KR20240026084A - Polycarbonate resin composition, method for preparing the same and molding products comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition, a manufacturing method thereof, and a molded article containing the same, and more specifically, A-1) Polycarbonate 20 to 75 with a melt index (300° C., 1.2 kg) of 15 to 25 g/10 min. weight%; B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and E) 1 to 7% by weight of a phosphazene compound; a polycarbonate resin composition containing the same, a manufacturing method thereof, and a molded article containing the same.
According to the present invention, a polycarbonate resin composition containing a high content of post-consumer recycled polycarbonate to increase the recycling rate and have excellent impact resistance, heat resistance, and flame retardancy, a manufacturing method thereof, and a molded article containing the same. It has the effect of providing.

Description

Polycarbonate resin composition, manufacturing method thereof, and molded product containing the same {POLYCARBONATE RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND MOLDING PRODUCTS COMPRISING THE SAME}

The present invention relates to a polycarbonate resin composition, a manufacturing method thereof, and a molded article containing the same. More specifically, the present invention relates to a high-content post-consumer recycled polycarbonate obtained by recycling plastic used and discarded by end consumers. It relates to a polycarbonate resin composition that has excellent flame retardancy, impact resistance, and heat resistance, a method for manufacturing the same, and a molded article containing the same.

Plastic has been used in various fields for decades due to its various advantages such as excellent productivity, lightness, and insulation, but due to its structural characteristics, it does not decompose easily, causing environmental pollution problems when landfilled. Various studies have been conducted to solve these problems, and one of them is recycling. Recycling waste plastic can solve environmental pollution problems and have a significant effect in terms of cost reduction.

IT, electrical/electronic, and automobile companies seek to recycle plastics used and discarded by end consumers in line with eco-friendly trends, but their use is subject to many restrictions due to their reduced mechanical properties compared to existing plastics.

Among various types of plastics, polycarbonate is an amorphous thermoplastic resin that has the advantages of high impact resistance at room temperature, excellent thermal stability and transparency, and high dimensional stability, making it a building material, exterior materials and parts for electrical and electronic products, automobile parts, and optics. It is widely used as a resin for various industrial purposes, including parts.

Polycarbonate has many advantages, but it has low impact resistance at low temperatures and the resin itself has no flame retardant properties, so it is dangerous if a fire occurs when applied to electrical, electronic and automotive devices. To solve this problem, when flame retardants are used in polycarbonate, mechanical properties such as impact resistance and heat resistance are deteriorated.

In addition, when post-consumer recycled polycarbonate is used in a thermoplastic resin composition, there is a problem that impact resistance and heat resistance are further reduced, so it is used only in small amounts.

Therefore, there is a need for the development of a thermoplastic resin composition that can increase the ratio of recycled resin by including a high content of post-consumer recycled polycarbonate in the thermoplastic resin composition, while also providing excellent flame retardancy, impact resistance, and heat resistance.

Korean Patent Publication No. 2011-0126425

In order to solve the problems of the prior art as described above, the present invention aims to provide a polycarbonate resin composition that is excellent in flame retardancy, impact resistance, and heat resistance even though it contains a high content of post-consumer recycled polycarbonate. Do it as

Additionally, the purpose of this disclosure is to provide a method for producing the polycarbonate resin composition.

Additionally, the present disclosure aims to provide a molded article containing the polycarbonate resin composition.

The above and other objectives of the present disclosure can all be achieved by the present invention described below.

In order to achieve the above object, the present substrate is A-1) 20 to 75% by weight of polycarbonate with a melt index (300 ℃, 1.2 kg) of 15 to 25 g/10min; B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and E) 1 to 7% by weight of a phosphazene compound.

The polycarbonate resin composition preferably includes A-1) 20 to 75% by weight of polycarbonate with a melt index (300° C., 1.2 kg) of 15 to 25 g/10 min; A-2) 0 to 50% by weight of polycarbonate having a melt index (300°C, 1.2 kg) of 5 g/10min or more to less than 15 g/10min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and E) 1 to 7% by weight of a phosphazene compound.

The polycarbonate resin composition preferably includes A-1) 20 to 75% by weight of polycarbonate with a melt index (300° C., 1.2 kg) of 15 to 25 g/10 min; A-2) 1 to 50% by weight of polycarbonate having a melt index (300°C, 1.2 kg) of 5 g/10min or more to less than 15 g/10min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and E) 1 to 7% by weight of a phosphazene compound.

The A-1) polycarbonate may preferably be a post-consumer recycling polycarbonate, and the A-2) polycarbonate may preferably be a general polycarbonate.

The B) polysiloxane-polycarbonate copolymer may preferably include an aromatic diol compound, a carbonate precursor, and polysiloxane.

The B) polysiloxane-polycarbonate copolymer preferably includes an aromatic polycarbonate-based first repeating unit represented by the following formula (1); and a second aromatic polycarbonate-based repeating unit having one or more siloxane bonds represented by the following formula (2). Alternatively, it may include a repeating unit represented by the following formula (3).

[Formula 1]

(In Formula 1, R ¹ to R ⁴ are each independently selected from hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen, and Z is unsubstituted or C _1-6 alkyl or C _6-20 C _1-10 alkylene substituted with aryl; C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl; oxygen; S; selected from SO, SO ₂ or CO.)

[Formula 2]

_{( In} Formula ₂ ^{, X 1 and} or C _6-20 aryl group, R ⁵ to R ⁸ are each independently hydrogen; unsubstituted or oxiranyl, C _1-10 alkoxy group substituted with oxiranyl, C substituted with C _6-20 aryl _1-15 alkyl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n2 is an integer from 30 to 120.

[Formula 3]

(In Formula 3, X ³ and X ⁴ are each independently C _1-10 alkylene, and R ⁹ _to R ¹² are each independently hydrogen; C _1-15 alkyl substituted with alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n ₁ is an integer of 30 to 120. am.)

The B) polysiloxane-polycarbonate copolymer preferably has an average size of siloxane domains of 20 nm or more.

The above C) glass fiber preferably has an average length of 1 to 15 mm, an average cross-sectional horizontal length of 15 to 45 ㎛, and an average cross-sectional vertical length of 2 to 15 ㎛.

D) The liquid phosphorus-based flame retardant is preferably bisphenol-A bis(diphenyl phosphate), triphenyl phosphate, and resorcinol. It may be one or more types selected from the group consisting of bis diphenyl phosphate).

The phosphazene compound E) may preferably be at least one selected from the group consisting of cyclic phosphazene compounds, chain-type phosphazene compounds, and cross-linked phosphazene compounds.

The weight ratio (D:E) of D) the liquid phosphorus-based flame retardant and E) the phosphazene compound may preferably be 1.2:1 to 3.0:1.

The polycarbonate resin composition preferably has an Izod impact strength of 11 kgf·cm/cm or more, as measured at room temperature with a notched specimen with a thickness of 3.2 mm according to ASTM D256.

The polycarbonate resin composition may preferably have a heat distortion temperature of 97° C. or higher as measured under a load of 18.6 kg using a specimen with a thickness of 6.4 mm according to ASTM D648.

The polycarbonate resin composition may preferably have a flame retardancy of grade V-0 or higher as measured by a specimen with a thickness of 0.8 mm based on the UL94 V test.

In addition, this substrate contains A-1) 20 to 75% by weight of polycarbonate with a melt index (300 ° C., 1.2 kg) of 15 to 25 g / 10 min, A-2) a melt index (300 ° C., 1.2 kg) of 5 g. /10 min or more to less than 15 g/10 min 0 to 50% by weight of polycarbonate, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) liquid phosphorus-based flame retardant 2 to 12 % by weight, and E) 1 to 7 wt% of a phosphazene compound, and kneading and extruding under conditions of 200 to 350 ° C. and 100 to 400 rpm. .

The method for producing the polycarbonate resin composition is preferably A-1) 20 to 75% by weight of polycarbonate with a melt index (300 ° C., 1.2 kg) of 15 to 25 g / 10 min, A-2) melt index (300 ° C.) , 1.2 kg) 1 to 50% by weight of polycarbonate having a weight of 5 g/10min or more to less than 15 g/10min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) Liquid phosphorus-based flame retardants 2 to 12 % by weight, and E) 1 to 7 wt% of a phosphazene compound, and may include kneading and extruding under conditions of 200 to 350° C. and 100 to 400 rpm.

Additionally, the present substrate provides a molded article comprising the polycarbonate resin composition.

According to the present invention, there is an effect of providing a polycarbonate resin composition that is excellent in flame retardancy, heat resistance, and impact resistance despite containing a high content of post-consumer recycled polycarbonate.

Furthermore, the polycarbonate resin composition according to the present invention can increase the content of post-consumer recycled polycarbonate, thereby increasing the recycling rate of waste plastic, providing the advantage of being eco-friendly, reducing greenhouse gases, and saving energy.

Hereinafter, the polycarbonate resin composition of the present invention will be described in detail.

The present inventors have found that when polycarbonate contains a high content of post-consumer recycled polycarbonate and also includes a combination of a liquid phosphorus-based flame retardant and a phasphazene compound, a polysiloxane-polycarbonate copolymer, and glass fiber in a predetermined amount, flame retardancy and heat resistance are improved. and impact resistance were both excellent, and based on this, further research was devoted to completing the present invention.

A detailed look at the polycarbonate resin composition according to this material is as follows.

The polycarbonate resin composition of the present invention includes A-1) 20 to 75% by weight of polycarbonate with a melt index (300° C., 1.2 kg) of 15 to 25 g/10 min; B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and E) 1 to 7% by weight of a phosphazene compound. In this case, while containing a high content of recycled polycarbonate, it has excellent flame retardancy, impact resistance, and heat resistance, and is environmentally friendly.

A-1) Polycarbonate with a melt index (300°C, 1.2 kg) of 15 to 25 g/10min

Above A-1) polycarbonate is, for example, 20 to 75% by weight, preferably 25 to 72% by weight, more preferably 28 to 72% by weight, even more preferably 30 to 62% by weight, based on the total weight of the polycarbonate resin composition. It may be % by weight, and within this range, the recycling rate is high, making it eco-friendly and reducing water and energy consumption, while providing excellent flame retardancy, heat resistance, and impact resistance.

A-1) polycarbonate preferably has a melt index of 17 to 22 g/10min, more preferably 19 to 21 g/10min, and has excellent physical property balance and impact resistance within this range.

In this description, the melt index is measured at 300°C and a load of 1.2 kg according to ASTM D1238.

The polycarbonate above A-1) may have a polydispersity index of, for example, more than 2.75, preferably 2.8 or more, more preferably 2.8 to 3.2, and even more preferably 2.8 to 3.0, and within this range the mechanical properties and physical properties It has excellent balance.

In this description, the polydispersity index refers to the distribution of molecular weight and is a value calculated by dividing the weight average molecular weight by the number average molecular weight. A high polydispersity index means that the standard deviation of the molecular weight distribution is large, meaning that there are more molecular weights larger or smaller than the weight average molecular weight.

In this description, unless otherwise defined, the weight average molecular weight and number average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze). As a specific example, GPC (Gel Permeation Chromatography) is performed using THF (tetrahydrofuran) as an eluent. It can be measured relative to a standard PS (standard polystyrene) sample through chromatography and waters breeze. As a specific measurement example, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml/min, the sample concentration is 20 mg/ml, the injection volume is 5 ㎕, and the column model is 1xPLgel 10㎛ MiniMix-B (250x4.6mm ) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), measuring device is Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature is 35 ℃, data Treatment can be measured using Agilent ChemStation S/W, and test methods (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

A-1) The polycarbonate may have a weight average molecular weight, for example, of 20,000 g/mol or more to less than 28,000 g/mol, preferably 22,000 to 27,000 g/mol, more preferably 24,000 to 27,000 g/mol, Within this range, excellent mechanical properties and physical property balance are achieved.

A-1) The polycarbonate may have a heat distortion temperature measured according to ASTM D648 of, for example, 124 ℃ or higher, preferably 127 ℃ or higher, more preferably 130 ℃ or higher, and even more preferably 130 to 140 ℃. Within this range, excellent mechanical properties and property balance are achieved.

In this material, the heat distortion temperature can be measured under a load of 18.6 kg with a specimen with a thickness of 6.4 mm according to ASTM D648.

The above A-1) polycarbonate may be, for example, post-consumer recycled polycarbonate, and in this case, it is environmentally friendly, saves energy and water, and reduces carbon emissions by recycling waste plastic.

In this description, the post-consumer recycled polycarbonate is not particularly limited if it is generally recognized as post-consumer recycled polycarbonate in the technical field to which the present invention pertains as long as it follows the definition of the present invention. For example, the post-consumer recycled polycarbonate is recycled from the collected waste plastic. It is polycarbonate, and as a specific example, it means that it is prepared as a usable raw material through selection, washing, and grinding from collected waste plastics. In addition, if necessary, it can be used in pellet form through an extrusion process, which has the advantage of not requiring additional processing such as additional purification. Since this post-consumer recycled polycarbonate has been processed more than once, it may contain additives such as colorants, lubricants, and/or mold release agents.

The post-consumer recycled polycarbonate may also be referred to as recycled polycarbonate or recycled polycarbonate, for example.

For example, the A-1) polycarbonate may be a polymerized resin containing an aromatic diol compound and a carbonate precursor.

Examples of the aromatic diol compound include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis( 4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA ), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 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-3chlorophenyl)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 α,ω-bis[3-(ο-hydroxyphenyl)propyl] It may be one or more types selected from the group consisting of polydimethylsiloxane, and preferably may be bisphenol A.

The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis ( Diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bihaloformate. In terms of production efficiency and physical properties, triphosgene, phosgene, or these It may be desirable to use a mixture of.

As a specific example, polycarbonate formed by polymerizing the aromatic diol compound and the carbonate precursor includes a repeating unit represented by the following formula (4).

[Formula 4]

In Formula 4, R' ₁ to R' ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen, and Z' is unsubstituted or C _1-6 alkyl or C _{6- 20} C _1-10 alkylene substituted with aryl, C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl, O, S, SO, SO ₂ , or CO.

Preferably, in Formula 4, R' ₁ to R' ₄ are each independently hydrogen or C _1-3 alkyl, and Z' may be unsubstituted or C _1-6 alkylene substituted with methyl or phenyl.

The polycarbonate A-1) may be, for example, one or more types selected from the group consisting of linear polycarbonate, branched polycarbonate, and polyester carbonate copolymer, and is preferably linear polycarbonate, in this case It has the advantage of improved fluidity and excellent appearance characteristics.

The linear polycarbonate resin may preferably be bisphenol-A polycarbonate, but is not limited thereto.

For example, the polycarbonate in A-1) may be a commercially available product as long as it follows the definition of the present invention.

A-2) Polycarbonate with a melt index (300°C, 1.2 kg) of 5 g/10min or more to less than 15 g/10min

A-2) Polycarbonate above has, for example, a melt index (300°C, 1.2 kg) of 5 g/10min or more. It may be less than 15 g/10min, preferably 7 to 12 g/10min, more preferably 9 to 11 g/10min, and within this range, excellent mechanical properties and heat resistance are achieved.

For example, the polycarbonate above A-2) may have a polydispersity index of 2.75 or less, preferably 2.6 or less, more preferably 2.5 or less, and even more preferably 2.3 to 2.5, and the mechanical properties within this range. and has excellent physical property balance.

A-2) The polycarbonate has a weight average molecular weight of, for example, 28,000 g/mol or more, preferably 29,000 g/mol or more, more preferably 30,000 g/mol or more, and even more preferably 30,000 to 37,000 g/mol. Within this range, excellent mechanical properties and physical property balance are achieved.

A-2) The polycarbonate may have a heat distortion temperature measured according to ASTM D648 of, for example, 124 ℃ or higher, preferably 127 ℃ or higher, more preferably 130 ℃ or higher, and even more preferably 130 to 140 ℃. Within this range, excellent mechanical properties and property balance are achieved.

The polycarbonate A-2) may be, for example, general polycarbonate.

In this description, the general polycarbonate is not particularly limited if it is generally recognized as general polycarbonate in the technical field to which the present invention pertains as long as it follows the definition of the present invention, and is contrasted with the post-consumer recycled polycarbonate of the present invention, and is polycarbonate. It may be polycarbonate or a correspondingly available polycarbonate that has not been subjected to molding processing such as injection after polymerization of the monomers constituting the carbonate.

The general polycarbonate may be referred to as, for example, virgin polycarbonate, new polycarbonate, fresh polycarbonate, or non-recycled polycarbonate.

The monomers constituting the A-2) polycarbonate may preferably be selected within the same range as those mentioned in the A-1) polycarbonate.

A-2) The polycarbonate is, for example, 0 to 50% by weight, preferably 1 to 50% by weight, more preferably 7 to 45% by weight, even more preferably 10 to 42% by weight, based on the total weight of the polycarbonate resin composition. It may be % by weight, more preferably 15 to 42 % by weight, and within this range there is an advantage of excellent impact resistance and heat resistance.

B) polycarbonate-polysiloxane copolymer

The B) polysiloxane-polycarbonate copolymer may include, for example, an aromatic diol compound, a carbonate precursor, and polysiloxane, and in this case, there is an advantage of improved impact resistance.

In the present invention, B) polysiloxane-polycarbonate copolymer is distinguished from A-1) polycarbonate in that polysiloxane is introduced into the polycarbonate main chain.

For example, the aromatic diol compound and carbonate precursor may be the same as those used in producing the polycarbonate A-1) described above.

The B) polysiloxane-polycarbonate copolymer may be manufactured, for example, by condensation polymerization of polycarbonate and polysiloxane, or may be manufactured by interfacial polymerization of an aromatic diol compound, carbonate precursor, and polysiloxane, but is not limited thereto. .

The B) polysiloxane-polycarbonate copolymer includes, for example, an aromatic polycarbonate-based first repeating unit represented by the following formula (1); and an aromatic polycarbonate-based second repeating unit having one or more siloxane bonds, represented by the following formula (2).

[Formula 1]

In Formula 1, R ¹ to R ⁴ are each independently selected from hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen, and Z is unsubstituted or C _1-6 alkyl or C _6-20 aryl. C _1-10 alkylene substituted with; C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl; Oxygen; S; It is selected from SO, SO ₂ or CO.

Preferably, in Formula 1, R ₁ to R ₄ are each independently hydrogen or C _1-3 alkyl, and Z may be unsubstituted or C _1-6 alkylene substituted with methyl or phenyl.

The first repeating unit represented by Formula 1 is preferably a polymerization of bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, and is represented by the following Formula 1-1.

[Formula 1-1]

The first repeating unit represented by Formula 1 is, for example, 20 to 95 mol%, preferably 30 to 85 mol%, more preferably 40 mol%, based on 100 mol% of the total repeating units in the polysiloxane-polycarbonate copolymer. It may be contained in an amount of from 80 mol%.

[Formula 2]

_{In Formula 2} ^{, X 1 and} selected from C _6-20 aryl groups, and R ⁵ to R ⁸ are each independently hydrogen; Unsubstituted or oxiranyl, C _1-10 alkoxy group substituted with oxiranyl, C _1-15 alkyl substituted with C _6-20 aryl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n2 is an integer of 30 to 120.

Preferably, in Formula 2, X ¹ and X ² are each independently C _2-10 alkylene, more preferably C _2-6 alkylene, most preferably isobutylene, and Y ¹ and Y ² may each independently be hydrogen.

More preferably, in Formula 2, R ⁵ to R ⁸ are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro. , bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

More preferably, R ⁵ to R ⁸ are each independently C _1-10 alkyl or C _1-6 alkyl, even more preferably C _1-3 alkyl, and particularly preferably methyl.

Additionally, in Formula 2, n ₂ may be an integer of 30 to 120, and preferably may be an integer of 34 to 110.

The second repeating unit represented by Formula 2 is preferably represented by the following Formula 2-1.

[Formula 2-1]

In Formula 2-1, R ⁵ to R ⁸ and n ₂ are the same as defined above.

The second repeating unit represented by Formula 2 is, for example, 5 to 80 mol%, preferably 15 to 70 mol%, more preferably 20 mol%, based on 100 mol% of the total repeating units in the polysiloxane-polycarbonate copolymer. It may be contained in an amount of from 60 mol%.

Preferably, the polysiloxane-polycarbonate copolymer may further include a third repeating unit represented by the following formula (3).

[Formula 3]

In Formula 3, X ³ and X ⁴ are each independently C _1-10 alkylene, and R ⁹ to R ¹² are each independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n ₁ is an integer of 30 to 120.

Preferably, in Formula 3, X ³ and X ⁴ may each independently be C _2-10 alkylene, preferably C _2-4 alkylene, and more preferably propane-1,3-diyl. .

In Formula 3, R ⁹ to R ¹² are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, io. , methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

Preferably, R ⁹ to R ¹² are each independently C _1-10 alkyl or C _1-6 alkyl, more preferably C _1-3 alkyl, and even more preferably methyl.

Additionally, in Formula 3, n ₁ may be an integer of 30 to 120, and preferably may be an integer of 34 to 110.

When the composition further includes a third repeating unit represented by Formula 3, the heat resistance and impact resistance of the composition are further improved.

The third repeating unit represented by Formula 3 is preferably represented by Formula 3-1 below.

[Formula 3-1]

In Formula 3-1, R ⁹ to R ¹² and n ₁ are the same as defined above.

For example, the third repeating unit represented by Formula 3 is 1 to 30 mol%, preferably 3 to 25 mol%, more preferably, based on a total of 100 mol% of the first repeating unit and the second repeating unit. may be further included in an amount of 5 to 20 mol%.

The B) polysiloxane-polycarbonate copolymer may have a weight average molecular weight of, for example, 1,000 to 100,000 g/mol, preferably 5,000 to 70,000 g/mol, more preferably 5,000 to 50,000 g/mol, within this range. It provides the advantage of easy processing and molding of the composition while satisfying impact resistance and heat resistance at the same time.

The B) polysiloxane-polycarbonate copolymer may have an average size of siloxane domains of, for example, 20 nm or more, preferably 20 to 60 nm, more preferably 30 to 60 nm, and within this range, polysiloxane-polycarbonate The siloxane domain of the copolymer can greatly improve impact resistance by acting as an impact modifier like rubber.

The term 'domain' used in the present invention refers to different unit chains dispersed in matrix chains. In addition, in the present invention, the 'average size of the siloxane domain' refers to the average size of the polysiloxane chains dispersed in the polycarbonate chain, specifically, the polysiloxane chain dispersed using the polycarbonate chain as a matrix, and more specifically, the polysiloxane chain. It may refer to the average size of an aggregate or aggregate.

In the present invention, the average size of the siloxane domain can be measured through shape analysis using a microscope, as a specific example, using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It was measured at room temperature. Preferably, the average size of the siloxane domains is an average value calculated after randomly selecting, for example, 10 siloxane domains from photographs taken through a microscope and measuring their sizes.

The B) polysiloxane-polycarbonate copolymer is, for example, 5 to 25% by weight, preferably 7 to 23% by weight, more preferably 9 to 20% by weight, even more preferably 9% by weight, based on the total weight of the polycarbonate resin composition. It may be from 16% by weight, and within this range, physical property balance and impact resistance are improved.

C) glass fiber

The C) glass fiber is, for example, 5 to 45% by weight, preferably 7 to 45% by weight, more preferably 7 to 40% by weight, even more preferably 7 to 28% by weight, based on the total weight of the polycarbonate resin composition. It can be, and within this range, it can provide excellent heat resistance while maintaining high mechanical properties, processability, etc.

For example, the C) glass fiber may have an average length of 1 to 15 mm, preferably 1 to 10 mm, more preferably 1 to 7 mm, and even more preferably 2 to 5 mm, and within this range, the resin and As the mechanical strength of the product is improved, the appearance characteristics of the final product are improved.

C) The glass fiber may have an average cross-sectional length of, for example, 15 to 45 ㎛, preferably 20 to 35 ㎛, more preferably 25 to 30 ㎛, and within this range, excellent fluidity and mechanical properties are achieved. There is.

C) The glass fiber may have an average cross-sectional length of, for example, 2 to 15 ㎛, preferably 2 to 12 ㎛, and more preferably 4 to 10 ㎛, and within this range, excellent fluidity and mechanical properties are achieved. There is.

C) The glass fiber may have an aspect ratio of the cross section of, for example, 1.5 to 5, preferably 2 to 4.7, more preferably 2.5 to 4.5, even more preferably 3 to 4.5, even more preferably 3.5 to 4.5, , within this range, fluidity and mechanical properties are excellent, and distortion and distortion are reduced in the final product, resulting in excellent dimensional stability.

In this description, the aspect ratio of the cross section is the ratio of the horizontal length to the vertical length. If the aspect ratio is 1, it is circular, and if it exceeds 1, it is oval.

For example, the glass fiber C) may be chopped glass fiber, and in this case, it has the advantage of excellent compatibility.

In this description, the chopped glass fiber is not particularly limited as long as it is chopped fiber glass commonly used in the technical field to which the present invention pertains.

In this material, the average length of the glass fiber, the horizontal length of the cross section, and the vertical length of the cross section can be measured by measurement methods commonly used in the technical field to which the present invention pertains. Specifically, 30 pieces are measured through a microscopic analysis method. It can be calculated as the average value.

The C) glass fiber may be surface treated with, for example, a silane-based compound or a urethane-based compound, and is preferably surface treated with one or more surface treatment agents selected from the group consisting of amino silane-based compounds, epoxy silane-based compounds, and urethane-based compounds. Treated ones can be used, and more preferably, they are surface-treated with an epoxy silane-based compound. In this case, the dispersibility in the resin composition is excellent, which has the effect of improving mechanical strength.

For example, the surface treatment agent is used in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, based on a total of 100% by weight of surface-treated glass fiber (glass fiber + surface treatment agent). Preferably, it may be included in the range of 0.1 to 0.8 wt%, more preferably in the range of 0.2 to 0.5 wt%, and within this range, the mechanical properties, physical property balance, and appearance of the final product are excellent.

The amino silane-based compound is not particularly limited in the case of amino silane, which is generally used as a coating agent for glass fiber, but examples include gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, and gamma-glycidoxypropyl triethoxy silane. Glycidoxypropyl methyldiethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxy propyl triethoxysilane Toxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyltriethoxy silane, gamma-acetoacetatepropyl trimethoxysilane, acetoacetatepropyl triethoxy silane , gamma-cyanoacetyl trimethoxy silane, gamma-cyanoacetyl triethoxy silane, and acetoxyaceto trimethoxy silane. In this case, it may be one or more types selected from the group consisting of excellent mechanical properties and heat resistance, and It has excellent surface properties.

The epoxy silane-based compound is not particularly limited in the case of epoxy silane, which is generally used as a coating agent for glass fiber, but examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, It may be one or more selected from the group consisting of 3-glycidyloxypropyl(dimethoxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, in which case it has excellent mechanical properties and heat resistance. The surface properties of the injection molded product are excellent.

Above C) glass fiber can be appropriately selected and used within the range commonly used in the industry as long as it follows the definition of the present invention.

D) Liquid phosphorus-based flame retardant

D) The liquid phosphorus-based flame retardant is, for example, 2 to 12% by weight, preferably 3 to 10% by weight, more preferably 3 to 8% by weight, even more preferably 4 to 7% by weight, based on the total weight of the polycarbonate resin composition. It may be included in %, and within this range, the resulting molded product has excellent impact resistance and heat resistance, has a beautiful appearance, and has excellent flame retardancy.

D) Liquid phosphorus-based flame retardant refers to a flame retardant that maintains a liquid state at room temperature. More specifically, it maintains a liquid state at room temperature under atmospheric pressure and has the function of imparting flame retardancy to the resin composition according to the present invention and controlling the melt index. At the same time, the resin composition according to the present invention stably satisfies flame retardant properties even with the use of a minimum amount of flame retardant, improves productivity, and solves problems in the appearance and processing of the resulting molded product. . In addition, by combining with the E) phosphazene compound described later, a synergistic effect is achieved in which flame retardancy of grade V-0 or higher is secured and impact resistance and heat resistance are further improved.

In the present disclosure, room temperature may be a point within the range of 20 ± 5°C.

Above D) liquid phosphorus-based flame retardants include, for example, bisphenol-A bis(diphenyl phosphate) (BPADP), triphenyl phosphate (tri-phenyl phosphate; TPP), and resorcinol bisdiphenyl. It is at least one selected from the group consisting of phosphate (resorcinol bis diphenyl phosphate; RDP), preferably bisphenol-A bis(diphenyl phosphate), and in this case, it has the advantage of having excellent impact resistance and heat resistance while ensuring flame retardancy. .

E) Phosphazene compounds

The E) phosphazene compound is, for example, 1 to 7% by weight, preferably 2 to 6% by weight, more preferably 2 to 5% by weight, even more preferably 3 to 4% by weight, based on the total weight of the polycarbonate resin composition. %, and within this range, flame retardancy is secured by combination with the liquid phosphorus-based flame retardant D), providing the advantage of improved impact resistance and heat resistance.

The E) phosphazene compound is, for example, an organic compound having a -P=N- bond in the molecule, and is preferably one selected from the group consisting of cyclic phosphazene compounds, chain-type phosphazene compounds, and cross-linked phosphazene compounds. It may be of more than one type, and is preferably a cyclic phosphazene compound. In this case, it has excellent flame retardancy and mechanical properties.

The cyclic phosphazene compound may preferably be a compound represented by the following formula (5).

[Formula 5]

In Formula 5, m is an integer of 3 to 25, and R ¹³ and R ¹⁴ are the same or different and represent an aryl group or an alkylaryl group.

In Formula 5, m is preferably an integer of 3 to 5.

The cyclic phosphazene compound represented by Formula 5 is more preferably a cyclic phenoxyphosphazene in which R ¹³ and R ¹⁴ are phenyl groups, and more preferably phenoxycyclotriphosphazene or octaphenoxycyclotetraphos. It may be one or more types selected from the group consisting of phazene, and decaphenoxycyclopentaphosphazene.

The chain phosphazene compound may preferably be a compound represented by the following formula (6).

[Formula 6]

In Formula ⁶ , n _is an integer from ₃ ^{to 10,000} , P(O)(OR ¹⁶ ) represents ₂ groups. R ¹⁵ and R ¹⁶ are the same or different and represent an aryl group or an alkylaryl group.

In Formula 6, n is preferably an integer of 3 to 100, more preferably an integer of 3 to 25.

The chain phosphazene compound represented by Formula 6 is preferably a chain phenoxphosphazene in which R ¹⁵ and R ¹⁶ are phenyl groups.

The cross-linked phosphazene compound is, for example, formed by cross-linking one or more phosphazene compounds selected from the group consisting of cyclic phosphazene compounds and chain-type phosphazene compounds with a cross-linking group represented by the following formula (7).

[Formula 7]

In Formula 7, A is -C(CH ₃ ) ₂ -, -SO ₂ -, -S-, or -O-, and I is an integer of 0 or 1.

In Formula 7, *━ and ━* are used to clarify that CH ₃ is not omitted but is a bond.

The cross-linked phosphazene compound is preferably a cross-linked phenoxyphosphazene compound obtained by cross-linking a cyclic phenoxyphosphazene compound in the formula (5) wherein R ¹³ and R ¹⁴ are phenyl groups by a cross-linking group represented by the formula (7), In Formula 6, a chain-type phenoxyphosphazene compound in which R ¹⁵ and R ¹⁶ are phenyl groups may be cross-linked by a cross-linking group represented by Formula 7, or a mixture thereof, and more preferably, Specifically, it may be a cross-linked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound is cross-linked by a cross-linking group represented by Formula 7 above.

When a combination of D) liquid phosphorus-based flame retardant and E) phosphazene compound is included, there is an advantage that both impact resistance and heat resistance are significantly improved while flame retardancy of V-0 grade or higher is realized due to the synergistic effect of the combination.

For example, the D) liquid phosphorus-based flame retardant may be included in a larger amount than the E) phosphazene compound, and in this case, there is an advantage in that superior flame retardancy can be achieved even with a small flame retardant content.

The weight ratio (D:E) of D) the liquid phosphorus-based flame retardant and E) the phosphazene compound is, for example, 1.2:1 to 3.0:1, preferably 1.2:1 to 2.7:1, more preferably 1.2:1 to 2.4. : 1, more preferably 1.2:1 to 2.2:1, even more preferably 1.3:1 to 2.1:1, particularly preferably 1.5:1 to 2.1:1, especially more preferably 1.7:1 to 2.1. : It can be 1, and within this range, even with a small content, better flame retardancy is realized and there is an advantage in that it has excellent impact resistance and heat resistance.

The total of D) liquid phosphorus-based flame retardant and E) phosphazene compound is, for example, 4 to 14% by weight, preferably 5 to 13% by weight, more preferably 6 to 12% by weight, based on the total weight of the polycarbonate resin composition. More preferably, it may be 7 to 11% by weight, and within this range, there is an advantage that flame retardancy, impact resistance, and heat resistance are all significantly improved.

For example, the polycarbonate resin composition may be impact modifier-free with a core-shell structure, and in this case, it has excellent impact resistance and heat resistance and more flame retardancy through the combination of D) liquid phosphorus-based flame retardant and E) phosphazene compound. There is an improvement effect. For example, the impact modifier of the core-shell structure may be an impact modifier of the core-shell structure containing methacrylate-butadiene-based rubber.

In this description, 'impact modifier-free of core-shell structure' means that the impact modifier of core-shell structure was not intentionally added when manufacturing the polycarbonate resin composition.

The polycarbonate resin composition includes, for example, heat stabilizers, flame retardant aids, lubricants, processing aids, plasticizers, coupling agents, light stabilizers, mold release agents, dispersants, anti-dripping agents, weathering stabilizers, antioxidants, compatibilizers, pigments, dyes, antistatic agents, It may contain one or more additives selected from the group consisting of anti-wear agents, fillers, and antibacterial agents, and in this case, the polycarbonate resin composition of the present material has the effect of realizing the necessary properties without deteriorating the original properties.

The additives may include 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on a total of 100 parts by weight of the polycarbonate resin composition. In this case, there is an effect of realizing the necessary physical properties without deteriorating the original physical properties of the polycarbonate resin composition of the present material.

For example, the heat stabilizer may be one or more selected from the group consisting of a hindered phenolic heat stabilizer, a diphenyl amine heat stabilizer, a sulfur-based heat stabilizer, and a phosphorus-based heat stabilizer, and preferably a hindered phenol-based heat stabilizer or a phosphorus-based heat stabilizer. It may be a stabilizer or a mixture thereof, and in this case, it prevents oxidation due to heat during the extrusion process and has excellent mechanical properties.

The hindered phenol-based heat stabilizer is, for example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene or a mixture thereof, preferably pentaerythritol tetrakis[3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate].

Examples of the diphenyl amine heat stabilizer include phenylnaphthylamine, 4,4'-dimethoxy diphenyl amine, 4,4'-bis(α,α-dimethylbenzyl) diphenyl amine, and 4-isopropoxy. It may be one or more types selected from the group consisting of diphenyl amine.

The sulfur-based heat stabilizer is, for example, dilauryl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, It may be one or more selected from the group consisting of urylstearyl-3,3'-thiodipropionic acid ester and pentaerythrityl tetrakis (3-laurylthiopropion ester), but is not limited thereto.

The phosphorus-based heat stabilizer is, for example, tris (mixed, mono and dinonylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4'-butylidene bis (3- Methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane, bis(2 ,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphanite, bis(2, 6-di-t-butyl-4-methylphenyl) pentaerythrityl-di-phosphite, 2,2'-ethylidene bis(4,6-di-t-butylphenyl)-2-ethylhexyl-phosphite , bis(2,4,6-di-t-butylphenyl) pentaerythritol-di-phosphite, triphenyl phosphite, diphenyldecyl phosphite, didecyl phenyl phosphite, tridecyl phosphite, trioctyl phosphite. It may be one or more selected from the group consisting of phyte, tridodecyl phosphite, trioctadecyl phosphite, tris nonylphenyl phosphite, and tridodecyl trithiophosphite, preferably bis(2,6-di -t-butyl-4-methylphenyl) pentaerythrityl-di-phosphite, but is not limited thereto.

The lubricant is, for example, selected from the group consisting of modified montanic acid wax, long chain ester of pentaerythritol, and fatty acid ester of neopentylpolyol. There may be one or more selected types.

For example, the UV absorber may be one or more selected from the group consisting of triazine-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, benzoate-based UV absorbers, and cyanoacrylate-based UV absorbers.

The triazine-based UV absorber is, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2 -Hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2 ,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)- 1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-( 2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5- It may be one or more selected from the group consisting of triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine.

The benzophenone-based ultraviolet absorbers include, for example, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2- Hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-di It may be one or more selected from the group consisting of hydroxy-4,4'-dimethoxy-benzophenone, and 2,2',4,4'-tetrahydroxy-benzophenone.

The benzotriazole-based ultraviolet absorbers include, for example, 2-(2'-hydroxy-5-methylphenyl)benzotriazole and 2-(2'-hydroxy3',5'-di-t-butylphenyl)benzotriazole. , 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy5'-methylphenyl)benzotriazole, 2-(2'-hyde Roxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'- Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetra Hydrophthalimidomethyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetra methylbutyl)-6-(2H-benzotriazol-2-yl ) Phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di- tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5 -It may be one or more selected from the group consisting of chlorobenzotriazole.

The cyanoacrylate-based ultraviolet absorber is, for example, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3-(3',4'-methylenedioxy) It may be phenyl)-acrylate, or a mixture thereof.

polycarbonate resin composition

The polycarbonate resin composition preferably has an Izod impact strength of 11 kgf·cm/cm or more, more preferably 13 kgf·cm/cm or more, as measured at room temperature with a notched specimen with a thickness of 3.2 mm according to ASTM D256. More preferably, it may be 15 kgf·cm/cm or more, and even more preferably 15 to 25 kgf·cm/cm, and within this range, the balance of physical properties is excellent.

The polycarbonate resin composition preferably has a heat distortion temperature of 97°C or higher, more preferably 105°C or higher, and even more preferably 110°C or higher, as measured under a load of 18.6 kg using a specimen with a thickness of 6.4 mm according to ASTM D648. More preferably, it is 113°C or higher, particularly preferably 115°C or higher, and even more preferably 115 to 125°C, and within this range, the physical property balance is excellent.

The polycarbonate resin composition preferably has a flame retardancy of V-0 grade or higher as measured by a specimen with a thickness of 0.8 mm based on the UL94 V test (Vertical Burning Test), and within this range, it has excellent impact resistance and heat resistance and high It has the effect of imparting flame retardancy.

Method for producing polycarbonate resin composition

The method for producing the polycarbonate resin composition of the present invention is A-1) 20 to 75% by weight of polycarbonate with a melt index (300 ° C., 1.2 kg) of 15 to 25 g / 10 min, A-2) melt index (300 ° C., 1.2 kg) 1.2 kg) 0 to 50% by weight of polycarbonate having a weight of 5 g/10min or more to less than 15 g/10min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) liquid Phosphorus-based flame retardants 2 to 12 % by weight, and E) 1 to 7 wt% of a phosphazene compound, and kneading and extruding under conditions of 200 to 350° C. and 100 to 400 rpm. In this case, impact resistance, heat resistance, and flame retardancy are all excellent.

The method for producing the polycarbonate resin composition shares all technical features of the polycarbonate resin composition described above. Therefore, description of the overlapping parts will be omitted.

The kneading and extrusion may be performed through, for example, a single-screw extruder, a twin-screw extruder, or a Banbury mixer, and in this case, the composition is uniformly dispersed, resulting in excellent compatibility.

For example, the kneading and extrusion may be performed within a barrel temperature of 200 to 350°C, preferably 220 to 330°C, more preferably 240 to 310°C, in which case the throughput per unit time is adequate and sufficient melting is achieved. Kneading can be possible and has the effect of not causing problems such as thermal decomposition of the resin component.

For example, the kneading and extrusion may be performed under conditions where the screw rotation speed is 100 to 400 rpm, preferably 150 to 350 rpm, and more preferably 200 to 300 rpm. In this case, the throughput per unit time is appropriate, so the process efficiency is high. It is excellent and has the effect of suppressing excessive cutting of glass fiber.

molded product

The molded product of the present base is characterized by containing the polycarbonate resin composition of the present base, and in this case, it contains a high content of post-consumer recycled polycarbonate, so it is environmentally friendly and has excellent impact resistance, heat resistance, and flame retardancy.

The molded article may be, for example, electrical and electronic components, automobile parts, or industrial materials.

The method for manufacturing the molded article of the present invention preferably includes: A-1) 20 to 75% by weight of polycarbonate with a melt index (300°C, 1.2 kg) of 15 to 25 g/10min, A-2) melt index (300°C, 1.2 kg); 1.2 kg) 0 to 50% by weight of polycarbonate having a weight of 5 g/10min or more to less than 15 g/10min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) liquid Phosphorus-based flame retardants 2 to 12 % by weight, and E) producing pellets by kneading and extruding them under conditions of 200 to 350°C and 100 to 400 rpm, including 1 to 7 wt% of a phosphazene compound, and injecting the produced pellets to produce molded articles. In this case, it contains a high content of post-consumer recycled polycarbonate, so it is environmentally friendly and has excellent impact resistance, heat resistance, and flame retardancy.

The manufactured pellets can be manufactured by, for example, sufficiently drying using a dehumidifying dryer or a hot air dryer and then injection processing.

In the above, the total weight of the polycarbonate resin composition in this substrate refers to A-1) polycarbonate with a melt index (300 ℃, 1.2 kg) of 15 to 25 g/10 min, B) polysiloxane-polycarbonate copolymer, and C) glass fiber. , D) refers to the total weight of the liquid phosphorus-based flame retardant and E) phosphazene compound, and A-2) polycarbonate with a melt index (300 ℃, 1.2 kg) of 5 g/10min or more to less than 15 g/10min. In this case, the total weight of the polycarbonate resin composition refers to the total weight of the components A-1), A-2), B), C), D) and E).

The manufacturing method of the molded product of the present invention is not particularly limited when using conditions, methods, and devices commonly used in the technical field to which the present invention pertains, as long as it follows the definition of the present invention.

In describing the polycarbonate resin composition, its manufacturing method, and molded article of the present disclosure, other conditions and equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry, and are not particularly limited. Specify.

Hereinafter, preferred examples are presented to aid understanding of the present description. However, the following examples are merely illustrative of the present description, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present description. It is natural that such variations and modifications fall within the scope of the attached patent claims.

The materials used in the examples and comparative examples are as follows.

* A-1) Polycarbonate with a melt index (300 °C, 1.2 kg) of 20 g/10 min according to ASTM D1238: Post-Consumer Recycled Polycarbonate (PCR-PC)

* A-2) Polycarbonate with a melt index (300 ℃, 1.2 kg) of 10 g/10min according to ASTM D1238: General polycarbonate (General PC; LG Chemical's PC1300-10)

* B-1) Polysiloxane-polycarbonate copolymer (Si-PC): SPC8100-02 (LG Chemical, average size of polyorganosiloxane domain is 50 nm to 60 nm)

* B-2) Impact modifier with core-shell structure (MBS): Impact modifier with core-shell structure containing methyl methacrylate-butadiene rubber (LG Chemical, EM538)

* C) Glass fiber: Glass fiber surface treated with a silane compound (average length 3 mm, average horizontal length of cross section 28 ㎛, average vertical length of cross section 7 ㎛)

* D) Liquid phosphorus-based flame retardant (BPADP): Bisphenol-A bis(diphenyl phosphate) (ADEKA, FP600)

* E) Phosphazene compound: Phenoxy phosphazene (Weihai Jinwei Chem Industry, HPC TP-JW01)

[Example]

After mixing the compositions and contents shown in Tables 1 to 3 below, they were mixed uniformly with a mixer, melted and kneaded in a twin-screw extruder (screw diameter 26 mm, L/D = 40), and then extruded at an extrusion temperature of 250 to 300 ℃ and screw. Polycarbonate resin composition pellets were prepared by extrusion under the condition of a rotation speed of 250 rpm. After drying it at 80 ℃ for more than 4 hours, a specimen for measuring physical properties was manufactured by injecting it at a nozzle temperature of 260 ℃ using an injection molding machine (ENGEL, 80MT), and then leaving it for more than 48 hours and measuring the physical properties.

division Example One 2 3 4 5 6 7 8 9 10 A-1) PCR-PC 30 30 30 30 71 30 30 30 30 30 A-2) General PC 43 42 37 41 - 10 10 5 43 43 B-1) Si-PC 10 10 15 10 10 10 10 15 10 10 B-2) MBS C) glass fiber 10 10 10 10 10 40 40 40 10 10 D) BDADP 4 5 5 6 5 7 6 6 3.5 5.5 E) Phosphazene 3 3 3 3 3 3 4 4 3.5 1.5 Properties impact strength
(kgf·cm/cm) 18 16 17 13 15 14 14 16 18 15 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0~V-1 V-0~V-1 HDT(℃) 118 116 114 113 117 97 98 98 119 118

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 A-1) PCR-PC 30 30 30 30 30 30 30 30 A-2) General PC 52 50 50 60 19 18 8 52 B-1) Si-PC 10 One B-2) MBS 2 2 3 2 2 C) glass fiber 10 10 10 10 40 40 40 10 D) BDADP 8 8 5 8 7 10 4 E) Phosphazene 3 3 3 Properties impact strength
(kgf·cm/cm) 5 7 9 8 10 13 11 18 Flame retardant V-0 V-1 V-1 V-2 V-1 V-1 V-1 V-1 HDT(℃) 110 109 112 138 94 97 90 120

division Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 A-1) PCR-PC 30 30 30 30 30 A-2) General PC 23 52 3 45 34 B-1) Si-PC 30 10 10 10 10 B-2) MBS C) glass fiber 10 One 50 10 10 D) BDADP 4 4 4 0 7 E) Phosphazene 3 3 3 5 9 Properties impact strength
(kgf·cm/cm) 10 60 15 17 10 Flame retardant V-1 V-1 V-1 V-NOT ^* V-0 HDT(℃) 114 137 100 125 101

V-NOT ^* : Flame retardant rating is not possible because it does not meet combustion standards based on the UL94 V test. In other words, the combustion time of the specimen is exceeded or burned out.

As shown in Tables 1 to 3, the polycarbonate resin composition of the present invention (Examples 1 to 10) was confirmed to have superior impact strength, flame retardancy, and heat distortion temperature compared to Comparative Examples 1 to 13. In addition, A-1) even if a high content of PCR-PC was included, it had the advantage of increasing the recycling rate by showing excellent impact strength, flame retardancy, and heat distortion temperature. In particular, Examples 1 to 8, in which the weight ratio (D:E) of D) liquid phosphorus-based flame retardant and E) phosphazene compound was 1.2:1 to 3.0:1, had better flame retardancy.

Specifically, Comparative Example 1, which does not contain B-1) Si-PC and E) phosphazene, has very low impact strength, and Comparative Example 1 and B-2) Comparative Example 2, which includes MBS impact modifier, has somewhat lower impact strength. However, the flame retardancy decreased.

In addition, Comparative Example 3 containing B-1) Si-PC and B-2) MBS impact modifier had reduced flame retardancy and impact strength, and Comparative Example 4 containing neither D) BDADP nor E) phosphazene. had low impact strength and very poor flame retardancy.

In addition, Comparative Example 5, which included B-2) MBS impact modifier instead of B-1) Si-PC and D) used BDADP alone, had low flame retardancy and heat distortion temperature, and B-2) instead of B-1) Si-PC. Comparative Example 6 including MBS impact modifier had low flame retardancy and heat distortion temperature, and D) Comparative Example 7 using BDADP alone had lower flame retardancy and heat distortion temperature.

In addition, B-1) Comparative Examples 8 and 9, in which the Si-PC content was outside the range of the present invention, had reduced flame retardancy, and Comparative Example 9 had low impact strength.

In addition, C) Comparative Examples 10 and 11, in which the glass fiber content was outside the range of the present invention, had poor flame retardancy.

In addition, D) Comparative Example 12, which did not contain BDADP, had poor flame retardancy to the extent that flame retardancy measurement was impossible, and E) Comparative Example 13, which contained phosphazene beyond the scope of the present invention, had reduced impact strength.

In conclusion, A-1) post-consumer recycled polycarbonate according to the present invention includes a combination of B) polysiloxane-polycarbonate copolymer, C) glass fiber, D) liquid phosphorus-based flame retardant, and E) phosphazene compound in a predetermined amount. The polycarbonate resin composition was confirmed to have excellent impact resistance, heat resistance, and flame retardancy. Furthermore, A-1) even though a high content of post-consumer recycled polycarbonate was used, impact resistance, heat resistance, and flame retardancy were all improved.

Claims (15)

A) 20 to 75% by weight of polycarbonate with a melt index (300° C., 1.2 kg) of 15 to 25 g/10 min;
B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer;
C) 5 to 45% by weight of glass fiber;
D) Liquid phosphorus-based flame retardant 2 to 12 weight%; and
E) 1 to 7% by weight of a phosphazene compound;
Polycarbonate resin composition.
According to paragraph 1,
The polycarbonate resin composition is A-2) characterized in that it contains 1 to 50% by weight of polycarbonate having a melt index (300 ℃, 1.2 kg) of 5 g/10min or more to less than 15 g/10min.
Polycarbonate resin composition.
According to paragraph 1,
A) The polycarbonate is characterized in that it is a post-consumer recycling polycarbonate.
Polycarbonate resin composition.
According to paragraph 1,
The B) polysiloxane-polycarbonate copolymer is characterized in that it includes an aromatic diol compound, a carbonate precursor, and polysiloxane.
Polycarbonate resin composition.
According to paragraph 1,
The B) polysiloxane-polycarbonate copolymer includes an aromatic polycarbonate-based first repeating unit represented by the following formula (1); And a second aromatic polycarbonate-based repeating unit having at least one siloxane bond represented by the following formula (2), or characterized by comprising a repeating unit represented by the following formula (3)
Polycarbonate resin composition.
[Formula 1]

(In Formula 1, R ¹ to R ⁴ are each independently selected from hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen, and Z is unsubstituted or C _1-6 alkyl or C _6-20 C _1-10 alkylene substituted with aryl; C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl; oxygen; S; selected from SO, SO ₂ or CO.)
[Formula 2]

_{( In} Formula ₂ ^{, X 1 and} or C _6-20 aryl group, R ⁵ to R ⁸ are each independently hydrogen; unsubstituted or oxiranyl, C _1-10 alkoxy group substituted with oxiranyl, C substituted with C _6-20 aryl _1-15 alkyl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n2 is an integer from 30 to 120.
[Formula 3]

(In Formula 3, X ³ and X ⁴ are each independently C _1-10 alkylene, and R ⁹ _to R ¹² are each independently hydrogen; C _1-15 alkyl substituted with alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; allyl; C _1-10 haloalkyl; or C _6-20 aryl, and n ₁ is an integer of 30 to 120. am.)
According to paragraph 1,
The B) polysiloxane-polycarbonate copolymer is characterized in that the average size of the siloxane domain is 20 nm or more.
Polycarbonate resin composition.
According to paragraph 1,
C) The glass fibers have an average length of 1 to 15 mm, an average cross-sectional length of 15 to 45 ㎛, and an average cross-sectional length of 2 to 15 ㎛.
Polycarbonate resin composition.
According to paragraph 1,
D) Liquid phosphorus-based flame retardants include bisphenol-A bis(diphenyl phosphate), triphenyl phosphate, and resorcinol bis diphenyl phosphate. ), characterized in that one or more types selected from the group consisting of
Polycarbonate resin composition.
According to paragraph 1,
The E) phosphazene compound is characterized in that it is at least one selected from the group consisting of cyclic phosphazene compounds, chain-type phosphazene compounds, and cross-linked phosphazene compounds.
Polycarbonate resin composition.
According to paragraph 1,
The weight ratio (D:E) of D) liquid phosphorus-based flame retardant and E) phosphazene compound is 1.2:1 to 3.0:1.
Polycarbonate resin composition.
According to paragraph 1,
The polycarbonate resin composition is a notched specimen with a thickness of 3.2 mm according to ASTM D256, and the Izod impact strength measured at room temperature is 11 kgf·cm/cm or more.
Polycarbonate resin composition.
According to paragraph 1,
The polycarbonate resin composition is characterized in that the heat distortion temperature measured under a load of 18.6 kg in a specimen with a thickness of 6.4 mm according to ASTM D648 is 97 ℃ or higher.
Polycarbonate resin composition.
According to paragraph 1,
The polycarbonate resin composition is characterized in that the flame retardancy measured by a specimen with a thickness of 0.8 mm based on the UL94 V test is V-0 grade or higher.
Polycarbonate resin composition.
A) 20 to 75% by weight of polycarbonate with a melt index (300°C, 1.2 kg) of 15 to 25 g/10min, A-2) a melt index (300°C, 1.2 kg) of 5 g/10min or more to 15 g/ 0 to 50% by weight of polycarbonate less than 10 min, B) 5 to 25% by weight of polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% of liquid phosphorus-based flame retardant. % by weight, and E) 1 to 7 wt% of a phosphazene compound, comprising kneading and extruding under conditions of 200 to 350 ° C. and 100 to 400 rpm.
Method for producing polycarbonate resin composition.
Characterized by comprising the polycarbonate resin composition of any one of claims 1 to 13.
Molded product.