there may be a problem of lowering the transparency. Therefore, from this point of view, the organic sulfonate-based metal salt is preferably included in an amount within the above-described range.

On the other hand, the organic sulfonate-based metal salt is excellent in flame retardancy, but there is a disadvantage in that it may cause bubbles during injection molding of a composition containing the same. Accordingly, there have been attempts to use sodium dodecylbenzenesulfonate as a flame retardant to replace organic sulfonate-based metal salts. However, sodium dodecylbenzenesulfonate has a disadvantage of lowering the transparency and mechanical strength of the polycarbonate resin.

Accordingly, the polycarbonate resin composition of the present invention does not contain sodium dodecylbenzenesulfonate, and by using a dioxybenzoin-based epoxy compound and phenylmethylsilicon oil described later in addition to the organic sulfonate-based metal salt, while maintaining flame retardancy. It is possible to prevent the generation of bubbles due to the organic sulfonate-based metal salt, thereby achieving excellent flame retardancy and workability at the same time.

(d) Deoxybenzoin Epoxy compound

Meanwhile, the polycarbonate resin composition according to the present invention further includes a dioxybenzoin-based epoxy compound to improve flame retardancy.

Here, the'deoxybenzoin-based epoxy compound' refers to a compound substituted with an epoxy group while having a deoxybenzoin parental structure, and contributes to the improvement of flame retardancy of the polycarbonate resin composition.

Preferably, the dioxybenzoin-based epoxy compound is represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

L ₁ and L ₂ are each independently C _1-10 alkylene,

R ₅ and R ₆ are each independently hydrogen, C _1-20 alkyl, or C _6-20 aryl.

More preferably, in Formula 3, L ₁ and L ₂ are methylene.

For example, a compound represented by the following Formula 3-1 may be used as the dioxybenzoin-based epoxy compound:

[Chemical Formula 3-1]

In addition, the dioxybenzoin-based epoxy compound is 0.05 parts by weight or more, or 0.08 parts by weight or more, 1.0 parts by weight or less, or 0.9 parts by weight, based on 100 parts by weight of the sum of the linear polycarbonate resin and the branched polycarbonate resin. It may be included in less than part.

If the content of the dioxybenzoin-based epoxy compound is too small, there may be a problem that dropping occurs when evaluating the flame retardancy, and on the contrary, if the content of the dioxybenzoin-based epoxy compound is too large, there may be a problem of lowering the transparency and lowering the impact strength. I can.

(e) Phenylmethyl silicone oil

Meanwhile, the polycarbonate resin composition according to the present invention further includes phenylmethyl silicone oil to improve flame retardancy.

Here,'phenylmethyl silicone oil' refers to a silicone polymer containing a methyl group and a phenyl group as a side chain or terminal substituent of a siloxane repeating unit, and preferably contains a methyl group as a terminal substituent and a phenyl group as a side chain substituent. It means a silicone polymer. Such phenylmethyl silicone oil contributes to the improvement of heat resistance and flame retardancy of the polycarbonate resin composition due to the repeated siloxane main chain, and may exhibit an effect of improving flame retardancy by essentially containing a phenyl group.

The phenylmethyl silicone oil may have a kinematic viscosity at 25° C. of 5 to 60 mm 2 /second. Specifically, the phenylmethyl silicone oil has a kinematic viscosity (mm 2 /sec) at 25°C of 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more. In addition, the kinematic viscosity (mm 2 /sec) at 25°C may be 50 or less, 40 or less, 30 or less, 25 or less, or 20 or less. When the kinematic viscosity of the phenylmethyl silicone oil is less than 5 mm 2 /sec, it is highly volatile and thus bubbles may be generated. Conversely, when it exceeds 60 mm 2 /sec, transparency may be deteriorated. Therefore, from this viewpoint, it is preferable to use a phenylmethyl silicone oil that satisfies the above-described kinematic viscosity range.

Preferably, the phenylmethyl silicone oil is a silicone polymer containing phenyl trimethicone repeating units. Specifically, the phenylmethyl silicone oil may be represented by the following Formula 4:

[Formula 4]

In Chemical Formula 4,

R ₇ and R ₈ are each independently C _1-10 alkyl, C _1-10 alkenyl, or C _6-10 aryl,

R ₉ is phenyl,

n is an integer from 0 to 10,

m is an integer from 1 to 10

More preferably, in Formula 4, at least one of _{R 7} and R _{8 may be phenyl.}

For example, as the phenylmethyl silicone oil, a compound represented by the following formula 4-1 in which all _{of R 7} to R _{9 in Formula 4 are phenyl may be used:}

[Formula 4-1]

In Formula 4-1, n and m are as defined in Formula 4.

In addition, the phenylmethyl silicone oil is 1.5 parts by weight or more, or 1.8 parts by weight or more, 5.0 parts by weight or less, or 4.5 parts by weight or less, based on 100 parts by weight of the sum of the linear polycarbonate resin and the branched polycarbonate resin. Can be included as.

If the content of the phenylmethyl silicone oil is too small, there may be a problem of lowering the flame retardancy. Conversely, when the content of the phenylmethyl silicone oil is too high, there may be a problem of lowering the transparency. Therefore, from this point of view, the phenylmethyl silicone oil is preferably included in an amount within the above range.

(f) ultraviolet absorber

On the other hand, the polycarbonate resin composition according to the present invention further includes an own line absorber in order to effectively block ultraviolet rays introduced from the outside.

As the ultraviolet absorber that can be used in the present invention, under the condition that the thickness of the specimen molded with the polycarbonate resin composition according to the present invention is 3 mm, the light transmittance at a wavelength of 380 nm is 20% or less, preferably 10% or less. Any UV absorber that can be used can be used without special restrictions.

Preferably, as the ultraviolet absorber, at least one selected from the group consisting of a benzotriazole compound, a benzophenone compound, an oxalanilide compound, a benzoic acid ester compound, and a triazine compound may be used.

For example, as the ultraviolet absorber, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2- (3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2- Hydroxy-5-(1,1,3,3,tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-benzo Triazole, 2-(3'-tert-butyl-2'-hydroxyphenyl-5'-methylphenyl)-5-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2 '-Hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenylphenyl)-5-benzotriazole or 2-(3',5'-di-tert-butyl-2 Benzotriazole compounds such as 2-(2'-hydroxyphenyl)-benzotriazole-based compounds such as'-hydroxyphenyl)benzotriazole; 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy- Benzophenone compounds such as 2-hydroxy benzophenone-based compounds having a 4,4'-dimethoxy functional group; 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butyl-benzoyl) resorcinol, benzoyl resorcinol, 2,4 -Di-tert-butylphenyl-3,5'-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-4hydroxybenzoate, octadecyl 3, Substituted benzoic acid such as 5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate Benzoic acid ester compounds such as compounds having an ester structure; Alternatively, a triazine compound having a 2,4,6-triphenyl-1,3,5-triazine skeleton may be used, but the present invention is not limited thereto.

In addition, the ultraviolet absorber is included in an amount of 0.1 parts by weight or more, or 0.2 parts by weight or more, 0.5 parts by weight or less, or 0.3 parts by weight or less, based on 100 parts by weight of the sum of the linear polycarbonate resin and the branched polycarbonate resin. I can.

If the amount of the ultraviolet absorber is too small, there may be a problem that weather resistance is deteriorated. Conversely, if the amount of the ultraviolet absorber is too large, there may be a problem that transparency and flame retardancy are lowered.

(g) additive

On the other hand, the polycarbonate resin composition according to the present invention includes the above-described (a) linear polycarbonate resin; (b) a branched polycarbonate resin; (c) organic sulfonate-based metal salts; (d) a dioxybenzoin-based epoxy compound; (e) phenylmethyl silicone oil; And (f) an impact modifier, if necessary, in addition to the ultraviolet absorber; Flow modifiers; Drip inhibitors such as fluorine-based polymers such as polytetrafluoroethylene (PTFE); Flame retardants such as phosphorus flame retardants; Surfactants; Nucleating agent; Coupling agents; Filler; Plasticizer; Lubricant; Antibacterial agents; Mold release agent; Heat stabilizer; Antioxidants; UV stabilizer; Compatibilizer; coloring agent; Antistatic agents; Pigment; dyes; It may further contain additives such as flame retardants.

The content of these additives may vary depending on the physical properties to be imparted to the composition. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, respectively, based on 100 parts by weight of the total of the linear polycarbonate resin and the branched polycarbonate resin.

However, in order to prevent the heat resistance, impact strength, and chemical resistance of the polycarbonate resin composition from being deteriorated by the application of the additive, the total content of the additive is the linear polycarbonate resin and the branched polycarbonate resin. It is appropriate that it is 20 parts by weight or less, or 15 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight in total.

The polycarbonate resin composition of the present invention as described above has a flame retardancy rating of V-O measured for a specimen having a thickness of 1.5 mm based on UL 94 vertical protocol evaluation conditions, and may exhibit excellent flame retardancy.

In addition, the polycarbonate resin composition may exhibit excellent drip-type flame retardancy as the number of drips measured for a film specimen having a thickness of 1.5 mm is 0 according to UL 94 Vertical Protocol.

In addition, the polycarbonate resin composition has a total combustion time (sec) of 40 seconds or less, 38 seconds or less, or 36 seconds or less, as measured for a film specimen having a thickness of 1.5 mm according to UL 94 Vertical Protocol, and has excellent flame retardancy. Can be indicated.

In addition, the polycarbonate resin composition has a haze of 0.01% or more, 1.0% or less, or 0.9% or less, or 0.8% or less, as measured for a film specimen having a thickness of 3 mm according to ASTM D1003. , It can show excellent transparency.

In addition, the polycarbonate resin composition has a flow length (Spiral length, cm) of 50 cm or more, or 51 cm or more, measured by injection molding at 330° C. using a spiral mold having a thickness of 2.5 mm and a width of 10 mm, or While being 53 cm or more, 65 cm or less, or 60 cm or less, or 58 cm or less may exhibit excellent processability.

In addition, the polycarbonate resin composition, according to ASTM D1238 (300 ℃ and 1.2 kg load; 10 minutes measured) melt index (MI) of 7 g / 10 minutes or more, or 8 g / 10 minutes or more, or 10 g / While 10 minutes or more, 50 g/10 minutes or less, or 30 g/10 minutes or less, or 20 g/10 minutes or less may exhibit excellent fluidity.

In addition, the polycarbonate resin composition has a flame retardancy rating measured for a film specimen having a thickness of 1.5 mm according to UL 94 Vertical Protocol, a UV exposure test (Weather-O-meter protocol) and a water exposure test (immersion) according to UL 746C. protocol) both before and after V-0, which can exhibit excellent weather resistance.

In addition, the polycarbonate resin composition is a UV exposure test according to UL 746C (Weather-O-meter protocol) and After the water exposure test (immersion protocol), each tensile impact value is 50% or more, or 60% or more, or 70% or more of the measured value before the exposure test, which can exhibit excellent weather resistance.

At the same time, the polycarbonate resin composition was subjected to a UV exposure test (Weather-O-meter protocol) and a water exposure test (immersion protocol) according to UL 746C when measuring the tensile strength of a film specimen having a thickness of 1.5 mm according to ASTM D638. ) After each tensile strength value is 50% or more, or 60% or more, or 70% or more of the measured value before the exposure test, it can exhibit excellent weather resistance.

Resin molded product

According to another embodiment of the present invention, a molded article including the polycarbonate resin composition described above is provided.

The molded article is an article obtained by molding by extrusion, injection, or casting using the above-described polycarbonate resin composition as a raw material. The molding method and its conditions may be appropriately selected and adjusted according to the type of the molded article.

As a non-limiting example, the molded article may be obtained by mixing and extrusion molding the polycarbonate resin composition into pellets, and then drying the pellets to inject.

In particular, the molded article may exhibit excellent processability, flame retardancy and weather resistance as it is formed from the polycarbonate resin composition, and may preferably be suitably used as a material for electric and electronic parts, lighting equipment parts, and the like.

Hereinafter, preferred embodiments are presented to aid in understanding the invention. However, the following examples are for illustrative purposes only, and the invention is not limited thereto.

< Example >

Materials used

In the following examples and comparative examples, the following materials were used.

(a) linear copolycarbonate resin

(a-1) LUPOY PC1080-70 manufactured by LG Chemical, a polycarbonate containing the repeating unit of Formula 1-2 (weight average molecular weight: 19,600 g/mol)

(a-2) LUPOY PC1300-30 manufactured by LG Chemical, a polycarbonate containing the repeating unit of Formula 1-2 (weight average molecular weight: 21,100 g/mol)

(a-3) LUPOY PC1300-15 manufactured by LG Chemical, a polycarbonate containing the repeating unit of Formula 1-2 (weight average molecular weight: 27,800 g/mol)

(b) branched polycarbonate resin

LUPOY PC1600-03 manufactured by LG Chemical, which is a polycarbonate having a weight average molecular weight of 37,600 g/mol and containing the repeating unit of Formula 1-2 and 2-1

-(c) organic sulfonate-based metal salt

FR-2025 manufactured by 3M, which is potassium perfluorobutane sulfonate (KPFBS)

-(d) Dioxybenzoin epoxy compound

BHBD (4,4'-bishydroxydeoxybenzoin) 69 g (0.3 mol) and Epichlorohydrin 243 ml (3 mol) were put into a round bottom flask, and 20% NaOH Solution (30 g NaOH distilled water 120 ml) was added dropwise at 70°C. After reacting for 1 hour, it was cooled to room temperature, and the product was extracted with chloroform. Washed with distilled water 3 times and dried over magnesium sulfate to give 80g (yield 78%) of a compound represented by the following formula 3-1.

[Chemical Formula 3-1]

.

.

-(e) phenylmethyl silicone oil

(e-1) KR-56A manufactured by SHINETSU, Japan, which is a phenylmethyl silicone oil having a kinematic viscosity at 25° C. of 15 mm 2 /second represented by the following Chemical Formula 4-1:

[Formula 4-1]

.

.

(e-2) KR-2710 manufactured by ShinEstu, Japan, which is a phenylmethyl silicone oil having a kinematic viscosity at 25°C of 50 mm 2 /sec.

(e-3) KR-511 manufactured by ShinEstu, Japan, which is a phenylmethyl silicone oil having a kinematic viscosity at 25°C of 100 mm 2 /sec.

(e-4) DC-550 manufactured by Dow Corning, a linear phenylmethyl silicone oil having a kinematic viscosity of 125 mm 2 /sec at 25°C

-(f) UV absorber

TINUVIN 329, a 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole) manufactured by BASF

-(g) additive

(g-1) Alkanox 240, a tris(2,4-di-t-butylphenyl)phosphite (tris(2,4-di-tert-butylphenyl)phosphite) manufactured by Addivant

(g-2) FACIL348, pentaerythrityl tetraethylhexanoate (PETS) manufactured by FACI

Example And Comparative example

After mixing the contents of each component as shown in Table 1 below, after pelletizing at a rate of 80 kg per hour in a twin screw extruder (L/D=36, Φ=45, barrel temperature: 240°C), JSW (main ) A specimen was prepared by injection molding at a cylinder temperature of 300°C and a mold temperature of 80°C using an N-20C injection molding machine.

Components and contents used in each Example and Comparative Example are shown in Tables 1 and 2, respectively.

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Linear
PC ¹⁾
(wt%) a a-1(15)
a-2(45) a-1(15)
a-2(45) a-1(15)
a-2(45) a-1(15)
a-2(45) a-1(15)
a-2(45) a-1(15)
a-2(45) a-3(80) Branched
PC ¹⁾
(wt%) b b(40) b(40) b(40) b(40) b(40) b(40) b(20) Organic phonate
Metal salt
(phr) ²⁾ c c(0.10) c(0.10) c(0.10) c(0.10) c(0.10) c(0.10) c(0.10) Deoxy
Benzoin
Epoxy compound
(phr) ²⁾ d d (0.10) d (0.10) d (0.10) d (0.80) d (0.10) d (0.10) d (0.10) Phenylmethyl silicone oil
(phr) ²⁾ e e-1(2.00) e-1(3.00) e-1(4.00) e-1(3.00) e-2(3.00) e-1(3.00) e-1(3.00) UV absorber
(phr) ²⁾ f f(0.25) f(0.25) f(0.25) f(0.25) f(0.25) f(0.50) f(0.25) Additive (phr) ^{2 )} g g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05) g-1 (0.05)
g-2 (0.05)

1) Weight% of the total weight of linear polycarbonate resin and branched carbonate resin

2) Parts by weight relative to the sum of 100 parts by weight of linear polycarbonate resin and branched carbonate resin

Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Comparative example
6 Comparative example
7 Comparative example
8 Comparative example
9 Comparative example
10 Linear
PC ¹⁾
(wt%) a a-3
(100) a-3
(100) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) a-1
(15)
a-2
(45) Branched
PC ¹⁾
(wt%) b - - b(40) b(40) b(40) b(40) b(40) b(40) b(40) b(40) Organic phonate
Metal salt
(phr) ²⁾ c c
(0.10) c
(0.10) c
(0.10) c
(0.10) c
(0.10) - c
(0.10) c
(0.10) c
(0.10) c
(0.10) Deoxy
Benzoin
Epoxy compound
(phr) ²⁾ d - d
(0.10) d
(0.10) d
(0.10) d
(0.10) d
(0.10) - d
(0.10) d
(0.10) d
(1.30) Phenylmethyl silicone oil
(phr) ²⁾ e - e-1
(2.00) e-3
(2.00) e-4
(2.00) e-1
(1.00) e-1
(2.00) e-1
(2.00) - e-1
(2.00) e-1
(2.00) UV absorber
(phr) ²⁾ f - f
(0.25) f
(0.25) f
(0.25) f
(0.25) f
(0.25) f
(0.25) f
(0.25) - f
(0.25) Additive (phr) ^{2 )} g g-1
(0.50)
g-2
(0.50) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05) g-1
(0.05)
g-2
(0.05)

1) Weight% based on the total weight of linear polycarbonate resin and branched carbonate resin 2) Parts by weight based on 100 parts by weight of the total of linear polycarbonate resin and branched carbonate resin

Test example

For the compositions of the Examples and Comparative Examples and each specimen formed therefrom, physical properties were measured in the following manner, and the results are shown in Tables 4 and 5, respectively.

1) Fluidity (Melt Index; MI): It was measured according to ASTM D1238 (300°C, 1.2kg condition).

2) Room temperature impact strength: measured at 23°C according to ASTM D256 (1/8inch, Notched Izod).

3) Haze: It was measured using a haze meter for a 3 mm thick specimen according to ASTM 1003.

4) Spiral length: It was measured as the average length of a total of 10 injection-molded products by injection molding at 330°C using a spiral mold having a thickness of 2.5 mm and a width of 10 mm.

5) Number of drips, total combustion time and UL94 grade: To evaluate flame retardancy, the number of drips, total combustion time and UL94 grade were evaluated according to the UL 94 Vertical Protocol. Specifically, five flame-retardant specimens with a thickness of 1.5 mm required for application of the flame-retardant test were prepared and evaluated according to the following.

First, after contacting a 20 mm high flame to the specimen for 10 seconds, the combustion time (t1) of the specimen was measured, and the combustion pattern was recorded. Then, when the combustion was terminated after the first welding, the burning time (t2) and the sparking time (glowing time, t3) of the specimen after welding for 10 seconds were measured, and the burning pattern was recorded. The same was applied.

At this time, the number of drips is expressed as the number of times whether or not particles that emit flame are dropped out of the five specimens, and the total combustion time represents the total combustion time (t1+t2+t3) of the five specimens, and UL94 rating. Was evaluated on the basis of the flame retardancy grade in Table 3 below.

Flame retardant grade V-0 V-1 V-2 Individual burning time (t1 or t2 for individual specimens) 10 seconds or less 30 seconds or less 30 seconds or less Total burning time of 5 specimens (sum of t1 and t2 of 5 specimens) 50 seconds or less 250 seconds or less 250 seconds or less Burning and sparking time after secondary welding (sum of t2 and t3 of individual specimens) 30 seconds or less 60 seconds or less 60 seconds or less Whether to drop sparkling particles none none has exist

6) Tensile impact and tensile strength before exposure test: Tensile impact was measured according to ASTM D1822 (1/8 inch), and tensile strength was measured according to ASTM D638 (1.5 mm).

7) UL 746C immersion protocol (Water exposure test): In accordance with the UL 746C standard, weather resistance was evaluated according to the water exposure test. Specifically, after preparing 5 specimens with a thickness of 1.5 mm required for test application, pretreatment was immersed in distilled water at 70°C for 7 days, immersed in distilled water at 23°C for 30 minutes, and then the tensile impact and tensile strength values were measured, and 7 in distilled water at 70°C. After daily immersion pretreatment, immersion at 23°C and 50% relative humidity for 2 weeks, and then the flame retardancy grade was measured.

8) UL 746C Weather-O-meter protocol (UV exposure test): In accordance with the UL 746C standard, weather resistance was evaluated according to the UV exposure test. Specifically, after preparing 5 specimens with a thickness of 1.5 mm necessary for test application, a Xenon-arc lamp according to ASTM G151 was prepared, irradiated with UV for 102 minutes, and exposed to UV and water spray for the remaining 18 minutes. After repeating one minute cycle for a total of 1000 hours, the flame retardancy grade, tensile impact, and tensile strength values for each specimen were measured. At this time, the test was ^{conducted under conditions in which a wavelength of 340 nm was irradiated with energy of 0.35 W/m 2} and the temperature of the black-panel was operated at 63° C. (error 3° C.).

In the UL 746C immersion protocol and UL 746C Weather-O-meter protocol, each of the tensile impact, tensile strength, and flame retardancy grades was measured in the same manner as before the exposure test to confirm the deterioration of physical properties before and after the exposure test. Specifically, the tensile impact was measured according to ASTM D1822 (1/8 inch), the tensile strength was measured according to ASTM D638 (1.5 mm), and the flame retardancy grade was measured according to the UL 94 Vertical Protocol.

division Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Fluidity (g/10 min) 15.8 16.7 17.9 16.8 16.2 17.6 15.6 Room temperature impact strength (J/min) 832 825 802 812 828 816 842 Haze (%) 0.39 0.45 0.78 0.53 0.44 0.61 0.52 Flow length (cm) 54.3 55.8 57.2 56.2 55.6 56.3 50.9 Number of drips (pcs) 0 0 0 0 0 0 0 Total combustion time (second) 31.7 30.9 30.2 25.3 30.6 35.8 33.1 UL94 rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 Before exposure test
Properties Tensile impact
(kJ/m ² ) 301 292 285 281 295 285 289 The tensile strength
(MPa) 63 61 60 60 61 62 63 UL746C
Immersion protocol Tensile impact
(kJ/m ² ) 268 258 251 252 259 250 261 The tensile strength
(MPa) 58 57 56 58 58 58 58 UL94
ranking V-0 V-0 V-0 V-0 V-0 V-0 V-0 UL746C
Weather-O-meter protocol Tensile impact
(kJ/m ² ) 255 248 249 251 257 244 258 The tensile strength
(MPa) 57 56 54 53 56 56 57 UL94
ranking V-0 V-0 V-0 V-0 V-0 V-0 V-0

division Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Comparative example
6 Comparative example
7 Comparative example
8 Comparative example
9 Comparative example
10 Fluidity (g/10 min) 15.1 17.4 15.6 15.2 14.6 15.3 15.5 13.6 14.8 17.4 Room temperature impact strength (J/min) 845 815 853 832 821 836 822 859 833 542 Haze (%) 0.23 0.36 2.18 45.1 0.33 0.28 0.32 0.28 1.82 1.34 Flow length (cm) 46.9 48.3 52.0 51.4 51.8 53.8 54.1 44.9 82.4 57.8 Number of drips (pcs) 5 5 4 2 3 5 3 4 0 0 Total combustion time (second) 78.2 36.8 40.1 31.1 31.2 58.3 37.3 42.3 33.3 31.7 UL94 rating V-2 V-2 V-2 V-2 V-2 V-2 V-2 V-2 V-0 V-0 Before exposure test
Properties Tensile impact
(kJ/m ² ) - - - - - - - - 322 234 The tensile strength
(MPa) - - - - - - - - 64 68 UL746C
Immersion protocol Tensile impact
(kJ/m ² ) - - - - - - - - 254 198 The tensile strength
(MPa) - - - - - - - - 58 60 UL94 rating - - - - - - - - V-0 V-0 UL746C
Weather-O-meter protocol Tensile impact
(kJ/m ² ) - - - - - - - - 184 201 The tensile strength
(MPa) - - - - - - - - 38 56 UL94 rating - - - - - - - - V-2 V-0

Referring to Tables 4 and 5, it can be seen that the flame-retardant polycarbonate resin composition of the present invention exhibits excellent transparency and flame retardancy. In addition, the flame-retardant polycarbonate resin composition of the present invention exhibits a tensile impact and tensile strength value of 70% or more of the measured value before the exposure test even after the water exposure test and UV exposure test, and assuming that the VO flame retardancy level before the exposure test was maintained, weather resistance It can also be seen that it is excellent.

Claims (19)

(a) a linear polycarbonate resin comprising a first repeating unit represented by the following formula (1);
(b) a branched polycarbonate resin comprising a first repeating unit represented by the following formula (1);
Based on 100 parts by weight of the sum of the linear polycarbonate resin and the branched polycarbonate resin,
(c) 0.04 to 0.6 parts by weight of an organic sulfonate-based metal salt;
(d) 0.05 to 1.0 parts by weight of a dioxybenzoin-based epoxy compound;
(e) 1.5 to 5.0 parts by weight of phenylmethyl silicone oil having a kinematic viscosity at 25° C. of 5 to 60 mm 2 /second; And
(f) 0.1 to 0.5 parts by weight of an ultraviolet absorber;
A polycarbonate resin composition comprising a,
The polycarbonate resin composition has a haze of 0.01% or more and 1.0% or less, as measured for a film specimen having a thickness of 3 mm according to ASTM D1003, and a film having a thickness of 1.5 mm according to UL 94 Vertical Protocol. The flame retardancy level measured for the specimen is V-0 both before and after the UV exposure test (Weather-O-meter protocol) and the water exposure test (immersion protocol) according to UL 746C.
Polycarbonate resin composition:
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.
The method of claim 1,
The first repeating unit represented by Formula 1 is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl) Sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A, 2,2-bis(4-hydroxyl) Phenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyl) Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2, 2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1- It is derived from at least one aromatic diol compound selected from the group consisting of phenylethane and bis(4-hydroxyphenyl)diphenylmethane,
Polycarbonate resin composition.
The method of claim 1,
The first repeating unit represented by Formula 1 is represented by the following Formula 1-2,
Polycarbonate resin composition:
[Formula 1-2]

.
The method of claim 1,
The branched polycarbonate resin comprises a first repeating unit represented by Chemical Formula 1 and a trivalent or tetravalent second repeating unit connecting the plurality of first repeating units to each other.
The method of claim 4,
The second repeating unit is 1,1,1-tris(4-hydroxyphenyl)ethane, 1,3,5-tris-(2-hydroxyethyl) cyanuric acid, 4,6-dimethyl-2, 4,6-tris-(4-hydroxyphenyl)-heptane-2,2,2-bis[4,4'-(dihydroxyphenyl)cyclohexyl]propane, 1,3,5-trihydroxybenzene , 1,2,3-trihydroxybenzene, 1,4-bis-(4', 4''-dihydroxytriphenylmethyl)-benzene, 2',3',4'-trihydroxyacetophenone , 2,3,4-trihydroxybenzoic acid, 2,3,4,-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2',4',6'-trihydroxy -3-(4-hydroxyphenyl)propiophenone, pentahydroxyflavone, 3,4,5-trihydroxyphenylethylamine, 3,4-trihydroxyphenylethyl alcohol, 2,4,5-tri Selected from the group consisting of hydroxypyrimidine, tetrahydroxy-1,4-quinone hydrate, 2,2',4,4'-tetrahydroxybenzophenone and 1,2,5,8-tetrahydroxyanthraquinone Which is derived from one or more branching agents.
Polycarbonate resin composition.
The method of claim 4,
The second repeating unit is represented by the following formula 2-1,
Polycarbonate resin composition:
[Formula 2-1]

.
The method of claim 4,
The branched polycarbonate resin comprises 98 to 99.999 mol% of the first repeating unit and 0.001 to 2 mol% of the second repeating unit,
Polycarbonate resin composition.
The method of claim 1,
The weight average molecular weight of the linear polycarbonate resin is 1,000 to 100,000 g/mol,
The weight average molecular weight of the branched polycarbonate resin is 10,000 to 100,000 g/mol,
Polycarbonate resin composition.
The method of claim 1,
Based on the total weight of the linear polycarbonate resin and the branched polycarbonate resin,
Including 50 to 80% by weight of the linear polycarbonate resin,
Containing 20 to 50% by weight of the branched polycarbonate resin,
Polycarbonate resin composition.
The method of claim 1,
The organic sulfonate-based metal salt is sodium trifluoromethyl sulfonate, sodium perfluoroethyl sulfonate, sodium perfluorobutyl sulfonate, sodium perfluoroheptyl sulfonate, sodium perfluorooctyl sulfonate, sodium trichloro Benzene sulfonate, sodium polystyrene sulfonate, potassium perfluorobutyl sulfonate, potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, potassium diphenylsulfone sulfonate, calcium perfluoromethane sulfonate, rubidium purple Selected from the group consisting of luorobutyl sulfonate, rubidium perfluorohexyl sulfonate, cesium trifluoromethyl sulfonate, cesium perfluoroethyl sulfonate, cesium perfluorohexyl sulfonate, and cesium perfluorooctyl sulfonate At least one of which is
Polycarbonate resin composition.
The method of claim 1,
The dioxybenzoin-based epoxy compound is represented by the following formula (3),
Polycarbonate resin composition:
[Formula 3]

In Chemical Formula 3,
L ₁ and L ₂ are each independently C _1-10 alkylene,
R ₅ and R ₆ are each independently hydrogen, C _1-20 alkyl, or C _6-20 aryl.
The method of claim 11,
The dioxybenzoin-based epoxy compound is represented by the following formula 3-1,
Polycarbonate resin composition:
[Chemical Formula 3-1]

.
The method of claim 1,
The phenylmethyl silicone oil is represented by the following formula (4),
Polycarbonate resin composition:
[Formula 4]

In Chemical Formula 4,
R ₇ and R ₈ are each independently C _1-10 alkyl, C _1-10 alkenyl, or C _6-10 aryl,
R ₉ is phenyl,
n is an integer from 0 to 10,
m is an integer from 1 to 10
The method of claim 13,
R ₇ to R ₉ are all phenyl,
Polycarbonate resin composition.
The method of claim 1,
The ultraviolet absorber is at least one selected from the group consisting of a benzotriazole compound, a benzophenone compound, an oxalanilide compound, a benzoic acid ester compound, and a triazine compound,
Polycarbonate resin composition.
delete The method of claim 1,
According to the UL 94 Vertical Protocol, the number of drips measured on a film specimen having a thickness of 1.5 mm is 0,
Polycarbonate resin composition.
The method of claim 1,
In accordance with UL 94 Vertical Protocol, the total burning time (sec) measured for a film specimen having a thickness of 1.5 mm is 40 seconds or less.
Polycarbonate resin composition.
Comprising the polycarbonate resin composition of any one of claims 1 to 15, 17 and 18,
Molded products.