KR102178647B1 - Polycarbonate based resin composition and molded articles thereof - Google Patents

Abstract

In the present invention, a polycarbonate-based resin composition and a molded article thereof showing excellent impact strength and external surface characteristics with high rigidity are provided.

Description

Polycarbonate resin composition and its molded article TECHNICAL FIELD [POLYCARBONATE BASED RESIN COMPOSITION AND MOLDED ARTICLES THEREOF}

The present invention relates to a polycarbonate-based resin composition exhibiting excellent impact strength and external surface properties with high rigidity and a molded article thereof.

Polycarbonate resin is a thermoplastic resin formed by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene, and has excellent impact strength, numerical stability, heat resistance, and transparency, and is used as an exterior material for electrical and electronic products, and automotive parts. , Construction materials, optical parts, etc.

Recently developed mobile phones have many high-priced premium products that apply metal and metal inserts, but these are high in unit price and difficult to supply, and therefore, low-end or low-cost products try to replace metal with high-rigidity plastic products. However, in order to replace metal, it must have high rigidity and excellent adhesion to resin. Accordingly, since it is difficult to apply materials such as nylon, development of glass fiber-reinforced polycarbonate-based high-stiffness materials is in progress.

However, in the material reinforced with such glass fiber, it is difficult to add a high content of glass fiber, and as the content of glass fiber increases, the stiffness of the polycarbonate-based material increases, but the impact strength decreases significantly, and the glass fiber protrudes. There is a disadvantage in that the appearance surface characteristics are deteriorated due to. In addition, when a separate impact modifier is used to solve the decrease in impact strength due to the reinforcement of the glass fiber, there is a disadvantage in that it is difficult to impart flame retardancy required to the housing material of the electronic device.

Accordingly, the development of a polycarbonate-based material capable of simultaneously improving stiffness, impact strength, and appearance characteristics is continuously required.

Accordingly, the present invention is to provide a polycarbonate-based resin composition exhibiting improved surface properties along with excellent impact resistance and rigidity.

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

According to an embodiment of the present invention,

Polycarbonate resin consisting of aromatic polycarbonate repeating units;

A copolycarbonate resin comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond;

Flat glass fibers; And

Including glycol-modified polyethylene terephthalate resin,

The flat glass fiber provides a polycarbonate-based resin composition in which the shape of the cross section of the glass fiber cut vertically with respect to the longitudinal direction is a rectangle or an ellipse, and an aspect ratio of 50 to 500 represented by Equation 1 below:

[Equation 1]

Aspect ratio (δ) = L/D

In Equation 1, L is the length of the flat glass fiber, and D is the length of the longest side of the cross section when the cross section of the glass fiber is cut perpendicular to the length direction, and D is the longest side of the elliptical cross section. It is the length of the diameter.

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

Hereinafter, a polycarbonate-based 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.

In addition, the meaning of'comprising' or'containing' as used herein specifies a specific characteristic, area, integer, step, action, element or component, and other specific characteristic, area, integer, step, action, element, or It does not exclude the addition of ingredients.

In addition, in the present specification, terms including ordinal numbers such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

Polycarbonate-based resin composition according to an embodiment of the present invention,

(a) a polycarbonate resin consisting of an aromatic polycarbonate-based repeating unit,

(b) a copolycarbonate resin comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond,

(c) a flat glass fiber having a rectangular or elliptical cross-section of the glass fiber cut vertically with respect to the longitudinal direction and having an aspect ratio of 50 to 500, and

(d) glycol-modified polyethylene terephthalate resin is included:

[Equation 1]

Aspect ratio (δ) = L/D

In Equation 1, L is the length of the flat glass fiber, and D is the length of the longest side of the cross section when the cross section of the glass fiber is cut perpendicular to the length direction, and D is the longest side of the elliptical cross section. It is the length of the diameter.

In the conventional glass fiber-reinforced polycarbonate-based resin composition, it is difficult to introduce a high content of glass fiber, and as the content of the glass fiber increases, mechanical properties such as impact strength are deteriorated.

On the other hand, in the present invention, the stiffness of the resin composition is increased by applying cocoon or flat glass fiber, and at the same time, the impact of the resin composition due to the use of the glass fiber is used by using a copolycarbonate resin in which a siloxane bond is introduced into the polycarbonate main chain. The decrease in strength was compensated, and the glass transition temperature was increased using glycol-modified polyethylene terephthalate to prevent the glass fibers from being exposed on the surface of the resin composition to deteriorate the appearance characteristics. As a result, the polycarbonate-based resin composition according to the present invention may exhibit high stiffness and excellent strength characteristics and surface appearance characteristics. Accordingly, the polycarbonate-based resin composition according to an embodiment of the present invention can be suitably used as a housing material for portable electronic devices such as a tablet PC.

Hereinafter, components that may be included in the polycarbonate-based resin composition according to an embodiment of the present invention will be described in detail.

(a) polycarbonate resin

The polycarbonate resin is a base resin included in the polycarbonate-based resin composition, and consists of an aromatic polycarbonate-based repeating unit.

Accordingly, the polycarbonate resin may be distinguished from a copolycarbonate resin described later in that it does not have an aromatic polycarbonate-based repeating unit having a siloxane bond.

Specifically, the aromatic polycarbonate-based repeating unit is formed by a reaction of a diol compound and a carbonate precursor, and may suitably include a repeating unit represented by the following Formula 1, and the structure of such a repeating unit is a copolycarbonate to be described later. It may be the same as the repeating unit contained in the resin, but may be different:

[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.

Preferably, each of R ₁ to R ₄ is independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is a linear 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.

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)- From one or more aromatic diol compounds selected from the group consisting of 1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and alpha,omega-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane It may have been.

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

As a non-limiting example, when bisphenol A as an aromatic diol compound and triphosgene as a carbonate precursor are polymerized, the repeating unit of Formula 1 may be represented by Formula 1-1 below.

[Formula 1-1]

In addition, as the carbonate precursor, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl One or more selected from the group consisting of carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate may be used, and preferably, triphosgene or phosgene may be used. have.

The polycarbonate resin having the above structure may have a weight average molecular weight of 1,000 to 100,000 g/mol, preferably 5,000 to 50,000 g/mol. More preferably, the weight average molecular weight (g/mol) is 1,000 or more, 5,000 or more, 10,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 27,000 or more, or 28,000 or more. Further, the weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.

In addition, the polycarbonate resin has a melt index of 5 g/10 minutes to 25 g/10 minutes, or 5 g/10 minutes to 15 g/10 minutes according to ASTM D1238 (300°C and 1.2 kg load; measured for 10 minutes) Having (MI) may be preferable in terms of stable expression of physical properties of the composition.

The above-described polycarbonate resin may be directly synthesized according to a well-known synthesis method of a general aromatic polycarbonate resin, or commercially available aromatic polycarbonate may be obtained and used.

In addition, the content of the polycarbonate resin may vary depending on the physical properties of the resin composition to be controlled. However, polycarbonate resin is a component included as a base resin together with a copolycarbonate resin to be described later, and if the content is too high, the content of the copolycarbonate resin is relatively reduced, so that the impact resistance (impact strength) of the resin composition is sufficient. In addition, if the content of the polycarbonate resin is too small, mechanical properties such as rigidity may not be sufficient. Accordingly, the polycarbonate resin may be included in an amount of 5 to 35% by weight, more preferably 8 to 30% by weight, based on the total content of the resin composition of one embodiment. When included in the above content range, it can exhibit excellent mechanical strength properties.

(b) Copolycarbonate resin

In the present invention, the term'copolycarbonate' means a copolymer including a polycarbonate-based repeating unit in which a polysiloxane structure is not introduced into the main chain and a polycarbonate-based repeating unit in which a polysiloxane structure is introduced into the main chain.

The copolycarbonate resin is a component capable of improving physical properties, in particular, mechanical strength, etc. of the polycarbonate resin described above, and at the same time compensating for a decrease in impact strength caused by the use of glass fibers, and an aromatic polycarbonate-based repeating unit ( Hereinafter, a first repeating unit) and an aromatic polycarbonate-based repeating unit having one or more siloxane bonds (hereinafter referred to as a second repeating unit).

That is, the copolycarbonate resin can be distinguished from the above-described polycarbonate resin (for example, having only an aromatic polycarbonate main chain without introducing a polysiloxane structure) in that a polysiloxane structure is introduced into the main chain of the polycarbonate.

The aromatic polycarbonate-based first repeating unit is specifically formed by reaction of a diol compound and a carbonate precursor, and may include a repeating unit represented by Formula 1 described above.

[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.

Here, R ₁ to R ₄ and Z may have the same or different structure as a group corresponding to the repeating unit constituting the polycarbonate resin described above.

As a non-limiting example, when bisphenol A as an aromatic diol compound and triphosgene as a carbonate precursor are polymerized, the repeating unit of Formula 1 may be represented by Formula 1-1 below.

[Formula 1-1]

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, and preferably, triphosgene or phosgene may be used.

Meanwhile, the second polycarbonate-based repeating unit having at least one siloxane bond is formed by reacting at least one siloxane compound and a carbonate precursor, and in a specific example, at least one repeating unit selected from the group consisting of the following formula (2) It may include, more suitably, may further include one or more repeating units selected from the group consisting of the following Formula 3:

[Formula 2]

In Chemical Formula 2,

Each X ₁ is independently C _1-10 alkylene,

Each Y ₁ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

Each R ₅ is 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,

m is an integer from 10 to 200

[Formula 3]

In Chemical Formula 3,

Each X ₂ is independently C _1-10 alkylene,

Each R ₆ is 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,

n is an integer from 10 to 200.

And, in Formula 2, preferably, each of X ₁ may be independently C _2-10 alkylene, more preferably C _2-6 alkylene, and most preferably isobutylene.

Preferably, in Formula 2, Y ₁ may be hydrogen.

In Formula 2, R ₅ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxyranylmethoxy)propyl, fluoro, chloro, bromo, iodo, and Oxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. In addition, preferably, each of R ₅ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

In Formula 2, m is an integer of 10 to 200, preferably i) an integer of 30 to 60, ii) an integer of 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, and may be an integer of 70 or less, 65 or less, or 60 or less.

For example, the repeating unit of Formula 2 may be represented by Formula 2-1:

[Formula 2-1]

In Formula 2-1, R ₅ and m are as defined above. Preferably, R ₅ is methyl.

And in Formula 3, each of X ₂ may be independently C _2-10 alkylene, preferably C _2-4 alkylene, and more preferably propane-1,3-diyl.

In Formula 3, each of R ₆ is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo , Methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R ₆ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

In Formula 3, n is an integer of 10 to 200, preferably i) an integer of 30 to 60, or ii) an integer of 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, and may be an integer of 70 or less, 65 or less, or 60 or less.

For example, the repeating unit of Formula 3 may be represented by the following Formula 3-1:

[Formula 3-1]

In Formula 3-1, R ₆ and n are as defined above. Preferably, R ₆ is methyl.

According to an embodiment of the present invention, the copolycarbonate resin may include one or more repeating units selected from the group consisting of Formula 2, and more suitably, one or more repeating units selected from the group consisting of Formula 3 It may contain more. In addition, the copolycarbonate resin may include two or more kinds of each repeating unit of Formulas 2 and/or 3 above.

When the repeating units of Formulas 2 and 3 were included together, or when two or more of each of the repeating units were included together, it was confirmed that the degree of improvement in room temperature impact strength, low temperature impact strength, and fluidity significantly increased. It is due to the result that the degree of improvement of physical properties by the unit worked complementarily.

The term'two or more kinds of repeating units' as used herein refers to two or more kinds of repeating units having different structures within the scope of each formula, or having the same structure, but the number of repeating units of silicon oxide in the structures of formulas 2 and 3 ( It means that n1 or n2) contains two or more different types.

For example, the term'two or more types of repeating units' as used herein means i) one repeating unit represented by Formula 2 and another repeating unit represented by Formula 2, or ii) represented by Formula 3 It means including one repeating unit and another repeating unit represented by Chemical Formula 3.

In each case including the two kinds of repeating units, the weight ratio between the two kinds of repeating units may be 1:99 to 99:1. Preferably, it may be 3:97 to 97:3, 5:95 to 95:5, 10:90 to 90:10, or 15:85 to 85:15, more preferably 20:80 to 80:20 Can be When included in the above weight ratio, it may exhibit superior room temperature impact strength, low temperature impact strength, and fluidity.

The repeating units represented by Formulas 2 and 3 may be derived from a siloxane compound represented by Formula 2-2 and a siloxane compound represented by Formula 3-2, respectively:

[Formula 2-2]

In Formula 2-2,

The X ₁ , Y ₁ , R ₅ and m are each as defined in Formula 2,

[Chemical Formula 3-2]

In Formula 3-2,

Each of X ₂ , R ₆ and n is as defined in Chemical Formula 2.

The meaning of "derived from a siloxane compound" means that the hydroxy group of each of the siloxane compounds reacts with the carbonate precursor to form the repeating units represented by Formulas 2 and 3, respectively. In addition, the carbonate precursor that can be used to form the repeating unit of Formulas 2 and 3 is as described in the carbonate precursor that can be used to form the repeating unit of Formula 1 described above.

By adjusting the content of the repeating unit represented by Formulas 2 and 3, physical properties of the copolycarbonate resin may be improved. Here, the weight ratio of the repeating unit corresponds to the weight ratio of the siloxane compound used in the polymerization of the copolycarbonate, such as the siloxane compound represented by Formulas 2-2 and 3-2.

In the copolycarbonate resin, the molar ratio of the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is 1:0.0001 to 1:0.01, or 1:0.0005 to 1:0.008 , Or 1:0.001 to 1:0.006, the weight ratio may be 1:0.001 to 1:1, or 1:0.005 to 1:0.1, or 1:0.01 to 1:0.03. When included in the above content ratio, it may exhibit superior room temperature impact strength, low temperature impact strength, and fluidity.

In addition, the copolycarbonate resin may include 90 to 99.999 wt% of the first repeating unit and 0.001 to 10 wt% of the second repeating unit based on the total weight of the copolycarbonate resin. When the first repeating unit and the second repeating unit are included within the above content ratio range, the copolycarbonate resin may exhibit excellent flowability and molding processability by having a molecular weight within an appropriate range. Accordingly, at room temperature of the resin composition Impact strength, low temperature impact strength, chemical resistance and fluidity can be improved. More preferably, it may include 90 to 95% by weight of the first repeating unit and 5 to 10% by weight of the second repeating unit based on the total weight of the copolycarbonate resin.

In addition, the copolycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g/mol, preferably 5,000 to 50,000 g/mol. Appropriate ductility and YI of the copolycarbonate resin may be secured within the weight average molecular weight range. More preferably, the weight average molecular weight (g/mol) is 1,000 or more, 5,000 or more, 10,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 27,000 or more, or 28,000 or more. Further, the weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.

The copolycarbonate resin can be prepared using the above-described aromatic diol compound, carbonate precursor, and one or more siloxane compounds, and physical properties such as weight average molecular weight can be appropriately controlled through control of the type and content of reactants and reaction conditions. I can. Details of polymerization are omitted.

The content of the copolycarbonate resin may vary depending on the physical properties of the composition to be controlled. However, if the content is too small, it is difficult to obtain a sufficient impact resistance improvement effect according to the use of copolycarbonate resin, and if the content is too high, the transparency of the resin composition may be lowered, and the effect of improving heat resistance and impact strength is at a critical value. Since it may reach or rather be degraded, specifically, the copolycarbonate resin may be included in 5 to 35% by weight, more preferably 5 to 30% by weight, based on the total content of the resin composition of one embodiment. When included in the above content range, it can exhibit improved impact resistance and heat resistance while maintaining excellent transparency.

(c) flat glass fiber

On the other hand, the resin composition of one embodiment includes flat glass fibers in the form of a cocoon or flat type in order to supplement the rigidity of the resin composition and improve the warpage characteristics and smoothness.

Specifically, the flat glass fiber has a rectangular or elliptical cross-section of the glass fiber cut vertically with respect to the longitudinal direction, and the aspect ratio represented by the following equation 1 is 50 to 200, more preferably 100 to 150 Can be.

[Equation 1]

Aspect ratio (δ) = L/D

In Equation 1, L is the length of the glass fiber, and D is the length of the longest side of the rectangular section, the length of the diameter of the circular section, or the length of the longest diameter of the elliptical section.

When the flat glass fibers having the above morphological and structural characteristics are used, the glass fibers maintain a very strong bonding force between the resins to adequately absorb external impacts through the space between the resin and the glass fibers, and thus the rigidity and toughness of the resin composition. The varnish can be improved, and by having a low aspect ratio (L/D), the bending characteristics and surface smoothness are increased, so that a rigid frame can be manufactured during plastic processing of thin film products.

If, outside the structural requirements of the glass fiber, the aspect ratio is less than 50, the resin composition and the molded article of one embodiment may become brittle, which is not preferable, and if the aspect ratio exceeds 200, the Due to the high possibility of surface protrusion, surface properties such as surface smoothness and product appearance may be deteriorated, and toughness and impact strength of molded products may be deteriorated.

In addition, the glass fiber has a length (L) of 2 to 5 mm under the conditions satisfying the above-described morphological and structural characteristics, and the shortest side is 5 to 15 μm or an elliptical shape if the cross section cut in the vertical direction to the length direction is a rectangle. In the case of, the shortest diameter may be 5 to 15 μm, more preferably 3 to 4 mm in length, and if the cross section of the glass fiber cut in the vertical direction is rectangular, the shortest side is 7 to 110 μm or , In case of an elliptical shape, the shortest diameter may be 7 to 10 μm.

If the length of the glass fiber is less than 2mm, there is a concern that the effect of developing rigidity may not be sufficient, and if it exceeds 5mm, there is a concern that the occurrence rate of appearance defects during product molding may increase relatively. In addition, when the cross section of the glass fiber of the present invention cut in the longitudinal direction is rectangular, the shortest side (the thickness of the glass fiber) is less than 5 µm, or in the case of an ellipse, the shortest diameter is less than 5 µm. ) May increase, and if the shortest side of the cross-section exceeds 15 μm or the shortest diameter exceeds 15 μm in the case of an elliptical shape, there is a concern of protruding the surface of the glass fiber.

In addition, the glass fiber may contain an epoxy silane group on the surface. When an epoxy silane group is included as a functional group on the surface, since the epoxy group forms a chemical bond with a functional group of another composition, the rigidity of the polycarbonate can be further improved.

The flat glass fiber may be included in a higher content than the conventional glass fiber due to its unique shape. However, if the content of the glass fiber is too high, the flowability deteriorates and the processing temperature increases, and there is a concern that the surface smoothness or appearance characteristics of the molded article may be deteriorated due to the protrusion of the glass fiber. In addition, when the content of the glass fiber is too small, it may not be sufficient to improve the strength or warpage characteristics of the resin composition and molded article of one embodiment. Accordingly, the flat glass fiber may be included in an amount of 40 to 60% by weight, more preferably 50 to 60% by weight, based on the total content of the resin composition of one embodiment. When included in the above content range, excellent processability can be exhibited, and as a result, surface smoothness and appearance characteristics of the molded article can be improved.

(d) glycol-modified polyethylene terephthalate

The glycol-modified polyethylene terephthalate (PETG) is an amorphous resin copolymerized by adding 1,4-cyclohexanedimethanol (CHDM) as a comonomer during the reaction of terephthalic acid and ethylene glycol, and has excellent transparency, impact resistance, and chemical resistance. It can be molded in a wide range of conditions. In the resin composition according to an embodiment of the present invention, the glycol-modified polyethylene terephthalate lowers the glass transition temperature of the resin composition to prevent the glass fibers from protruding over the surface, thereby improving the surface appearance characteristics of the resin composition. do. In addition, unlike polyethylene terephthalate (PET), which is a crystalline polyester produced by the polycondensation reaction of terephthalic acid (TPA) and ethylene glycol (EG), it is amorphous, so it can exhibit excellent transparency without whitening even when heat is applied. have.

In addition, compared to polyethylene terephthalate (PET), compatibility with polycarbonate is excellent, and impact strength is excellent.

Specifically, PETG may be a compound represented by Formula 4:

[Formula 4]

In Formula 4, x and y are molar ratios of each repeating unit, and may be determined from the weight average molecular weight of glycol-modified polyethylene terephthalate.

Specifically, in the PETG, the repeating unit structure derived from CHDM may be included in 20% by weight or less based on the total weight of the PETG polymer. When the content of the repeating unit structure derived from CHDM is 20% by weight or less, the glass transition temperature in the resin composition may be lowered to exhibit a better appearance surface property improvement effect, and more specifically, the content of the repeating structure derived from CHDM is 1 to 10% by weight, more More specifically, when it is 1 to 5% by weight, the effect of external surface characteristics can be further improved.

In addition, the PETG may have a glass transition temperature (Tg) of 150 to 190°C, more preferably 170 to 180°C. When it has a glass transition temperature in the above range, it is possible to exhibit a better effect of improving the appearance surface characteristics.

The content of PETG may vary depending on the physical properties of the composition to be controlled. However, if the content is too small, the effect of reducing the glass transition temperature and improving the appearance surface characteristics accordingly may be insignificant, and if the content is too high, separation of the polycarbonate and PETG may cause a peeling phenomenon or an ester exchange reaction. Since there is a concern, the PETG may be included in 1 to 10% by weight, more preferably 5 to 10% by weight based on the total weight of the polycarbonate-based resin composition. When included within the above content range, it can exhibit excellent external surface properties.

(5) Other additives

In addition, the polycarbonate-based resin composition of one embodiment may further include a phosphorus-based flame retardant in addition to each component described above.

Examples of the phosphorus-based flame retardant include a monophosphate compound, a phosphate oligomer compound, a phosphonate oligomer compound, a phosphonitrile oligomer compound, or a phosphonic acid amide compound, and any one or a mixture of two or more thereof may be used.

Among them, a phosphoric acid ester compound represented by the following formula (5) may be preferably used:

[Formula 5]

In Chemical Formula 5,

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently a halogen-free aromatic group,

,

또는

이고; 상기 R⁷ 내지 R¹⁴는 각각 독립적으로 수소 원자 또는 C_1-5 알킬기이고; 상기 G는 직접 결합(direct binding), O, S, SO₂, C(CH₃)₂, CH₂, CHPh를 나타내고, 상기 Ph는 페닐기이고,Q is

,

or

ego; Each of R ⁷ to R ¹⁴ is independently a hydrogen atom or a C _1-5 alkyl group; Wherein G represents direct binding, O, S, SO ₂ , C(CH ₃ ) ₂ , CH ₂ , CHPh, and Ph is a phenyl group,

n is an integer greater than or equal to 1,

k and m are each an integer of 0 or more and 2 or less, and (k+m) is an integer of 0 or more and 2 or less.

The phosphoric acid ester compound has a high level of V-0 or V-1 according to the UL 94 V Test while minimizing the deterioration of the intrinsic properties of the above-described polycarbonate resin and the effect of improving physical properties due to the addition of the copolycarbonate resin. It enables the expression of flame retardancy.

In addition, the phosphoric acid ester compound represented by Chemical Formula 5 may include a mixture of different n or condensed phosphoric acid esters having different structures.

In Formula 5, n is an integer greater than or equal to 1, and the upper limit thereof is preferably 40 or less in terms of expression of flame retardancy; It may be preferably 1 to 10, more preferably 1 to 5.

In Formula 5, k and m are each an integer of 0 or more and 2 or less, and (k+m) is an integer of 0 or more and 2 or less; Preferably, it may be an integer of 0 or more and 1 or less, and more preferably 1 each.

In Q of Formula 5, R ⁷ to R ¹⁴ are each independently a hydrogen atom or a C _1-5 alkyl group; Specifically, it may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, neopentyl, and the like; Preferably hydrogen, methyl or ethyl; More preferably, it may be hydrogen.

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ of Formula 5 are each independently a halogen-free aromatic group, and specifically, may be an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton. In addition, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may each be substituted with an organic residue having 1 to 8 carbon atoms that does not contain halogen. For example, the Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently phenyl, tolyl, cresyl, xylyl, isopropylphenyl, butylphenyl, tert-butylphenyl, di-tert-butylphenyl, p-cumylphenyl and the like.

In a more specific example, the phosphoric acid ester compound represented by Formula 5 may be a compound represented by Formulas 5-1 to 5-4:

[Chemical Formula 5-1]

[Formula 5-2]

[Chemical Formula 5-3]

[Chemical Formula 5-4]

In Formulas 5-1 to 5-4, a, b, c, and d are each independently an integer of 1 or more.

As a non-limiting example, commercially available phosphoric acid ester compounds include PX-200, PX-201, PX-202, CR-733S, CR-741, CR747 (above DAIHACHI CHEMICAL INDUSTRY Co., Ltd.); FP-600, FP-700, FP-800 (ADEKA Co.), etc. are mentioned.

Meanwhile, the phosphorus-based flame retardant may be included in an amount of 1 to 10% by weight, or 1 to 5% by weight, based on the total content of the resin composition of one embodiment. As a result, while the resin composition of one embodiment can exhibit excellent flame retardancy, it is possible to minimize a decrease in mechanical properties of a molded article due to the addition of the flame retardant.

In addition, the polycarbonate-based resin composition of one embodiment may further include an impact modifier for reinforcing the impact strength of the resin composition and the molded article thereof.

The impact modifier may include an ethylene-based impact modifier, or an impact modifier of a rubber-modified vinyl-based graft copolymer, and any one or a mixture of two or more of them may be used.

As the ethylene-based impact modifier, an ethylene methyl acrylate copolymer capable of enhancing toughness of a resin composition and a molded article thereof and improving flow characteristics may be used.

More specifically, the ethylene methyl acrylate copolymer may include 15 to 50% by weight of methyl acrylate based on the total weight of the copolymer. When the methyl acrylate is included in the above content range, it may exhibit a sufficient effect of improving toughness along with better processability.

In addition, the rubber-modified vinyl-based graft copolymer is specifically, a vinyl-based unsaturated monomer is grafted into a core structure including at least one rubber selected from the group consisting of diene-based rubber, acrylate-based rubber, and silicone-based rubber. It may be a graft copolymer having a core-shell structure formed therein.

In the impact modifier in the form of such a graft copolymer, as the rubber, at least one type of diene-based rubber, acrylate-based rubber, or silicone-based rubber having 4 to 6 carbon atoms may be used, and in terms of structural stability of the impact modifier, Silicone rubber, acrylate rubber or silicone-acrylate rubber may be more appropriately used.

In a more specific example, the acrylate-based rubber is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, or a rubber formed from a (meth) acrylate monomer such as hexyl (meth) acrylate may be used, and ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate for the formation of such rubber , 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, allyl (meth) acrylate, or triallyl cyanurate, such as a curing agent may be further used. .

In addition, as the silicone rubber, those manufactured from cyclosiloxane may be used. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrosiloxane, and octaphenylcyclotetrasiloxane. Those prepared from one or more selected from the group consisting of may be used. In addition, for the formation of the silicone rubber, a curing agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, or tetraethoxysilane may be further used.

In addition, in the above-described impact modifier, as the vinyl-based unsaturated monomer grafted onto the rubber, one or more types of an aromatic vinyl-based monomer or a monomer copolymerizable with the aromatic vinyl-based monomer may be used.

The aromatic vinyl monomer may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, or ethylstyrene. These may be used alone or in combination of two or more. In addition, as the monomer copolymerizable with the aromatic vinyl-based monomer, a vinyl cyanide compound, an alkyl (meth)acrylate having 1 to 12 carbon atoms, (meth)acrylate or an alkyl or phenyl substituted maleimide having 1 to 12 carbon atoms may be used. I can. These may be used alone or in combination of two or more.

The impact modifier in the form of the rubber-modified vinyl-based graft copolymer described above may be directly synthesized according to a method well known to those skilled in the art, or may be obtained and used commercially.

The above-described impact modifier may be included in an amount of 1 to 10% by weight, more preferably 2 to 5% by weight, based on the total content of the resin composition of one embodiment. When the content of such an impact modifier is excessively large, there is a possibility that the effect of improving the additional impact strength is substantially absent or the rigidity is rather lowered, and on the contrary, when the content of the impact modifier is too small, the resin composition and molded article of one embodiment The impact resistance, such as the impact strength of, may not be sufficient.

In addition to the above compounds, the polycarbonate-based resin composition according to an embodiment of the present invention includes a coupling agent as needed; Heat stabilizer; Lubricant; drip inhibitors such as fluorine-based polymers such as polytetrafluoroethylene (PTFE); Surfactants; Nucleating agent; Filler; Plasticizer; Antibacterial agents; Mold release agent; Antioxidants; UV stabilizer; Compatibilizer; coloring agent; Antistatic agents; Pigment; dyes; Additives such as flame retardants may be additionally included.

The content of these additives may vary depending on the physical properties to be given to the composition. For example, the additive may be included in an amount of 1 to 10% by weight, or 1 to 5% by weight, based on the total content of the resin composition. When included within the above content range, the effect of using the additive can be sufficiently implemented without deteriorating the physical properties of the resin composition according to the invention.

According to another embodiment of the present invention, a molded article comprising the above-described polycarbonate-based resin composition 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-based resin composition into pellets, and then drying the pellets to inject.

In particular, as the molded article is formed from the polycarbonate-based resin composition, it can exhibit low deformation characteristics, excellent impact strength and surface characteristics of the exterior, and excellent flame retardancy, and can be suitably used as a housing material for portable electronic devices such as tablet PCs. I can.

The polycarbonate-based resin composition and the molded article thereof according to the present invention exhibit external surface characteristics with high stiffness and excellent impact strength. Accordingly, it is useful as a housing material for portable electronic devices such as a tablet PC.

1 to 3 are photographs of the specimen surfaces prepared in Example 1, Comparative Example 1, and Comparative Example 3, respectively, observed with a confocal microscope (magnification: 5x).

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

Manufacturing Example 1

Preparation of polyorganosiloxane (AP-PDMS, n=34)

After mixing 47.6 g (160 mmol) of octamethylcyclotetrasiloxane and 2.4 g (17.8 mmol) of tetramethyldisiloxane, the mixture was mixed with 1 part by weight of acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane. Put together in a 3L flask and reacted at 60°C for 4 hours. After completion of the reaction, it was diluted with ethyl acetate and rapidly filtered using celite. The repeating unit (n1) of the thus obtained unmodified polyorganosiloxane was 34 as a result of ¹ H NMR.

To the obtained terminal unmodified polyorganosiloxane, 4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added and reacted at 90° C. for 3 hours. After completion of the reaction, the unreacted siloxane was removed by evaporation under conditions of 120°C and 1 torr. The terminal-modified polyorganosiloxane thus obtained was named AP-PDMS (n1=34). AP-PDMS is a pale yellow oil, and it was confirmed that the repeating unit (n1) was 34 through ¹ H NMR using Varian 500MHz, and further purification was not required.

Manufacturing Example 2

Preparation of polyorganosiloxane (MBHB-PDMS, n2=58)

After mixing 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 mmol) of tetramethyldisiloxane, the mixture was mixed with 1 part by weight of acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane. Put together in a 3L flask and reacted at 60°C for 4 hours. After completion of the reaction, it was diluted with ethyl acetate and rapidly filtered using Celite. The repeating unit (n2) of the terminal unmodified polyorganosiloxane thus obtained was 58 as a result of ¹ H NMR.

6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate (3-methylbut-3-enyl 4-hydroxybenzoate) and Carlsted's platinum catalyst (Karstedt's) in the obtained terminal unmodified polyorganosiloxane platinum catalyst) 0.01 g (50 ppm) was added and reacted at 90°C for 3 hours. After completion of the reaction, the unreacted siloxane was removed by evaporation under conditions of 120°C and 1 torr. The terminal-modified polyorganosiloxane thus obtained was named MBHB-PDMS (n2=58). MBHB-PDMS is a pale yellow oil, and it was confirmed that the repeating unit (n2) was 58 through ¹ H NMR using Varian 500MHz, and further purification was not required.

Manufacturing Example 3

Preparation of copolycarbonate resin

1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved in an N ₂ atmosphere. Here, a mixture of 4.3 g of PTBP (para-tert butylphenol), 4.72 g of AP-PDMS (n1 = 34) according to Preparation Example 1, and 0.52 g of MBHB-PDMS (n2 = 58) according to Preparation Example 2 was mixed with MC (methylene chloride). ) And put in. Then, 128 g of TPG (triphosgene) was dissolved in the MC, and the pH was maintained at 11 or higher and added for 1 hour to react. After 10 minutes, 46 g of TEA (triethylamine) was added to perform a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed 3 times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120° C. to finally obtain a copolycarbonate resin (Mw=30,500 g/mol).

Examples and Comparative Examples

Each component was added to the composition shown in Table 1, mixed well with a mixer, and then melt-extruded in a temperature range of 250 to 320°C with a twin screw extruder to prepare pellets. The prepared pellet was dried at 80° C. for 4 hours and then injected to prepare a specimen for physical property evaluation. The prepared specimen was used after standing at room temperature for 48 hours or more.

Components used in each Example and Comparative Example are as follows.

(A) Bisphenol A polycarbonate resin (PC)

Polycarbonate resin is a polymer of bisphenol A, its melt index (MI) was measured as a weight (g) measured for 10 minutes under a temperature of 300° C. and a load of 1.2 kg according to ASTM D1238. As a result of this measurement, an aromatic polycarbonate resin having a melt index of 22 g/10 min was used (PC1300-10™, LG Chem.).

(B) Copolycarbonate resin (Si-PC)

The copolycarbonate resin prepared in Preparation Example 3 was used (PC 8000-05™, LG Chem.).

(C1) flat glass fiber

The cross section cut in the vertical direction with respect to the longitudinal direction is an oval, the length (L) is 3 mm, the longest diameter (width, D) of the ellipse is 28 μm and the shortest diameter is 7 μm, calculated by Equation 1 below. The aspect ratio (δ) was 107, and a glass fiber surface-treated with an epoxy silane compound was used (CSG3PA-830™ by Nittobo).

[Equation 1] Aspect ratio (δ) = L/D

(In Equation 1, L is the length of the glass fiber, and D is the length of the longest diameter of the elliptical cross section)

(C2) Glass fiber

The cross section cut in the vertical direction to the longitudinal direction is circular, the length (L) is 3 mm, the diameter (D) in the circle is 10 to 13 μm, the aspect ratio (δ) is 231 to 300, and the surface is made of epoxy silane. The treated glass fiber was used (manufactured by Owens Corning).

(D1) Glycol-modified polyethylene terephthalate (PETG)

Glycol-modified polyethylene terephthalate from SK Chemicals, SKYGREEN PETG S2008™ (content of repeating structure derived from CHDM in PETG: 5% by weight, glass transition temperature (Tg): 176°C) was used.

(D2) Polyethylene terephthalate (PET)

(E) Flame retardant

Bisphenol phosphate PX-200™ (Melting Point: 97°C, P content = 9.0% by weight) manufactured by Dai-Hachi, Japan was used.

(F) Impact modifier

DuPont's ethylene methyl acrylate copolymer Elvaloy 1330AC™ was used.

(G) Coupling agent: Momentive's A-187™ was used.

(H) Thermal stabilizer: IR1076™ from Ciba was used.

(I) Lubricant: Faci's PETS-AHS™ was used.

(weight%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PC 33 23 8 43 38 - - 23 23 Si-PC 5 15 30 0 0 43 38 15 15 Flat glass fiber
(C1) 50 50 50 50 50 50 50 - 50 Fiberglass
(C2) - - - - - - - 50 - taking over
Flame retardant 4 4 4 4 4 4 4 4 4 PETG 5 5 5 - 5 - 5 5 - PET - - - - - - - - 5 Impact modifier 2 2 2 2 2 2 2 2 2 Coupling agent 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Heat stabilizer 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Lubricant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 total 100 100 100 100 100 100 100 100 100

Test example

Physical properties were measured in the following manner for each specimen formed from the compositions of the Examples and Comparative Examples, and the results are shown in Table 2 below.

(1) Flow Index (MI): According to ASTM D1238, it was calculated as weight (g) measured for 10 minutes under a temperature of 300° C. and a load of 1.2 kg.

(2) Flexural elasticity: It was measured by ASTM D790 method.

(3) Impact strength (IZOD): Measured in 1/8 inch (Notched Izod, J/m) under 23° C. according to ASTM D256.

(4) Visual evaluation of appearance: Through injection into the product injection mold, it was visually checked whether or not the gate mark and white fog phenomenon were improved, and evaluated according to the following criteria.

◎: Excellent appearance

○: Good appearance

X: Poor appearance

The specimen surfaces prepared in Example 1, Comparative Example 1, and Comparative Example 3 were observed with a confocal microscope (Model: Keyence VK-X200, magnification: 5x (measurement area: 2.5 mm)), and the results are shown in FIGS. 1 to 3 Each is shown in.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Flow index
(g/10min) 14 12 10 14 15 8 8 12 15 Flexural elasticity (kgf/cm ² ) 152,000 150,000 145,000 150,000 150,000 130,000 130,000 140,000 155,000 Impact strength
(kgcm/cm) 17 18 20 8 9 17 20 15 12 Visual evaluation of the appearance ⊙ ⊙ ⊙ O O X X X O

Referring to FIGS. 1 to 3 together with Table 2, Examples 1 to 3 exhibited excellent impact strength and appearance characteristics while exhibiting high rigidity compared to Comparative Examples 1 to 6.

Claims (19)

Based on the total weight of the polycarbonate resin composition,
5 to 35% by weight of a polycarbonate resin composed of an aromatic polycarbonate-based repeating unit;
5 to 35% by weight of a copolycarbonate resin comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond;
50 to 60% by weight of flat glass fibers; And
Including 1 to 10% by weight of glycol-modified polyethylene terephthalate resin,
The flat glass fiber is a polycarbonate-based resin composition having a shape of a rectangle or an elliptical cross section of the glass fiber cut vertically with respect to the longitudinal direction and an aspect ratio of 50 to 200 represented by Equation 1 below:
[Equation 1]
Aspect ratio (δ) = L/D
In Equation 1, L is the length of the flat glass fiber, and D is the length of the longest side of the cross section when the cross section of the glass fiber is cut perpendicular to the length direction, and D is the longest side of the elliptical cross section. It is the length of the diameter.
The method of claim 1,
The aromatic polycarbonate-based repeating unit in the polycarbonate resin comprises one or more repeating units selected from the group consisting of the following formula (1), a polycarbonate-based resin composition:
[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 method of claim 1,
The aromatic polycarbonate-based repeating unit in the polycarbonate resin comprises a repeating unit represented by the following Formula 1-1, a polycarbonate-based resin composition:
[Formula 1-1]

.
The method of claim 1,
The polycarbonate resin has a melt index of 5 g/10 minutes to 25 g/10 minutes under a temperature of 300° C. and a load of 1.2 kg, a polycarbonate resin composition.
The method of claim 1,
The aromatic polycarbonate-based repeating unit in the copolycarbonate resin includes a repeating unit represented by Formula 1 below,
The aromatic polycarbonate-based repeating unit having at least one siloxane bond includes a repeating unit represented by the following formula (2), a polycarbonate-based resin composition:
[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 unsubstituted or substituted by phenyl or a C _1-10 alkylene, or C _1-10 unsubstituted or substituted with a C _3-15 alkyl cycloalkylene, O, S, SO, SO _2, or CO, and;
[Formula 2]

In Chemical Formula 2,
Each X ₁ is independently C _1-10 alkylene,
Each Y ₁ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,
Each R ₅ is 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,
m is an integer from 10 to 200.
The method of claim 5,
The repeating unit of Formula 2 is a polycarbonate-based resin composition represented by Formula 2-1:
[Formula 2-1]

In Formula 2-1,
Each of R ₅ and m is as defined in Chemical Formula 2.
The method of claim 1,
The aromatic polycarbonate-based repeating unit having at least one siloxane bond in the copolycarbonate resin further comprises a repeating unit represented by the following formula (3), a polycarbonate-based resin composition:
[Formula 3]

In Chemical Formula 3,
Each X ₂ is independently C _1-10 alkylene,
Each R ₆ is 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,
n is an integer from 10 to 200.
The method of claim 7,
The repeating unit of Formula 3 is a polycarbonate-based resin composition represented by Formula 3-1:
[Formula 3-1]

In Formula 3-1,
Each of R ₆ and n is as defined in Chemical Formula 3.
The method of claim 1,
The copolycarbonate resin comprises 90 to 99.999% by weight of the aromatic polycarbonate-based repeating unit and 0.001 to 10% by weight of the aromatic polycarbonate-based repeating unit having one or more siloxane bonds based on the total weight of the copolycarbonate resin. Polycarbonate resin composition containing.
The method of claim 1,
The copolycarbonate resin is a polycarbonate-based resin composition having a weight average molecular weight of 1,000 to 100,000 g/mol.
The method of claim 1,
The flat glass fiber has a length (L) of 2 to 5 mm, the shortest side is 5 to 15 µm when the cross section cut in the vertical direction with respect to the length direction is a rectangle, and the shortest diameter is 5 to 15 µm in the case of an elliptical shape. Μm, a polycarbonate resin composition.
The method of claim 1,
The flat glass fiber comprises an epoxy silane group on the surface, polycarbonate-based resin composition.
The method of claim 1,
The glycol-modified polyethylene terephthalate contains a repeating unit structure derived from 1,4-cyclohexanedimethanol in an amount of 20% by weight or less based on the total weight of the glycol-modified polyethylene terephthalate.
The method of claim 1,
The glycol-modified polyethylene terephthalate has a glass transition temperature of 150 to 190 ℃, polycarbonate-based resin composition.
The method of claim 1,
The polycarbonate-based resin composition further comprises one or more additives selected from the group consisting of an impact modifier, a phosphorus-based flame retardant, a coupling agent, a heat stabilizer, and a lubricant.
The method of claim 15,
The impact modifier is a polycarbonate-based resin composition comprising at least one of an ethylene methyl acrylate copolymer and a rubber-modified vinyl-based graft copolymer.
The method of claim 15,
The phosphorus-based flame retardant comprises a phosphoric acid ester-based compound represented by the following formula (5), a polycarbonate-based resin composition:
[Formula 5]

In Chemical Formula 5,
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently a halogen-free aromatic group,
Q is

,

or

ego,
R ⁷ to R ¹⁴ are each independently a hydrogen atom or a C _1-5 alkyl group,
G is a direct bond, O, S, SO ₂ , C(CH ₃ ) ₂ , CH ₂ , or CHPh (where Ph is a phenyl group),
k and m are each an integer of 0 or more and 2 or less, and (k+m) is an integer of 0 or more and 2 or less,
n is an integer of 1 or more.
The method of claim 1,
Based on the total weight of the polycarbonate resin composition
5 to 35% by weight of the polycarbonate resin,
5 to 35% by weight of the copolycarbonate resin,
50 to 60% by weight of the flat glass fiber, and
Including 1 to 10% by weight of the glycol-modified polyethylene terephthalate,
1 to 10% by weight of an impact modifier, and
Polycarbonate-based resin composition further comprising 1 to 10% by weight of a phosphorus-based flame retardant.
A molded article comprising the polycarbonate resin composition of any one of claims 1 to 18.

Images