WO2016089137A1

WO2016089137A1 - Copolycarbonate composition and article comprising same

Info

Publication number: WO2016089137A1
Application number: PCT/KR2015/013159
Authority: WO
Inventors: 고운; 반형민; 황영영; 박정준; 홍무호; 이기재; 전병규; 손영욱; 고태윤
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-04
Filing date: 2015-12-03
Publication date: 2016-06-09

Abstract

The present invention relates to a copolycarbonate resin composition comprising copolycarbonate, of which a certain siloxane compound is introduced to the main chain of polycarbonate, and a UV stabilizer. The copolycarbonate resin composition has excellent weatherability, and thus articles produced using the same are characterized by having low degradation in surface qualities and properties due to ultraviolet rays, etc. following external exposure.

Description

[Name of invention]

Copolycarbonate Compositions and Articles Comprising the Same

[Cross Citation with Related Application (s)]

. This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0173005 dated December 4, 2014 and Korean Patent Application No. 10-2015-0159987 dated November 13, 2015. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a copolycarbonate composition having excellent weather resistance and an article comprising the same.

Background Art

Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have excellent impact strength, numerical stability, heat resistance and transparency, and are used for exterior materials, automobile parts, building materials, and optical parts of electric and electronic products. It is applied to a wide range of fields. In order to apply such polycarbonate resins in recent years, many studies have been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic dialkyl compounds to introduce units having different structures into the main chain of polycarbonate. . Products made of polycarbonate resin, when exposed to the outside will exhibit a decrease in surface quality and physical properties due to ultraviolet rays and the like. Therefore, weather resistance which does not reduce the physical property of a polycarbonate resin is calculated | required by such an ultraviolet-ray. Accordingly, the present inventors have completed the present invention by confirming that a copolycarbonate resin composition including a copolycarbonate and a UV stabilizer in which a specific siloxane compound is introduced into a polycarbonate backbone as described below has excellent physical properties such as weather resistance. . [Content of invention]

[Problem to solve]

The present invention is to provide a copolycarbonate composition excellent in weatherability.

The present invention also provides an article comprising the copolycarbonate composition.

[Measures of problem]

In order to solve the above problems, the present invention (a) an aromatic polycarbonate-based first repeating unit; And (b) a copolycarbonate comprising an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and (b) a UV stabilizer, wherein ΔΥ of Formula 1 is 7 or less. do:

[Equation 1]

Δ ΥΙ = YK500 hours)-YK0 hours)

In Equation 1,

YK0 hours) is a YI (Yel low Index) value measured according to ASTM D1925 for the copolycarbonate composition,

YK500 time) ASTM D4329 The copolycarbonate a second ultraviolet light of 340 nm at 60 ^° C Dangerous after 500 hours with the light amount of 0.55 w / m ² irradiation, a YI (Yel measured according to ASTM D1925 low Index on the basis of the ) Value. When the product is manufactured using the copolycarbonate, the product is exposed to the outside, resulting in deterioration of surface quality and physical properties due to ultraviolet rays. Therefore, in order to minimize the degradation of physical properties due to such ultraviolet rays, the present invention is characterized by using a UV stabilizer together with a copolycarbonate. Hereinafter, the present invention will be described in more detail. Copolycarbonate Copolycarbonate according to the present invention, an aromatic polycarbonate-based first repeating unit; And aromatic polycarbonate-based second repeating units having one or more siloxane bonds. The aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic diol compound and a carbonate precursor, and is preferably represented by the following Chemical Formula 1.

[Formula 1]

^ R,

In Chemical Formula 1,

Ri to ¾ are each independently hydrogen, d- ₁₀ alkyl, d-ra alkoxy, or halogen,

₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO - X are either unsubstituted or substituted with dH) alkylene, unsubstituted or alkyl substituted in the phenyl by C _3. In Formula 1, preferably, ¾ to R ₄ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, X is straight or branched chain d-) alkylene which is 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, X is cyclonucleic acid-1, 1-diyl, 0, S, SO, S0 ₂ , or CO. Preferably, the repeating unit represented by Formula 1 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl ) Sulfoxide, Bis (4- Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1, 1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2, 2-bis (4-hydroxyphenyl) butane, 1, 1 Bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichloro Phenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy ᅳ 3-chlorophenyl) propane, 2, 2-bis (4—hydr 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 any one or more aromatic di selected from the group consisting of a, c —bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane may be derived from the compound. The term “derived from an aromatic diol compound” means that a hydroxyl group and a carbonate precursor of an aromatic diol compound react to form a repeating unit represented by the formula (1). For example, when bisphenol A as an aromatic di compound and triphosgene as a carbonate precursor are polymerized, the repeating unit represented by Formula 1 is represented by the following Formula 1-1.

1-1]

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, and bis. At least one selected from the group consisting of (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used. Preferably, triphosgen or Phosgene can be used. The aromatic polycarbonate-based second repeating unit having one or more siloxane bonds is formed by reacting at least one siloxane compound and a carbonate precursor, preferably a repeating unit represented by the following Formula 2 and the following formula 3 Contains the unit:

In Chemical Formula 2,

Each Xi is independently d-κ) alkylene,

Each ¾ is independently hydrogen; The dK) is substituted by unsubstituted or substituted oxiranyl, oxiranyl alkoxy, or C ₆ - ₂₀ aryl substituted with a _C-15 alkyl; halogen; d-κ) alkoxy; Allyl; du) haloalkyl; ₂₀ is an aryl, - or C ₆

n is an integer of 10 to 200,

In Chemical Formula 3,

¾ are each independently d-K) alkylene,

Yr each independently hydrogen, _C6 alkyl, halogen, hydroxy, d- ₆ alkoxy or C ₆ - ₂₀ aryl, and,

Each R ₆ is independently hydrogen; Unsubstituted or oxiranyl, the dw-alkoxy substituted by oxiranyl group, or a C ₆ - ₂₀ aryl substituted with a d- ₁₅ alkyl; halogen; Cwo alkoxy; Allyl; d- ₁₀ haloalkyl; ₂₀ is an aryl, - or C ₆

m is an integer of 10-200. In the above formula (2), preferably, ¾ are each independently C ₂ - ₄ alkylene and is, most preferably, _{propane-1,3-diyl-10} alkylene, more preferably C _2. Also preferably, ¾ is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo iodo, methoxy , Ecoxy, propoxy, allyl, 2, 2, 2-trifluoroethyl, 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably, ¾ is each independently d- ₁₀ alkyl, more preferably d-6 alkyl, more preferably d- ₃ alkyl, most preferably methyl. Also preferably, the n is 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 31 or more, 32 or less, 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, or 37 or less Is an integer. In Formula 3, preferably, ¾ are each independently a C ₂ - to ₁₀ alkylene, more preferably C ₂ - ₆ alkylene and most preferably isobutylene. Also preferably, ^ is hydrogen. Also preferably, ¾ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, medo hydroxy, ^- a hydroxy, propoxy, allyl, 2,2,2-trifluoro-ethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, ¾ is each independently d- ₁₀ alkyl, more preferably d- ₆ alkyl, more preferably d- ₃ alkyl, most preferably methyl. Also preferably, m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or 62 or less Is an integer. The repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) are derived from the siloxane compound represented by the following formula (2-1) and the siloxane compound represented by the following formula (3-1), respectively.

In Formula 2-1, the definitions of XR ₅ and _n are the same as defined above.

In Chemical Formula 3-1, ¾, Yi, R ₆ and m are the same as defined above. The term “derived from the siloxane compound” means that the hydroxyl group and the carbonate precursor of each siloxane compound react to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 . In addition, the carbonate precursors that can be used to form the repeating units of Formulas 2 and 3 are the same as those described above for the carbonate precursors that can be used to form the repeating units of Formula 1. The method for producing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 is as follows. [Banungsik 1]

6

In Scheme 1,

'Is C ₂ _ ₁₀ alkenyl,

The definitions of Xi, ¾ and n are as defined above,

3-1

In the reaction form 2,

Alkenyl and ₁₀ know, - ¾ 'is C ₂

The definitions of X ₂ , Yi, R ₆ and m are as defined above. The reactions of the reactions 1 and 2 are preferably carried out under a metal catalyst. It is preferable to use a Pt catalyst as the metal catalyst, Pt Ashby catalyst, Karlstedt catalyst, Lamoreaux catalyst, Speyer catalyst, PtCl ₂ (C0D),

At least one selected from the group consisting of PtCl ₂ (benzonitrile) ₂ , and ¾PtBr ₆ can be used. The metal catalyst is 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight or more, 1 part by weight, 0.1 part by weight, or 0.05 part by weight based on 100 parts by weight of the compound represented by Chemical Formula 7 or 9. It can be used in parts or less. In addition, the reaction temperature is preferably so to locrc. In addition, the reaction time is preferably 1 hour to 5 hours. In addition, the compound represented by Chemical Formula 7 or 9 may be prepared by reacting organodisiloxane and organocyclosiloxane under an acid catalyst, and may adjust n and m by adjusting the content of the reactant. The reaction temperature is preferably 50 to 70 ^° C. In addition, the reaction time is preferably 1 hour to 6 hours. As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane and nuxaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane may be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. The organodisiloxane may be used in an amount of 0.01 parts by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxane. As the acid catalyst, at least one selected from the group consisting of ¾SO ₄ , HC10 ₄ , AICI 3, SbCl ₅ , SnCl _4, and acidic clay may be used. Also, the mountain 59

The catalyst may be used in an amount of 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 10 parts by weight, 5 parts by weight, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. The weight ratio between the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20. The weight ratio of the repeating unit corresponds to an increase ratio of a siloxane compound, for example, the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1. Preferably, the repeating unit represented by Formula 2 is

It is represented by 2-2:

[Formula 2-2]

In Formula 2-2, R ₅ and n are as defined above. Preferably, ¾ is methyl. Also preferably, the repeating unit represented by Formula 3 is represented by the following Formula 3-2:

As defined above in Chemical Formula 3-2. Preferably, ¾ is methyl. Also preferably, the copolycarbonate according to the present invention includes all of the repeating units represented by Formula 1-1, the repeating units represented by Formula 2-2, and the repeating units represented by Formula 3-2. . Copolycarbonates according to the present invention can be prepared by a process comprising the step of polymerizing an aromatic di compound, a carbonate precursor and one or more siloxane compounds. The aromatic dialkyl compound, carbonate precursor and one or more siloxane compounds are as described above. In the polymerization, the at least one siloxane compound is at least 0.01 wt%, at least 0.5 wt%, at least 1 wt%, or at least 1.5 wt%, based on 100 wt% of the total amount of the aromatic dialkyl compound, the carbonate precursor, and the at least one siloxane compound. 20 wt% or less, 10 wt% or less, 7 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, or 2 wt% or less can be used. In addition, the aromatic diol compound is at least 40% by weight, at least 50% by weight, or at least 55% by weight, at least 80% by weight, 70% by weight relative to 100% by weight of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. Up to 65 weight percent. In addition, the carbonate precursor is at least 10% by weight, at least 20% by weight, or at least 30% by weight, at most 60% by weight, at most 50% by weight, based on 100% by weight of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. Or 40 weight or less. In addition, as the polymerization method, for example, an interfacial polymerization method may be used. In this case, the polymerization reaction is possible at atmospheric pressure and low temperature, and the molecular weight is easily controlled. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include a step of introducing a coupling agent after prepolymerization (pre-polymer i zat ion), for example, and then polymerizing again, in which case a high molecular weight copolycarbonate may be obtained. The materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or an amine compound such as pyridine can be used. The organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of polycarbonate, and halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used as an example. In addition, the interfacial polymerization is a reaction such as triethylamine, tetra-n-butylammonium bromide, tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. to promote reaction. Accelerators may additionally be used. The reaction temperature of the interfacial polymerization is preferably 0 to 40 ^° C, the reaction time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH in 9 or more or 11 or more in interfacial polymerization reaction. In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of polymerization, after the start of polymerization or after the start of polymerization. Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is large. The molecular weight modifier may be, for example, 0.01 part by weight, 0, 1 part by weight, or 1 part by weight, 10 parts by weight, 6 parts by weight, or 5 parts by weight or less based on 100 parts by weight of an aromatic diol compound. It is possible to obtain a desired molecular weight within this range, and / or preferably, the molar ratio of the aromatic polycarbonate-based second repeating unit having one repeating unit and at least one real-specific bond is 1: 0.001-. 0.006 and / or weight ratio 1: 0.01-0.03. Also preferably, the copolycarbonate may have a weight average molecular weight

1,000 to 100,000 g / mol, more preferably 15,000 to 35,000 g / irol. More preferably, the weight average molecular weight (g / mol) is at least 20,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or at least 28,000. In addition, the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less.

UV Stabilizer

The copolycarbonate composition according to the present invention comprises a UV stabilizer in order to improve the physical properties of the above-mentioned copolycarbonate, in particular weather resistance. The UV stabilizer used in the present invention is not particularly limited as long as it can improve weather resistance of the copolycarbonate. Preferably, the UV stabilizer comprises a benzotriazole structure, more preferably represented by the following general formula (4):

[Formula 4]

In Chemical Formula 4,

R ₇ to R ₁₀ are each independently hydrogen, hydroxy, halogen, or a hydrocarbon group having 1 to 12 carbon atoms

Y ₂ and X ₃ are each independently hydrogen; A hydrocarbon group having 1 to 40 carbon atoms; Herein, the hydrocarbon group may further include a nitrogen atom or an oxygen atom. Specifically, the UV stabilizer, 2- (5-methyl-2-hydroxyphenyl) benzotriazole (Tinuvin® P), 2- [2-hydroxy-3, 5-bis (α, α-dimethyl) Benzyl) phenyl] -2H-benzotriazole (Tinuvin® 234) ᅳ 2- (3,5-di-t_butyl-2-hydroxyphenyl) benzotriazole (Tinuvin® 320), 2- (3_t-butyl 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (Tinuvin® 326), 2- (3 'ᅳ 5'-di-t-butyl-2' ᅳ hydroxyphenyl) -5-chloro Benzotriazole (Tinuvin® 327), 2- (3,5-di—t-amyl-2-hydroxyphenyl) benzotriazole (Tinuvin® 328) and 2- (2-hydroxy— 5-t-octyl Any one selected from the group consisting of phenyl) benzotriazole (Tinuvin® 329) can be used. Copolycarbonate Composition

The copolycarbonate composition according to the present invention includes the copolycarbonate and the UV stabilizer described above. Meanwhile, in the present invention, 'weather resistance' as in Equation 1 is evaluated. Equation 1 is a YI (Yel low Index) value measured according to ASTM D1925 for the copolycarbonate composition (YI (0 hours)), the copolycarbonate composition according to ASTM D4329 specific conditions (silver degree: 60 ^° C, UV wavelength: 340 nm, light intensity: 0.55 w / m ² , irradiation time: 500 hours), and then subjected to ASTM D1925. It means the difference between YI (Yellow Index) value (YI (500 hours)) measured according to this. Therefore, a smaller value means less deformation and more excellent weather resistance. On the other hand, the irradiation of ultraviolet rays may use a device generally known in the art, for example, Q-LAB's QUV-A Accelerated Weathering Test chamber can be used. Preferably, ΔΥΙ of Equation 1 is 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, 4.5 or less, 4.0 or less, 3.5 or less, or 3.0 or less. The smaller the Δ Ι is, the better the weather resistance is, so the lower limit is 0. For example, the ΔΥΙ is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 It may be abnormal. Also preferably, the copolycarbonate composition has a weight average molecular weight of 1,000 to 100,000 g / mol, more preferably 15,000 to 35,000 g / ηωΐ. More preferably, the weight average molecular weight (g / mol) is at least 20,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or at least 28,000. The weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. Also preferably, the copolycarbonate composition has a room temperature impact strength of 700 to 1000 J / m measured at 23 ^° C based on ASTM D256 (l / 8 inch, Notched Izod). More preferably, the room temperature layer strength (J / m) is 710 or more, 720 or more, 730 or more, 740 or more, 750 or more, or 760 or more. In addition, the room temperature impact strength (J / m) is the higher the value is excellent, there is no upper limit, for example, 850 or less, 840 or less, 830 or less, 820 or less, 810 or less, 800 or less, or 790 or less. Also preferably, the copolycarbonate composition, based on ASTM D256 1/8 inch, Notched Izod) low temperature layer strength measured at -30 ^° C 600 to 800 J / m. More preferably, the low temperature impact strength (J / m) is 610 or more, 620 or more, 630 or more, 640 or more, or 650 or more. In addition, the low temperature impact strength (J / m) is the higher the value is better, there is no upper limit, for example, 750 or less, 740 or less, 730 or less, 720 or less, 710 or less, 700 or less, or 690 or less. Also preferably, the copolycarbonate composition has a MHmelt index measured according to ASTM D1238 (300 ° C., 1.2 kg condition) of 5 to 20 g / 10 min. More preferably, the MI (g / 10 min) is 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more, 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less. In addition, the copolycarbonate composition according to the present invention can adjust the physical properties of the copolycarbonate by using a polycarbonate as necessary. The polycarbonate is distinguished from the copolycarbonate according to the present invention in that a polysiloxane structure is not introduced into the main chain of the polycarbonate. Preferably, the polycarbonate is represented by the following formula (5).

[Formula 5]

In Chemical Formula 5,

R'i to R'4 are each independently hydrogen, alkyl, alkoxy, or halogen,

X ¹ is unsubstituted or substituted by a Cwo alkylene, unsubstituted or C _wo-alkyl substituted by phenyl C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO. Also preferably, the polycarbonate may have a weight average molecular weight

15,000 to 35,000. g / mol. More preferably, the extended average molecular weight (g / mol) is at least 20,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or at least 28,000. In addition, the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. The repeating unit represented by the formula (5) is formed by reacting an aromatic di compound and a carbonate precursor. The aromatic diol compound and carbonate precursor which can be used are the same as described above in the repeating unit represented by the formula (1). Preferably, the formula (5) to R'4 and X ', are the same as the ¾ to and X of the formula (1) described above, respectively. Also preferably, the repeating unit represented by Chemical Formula 5 is represented by the following Chemical Formula 5-1.

5-1]

In the copolycarbonate composition, the increase ratio of copolycarbonate and polycarbonate is preferably 99: 1 to 1:99, more preferably 90:10 to 50:50, most preferably 20:80 to 80 : 20. Articles Containing Copolycarbonate Compositions

The present invention also provides an article comprising the copolycarbonate composition described above. Preferably, the article is an injection molded article. In addition, the article may further include one or more selected from the group consisting of, for example, antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, layer enhancers, fluorescent brighteners, pigments and dyes. Can be. In the method for producing the article, the copolycarbonate composition according to the present invention and an additive such as an antioxidant is mixed using a mixer, and then the mixture is extruded into an extruder to prepare pellets, and the pellets are dried and then injected. It may include the step of injection into the molding machine. As described above, since the copolycarbonate composition according to the present invention has excellent weather resistance, the product manufactured using the same has a characteristic of less surface quality deterioration and physical property deterioration due to ultraviolet rays due to exposure to the outside. 【Effects of the Invention】

As described above, the copolycarbonate composition according to the present invention has excellent weather resistance, and the product manufactured by using the same has a feature that the surface quality decreases due to ultraviolet rays and the deterioration of physical properties is less. [Specific contents to carry out invention]

Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

47.60 g of octamethylcyclotetrasiloxane (160 μl) and tetramethyldisiloxane g (17.8 μl) were mixed, and then the mixture was 1 part by weight of acidic clay (DC-A3) relative to 100 parts by weight of octamethylcyclotetrasiloxane was added to a 3L flask and reacted at 60 ^° C. for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (n) of the terminal unmodified polyorganosiloxane thus obtained is. ^It was 34 when confirmed by ¹ H NMR. 4.81 g (35.9 르 ol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the obtained terminal unmodified polyorganosiloxane at 90 ^° C. for 3 hours. Reacted. After completion of the reaction, Mibanung siloxane was removed by evaporation under conditions of 120 ^° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named 'AP-34'. AP-34 is a light yellow oil, and it was confirmed that the repeating unit (n) was 34 by ¾ NMR using a Varian 500 MHz. No further purification was necessary. -58

47.60 g of octamethylcyclotetrasiloxane and 160 g of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (1 weight of acidic clay (DC-A3)). The mixture was poured into a 3L flask and reacted at 60 ^° C for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using acelite. The repeating unit (m) of the terminal unmodified polyorganosiloxane thus obtained was 58 as confirmed by ¾ MR. 6.13 g (29.7 醒 ol) of 3-methylbut-3-enyl 4-hydroxybenzoate and a Carlsted platinum catalyst were added to the terminal unmodified polyorganosiloxane obtained above. 0.01 g (50 ppm) of Karstedt's platinum catalyst was added thereto and reacted at 90 ^° C. for 3 hours. After completion of reaction, Mibanung siloxane was removed by evaporation at 120 ^° C and 1 torr. The terminal modified polyorganosiloxane thus obtained was named 'MB-58'. MB-58 was a light yellow oil, and it was confirmed that the repeating unit (m) was 58 by ¾ NMR using a Varian 500 MHz. No further purification was necessary. Preparation Example 3 EU-50

47.60 g of octamethylcyclotetrasiloxane and 160 g of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane and 1 part by weight of acidic clay (DC-A3). Placed in a 3L flask with and reacted at 60 ^° C for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (n) of the terminal unmodified polyorganosiloxane thus obtained was 50 as confirmed by ¾ NMR. 6.13 g (29.7 隱 ol) of Eugenol and Karlstedt's platinum catalyst were obtained in the terminal unmodified polyorganosiloxane.

0.01 g (50 ppm) was added thereto and reacted at 90 ^° C. for 3 hours. After completion of the reaction, Mibanung siloxane was removed by evaporation under conditions of 120 ^° C. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named 'EU-50'.

EU-50 is a light yellow oil, and the repeating unit (n) was found to be 50 by NMR using a Varian 500 MHz, and no further purification was necessary. Preparation Example 4 Preparation of Polycarbonate (PC)

Water Γ 784 g, NaOH 385 g and BPA (bisphenol A) 232 g was added to the polymerization reactor, and the mixture was dissolved under N ₂ atmosphere. Dissolve 4.3 g of PTBP (para-tert butyl phenol) and 128 g of TPG (triphosgene) in MC for 1 hour while maintaining the pH above 11, and then add 46 g of TEA (triethylamine) after 10 minutes. Coupling reactions were made. Total reaction time 1 hour 20 minutes Afterwards, the pH was lowered to 4 to remove TEA, and washed three 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 methanol and nucleic acid mixture solution, which was then dried at 120 ^° C. to obtain a final copolycarbonate. The polycarbonate thus obtained was named 'PC'. Example 1

(Step 1)

1784 g of water, 385 g of NaOH, and 232 g of BPA (bi sphenol A) were added to the polymerization reactor, and mixed and dissolved under an N ₂ atmosphere. In addition, a mixture of 4.3 g of PTBP (para-tert butyl phenol), 5.91 g of AP-34 prepared in Preparation Example 1, and 0.66 g of MB-58 prepared in Preparation Example 2 (weight ratio 90: 10) was added to MC methylene chloride. ) And dissolved. Then, 128 g of TPG (tr iphosgene) was dissolved in MC and maintained for 1 hour while maintaining the pH above 11. After 10 minutes, 46 g of TEA (tr i ethylamine) was added to carry out a coupling reaction. I was. 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 three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation of methane in a mixture of nucleic acid and nucleic acid, which was then dried at 12 CTC to give a final copolycarbonate.

(Step 2)

A copolycarbonate composition was prepared by mixing 0.3 parts by weight of Tinuvin® 329 with a UV stabilizer based on 100 parts by weight of the copolycarbonate prepared in Step 1. Example 2

80 parts by weight of copolycarbonate prepared in Step 1 of Example 1, 20 parts by weight of polycarbonate (PC) prepared in Preparation Example 4 and 0.3 parts by weight of Tinuvin® 329 as a UV stabilizer were mixed to obtain a copolycarbonate composition. Prepared. Example 3

A copolycarbonate composition was prepared by mixing 0.2 parts by weight of Tinuvin® 329 with 100 parts by weight of the copolycarbonate prepared in Step 1 of Example 1 and a UV stabilizer. Comparative Example 1

Copolycarbonate prepared in Step 1 of Example 1 was used as Comparative Example 1. Comparative Example 2

Except for using 6.57 g of polyorganosiloxane (100 wt% of polyorganosiloxane (EU-50) of Preparation Example 3), a copolycarbonate prepared in the same manner as in Step 1 of Example 1 was compared. Example 2 was set. Comparative Example 3

Copolycarbonate composition was prepared by mixing 0.3 parts by weight of Tinuvin® 329 with a UV stabilizer based on 100 parts by weight of the copolycarbonate prepared in Comparative Example 2, which was referred to as Comparative Example 3. Comparative Example 4

Polycarbonate (PC) prepared in Preparation Example 4 was referred to as Comparative Example 4. The content of the main components used in the preparation of the Examples and Comparative Examples is shown in Table 1 below.

Table 1

PTBP 4.3 g 4.3 g 4.3 g 4.3 g 4.3 g

UV 0.3 0.3 0.2 0.3 Stabilizer ^υ

(Part by weight)

1) Tinuvin® 329, content relative to 100 parts by weight of copolycarbonate

2) 80 parts by weight of copolycarbonate prepared in Step 1 of Example 1, and 20 parts by weight of polycarbonate of Preparation Example 4

3) 100 parts by weight of copolycarbonate prepared in Step 1 of Example 1 Experimental Example

0.050 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3,5-di-tert-butyl) in each of the copolycarbonate compositions prepared in Examples and Comparative Examples After adding 0.010 parts by weight of -4-hydroxyphenyl) propionate and 0.030 parts by weight of pentaerythritol tetrastearate, and pelletizing it using a Φ30 讓 twin screw extruder with a vent, JSW Co., Ltd. N- 20C injection molding machine with a cylinder temperature of 30 ^(C, a mold temperature of 8 ^(and injection molding the molded test specimens in C. was measured by the following method for its characteristics, the results are shown in Table 2.

1) Weight average molecular weight (g / mol): Agilent 1200 series was calibrated by PC standard.

2) Phase silver layer strength and low temperature layer strength (J / m): measured at 23 ^° C and -30 ^° C, respectively, in accordance with ASTM D256 (l / 8 inch, Notched Izod).

3) Flowability (MI, g / 10 min): Measured according to ASTM D1238 (300 ^° C., 1.2 kg conditions).

4) Weather resistance (ΔΥΙ): After injection molding the specimen (horizontal / vertical / thickness = 60 醒 / 40 瞧 / 3 3) at 300 ^° C, it is color-Eye 7000A (X-rite company) according to ASTM D1925. YKYellow Index) was measured using. Subsequently, according to ASTM D4329, the specimen was placed in a QUV—A Accelerated Weathering Test chamber (temperature: 601 ：, UV wavelength: 340 皿， light quantity: 0.55 w / m ² ) of Q-LAB. According to D1925, YKYellow Index was measured using Color-Eye 7000A (Xrite Co., Ltd.) (YI (500 hours)). YI (500 times) and YI The difference of (0 hours) was calculated. On the other hand, the YI (Yel low Index) measurement conditions were as follows.

-Measurement silver: room temperature (23 ^° C)

-Aperture s i ze: Large area of view

Measurement method: transmittance measurement in spectral range (360 nm to 750 nm) [Table 2]

As shown in Table 2, in the case of the embodiment according to the present invention it was confirmed that the weather resistance is significantly superior to the comparative example. In particular, when compared with Comparative Example 1 having a difference in that it does not contain a UV stabilizer, it was confirmed that the effect of improving weather resistance is remarkably excellent. In addition, it was confirmed that the weather resistance was remarkably superior to Comparative Example 3 containing a UV stabilizer but copolycarbonate is different.

Claims

[Patent Claims]

[Claim 1]

(a) aromatic polycarbonate-based crab 1 repeating unit; And a copolycarbonate comprising an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and (b) a UV stabilizer,

ΔΥΙ of the following formula 1 is 7 or less,

Copolycarbonate Compositions:

[Equation 1]

Δ ΥΙ-YK500 hours)-YI (0 hours)

In Equation 1,

YK0 hour) is a YKYel low Index) value measured according to ASTM D1925 for the copolycarbonate composition,

YK500 hours) was measured according to ASTM D1925 after measuring the copolycarbonate composition at 60 ^° C. for 500 hours at 340 nm UV light at 0.55 w / m ² according to ASTM D4329. it means.

[Claim 2]

According to claim 1,

The ΔΥΙ is characterized in that less than 3.5

Copolycarbonate composition.

[Claim 3]

According to claim 1,

The copolycarbonate is characterized in that the weight average molecular weight of 1, 000 to 100, 000 g / mol,

Copolycarbonate composition.

[Claim 4]

The method of claim 1,

The copolycarbonate composition further comprises a polycarbonate Characterized in that

Copolycarbonate composition.

[Claim 5]

The method of claim 4,

The polycarbonate is characterized in that the polysiloxane structure is not introduced into the main chain of the polycarbonate,

Copolycarbonate composition. [Claim 6]

The method of claim 4,

The polycarbonate is characterized in that it comprises a repeating unit represented by the following formula (5),

Copolycarbonate Compositions:

[Formula 5]

In Chemical Formula 5,

'l to R' 4 are each independently hydrogen, ealkyl, d-H) alkoxy, or halogen,

Z 'is unsubstituted or substituted with d- ₁₀ alkylene, unsubstituted or alkyl-substituted phenyl C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO.

[Claim 7]

According to claim 11,

The first repeating unit is represented by the following formula 1, copolycarbonate composition:

[Formula 1]

In Chemical Formula 1,

Ri to R4 are each independently hydrogen, CHC) alkyl, d- ₁₀ alkoxy, or halogen,

X is a C ₃ substituted by an ₁₀ alkylene, unsubstituted or CHO-alkyl substituted by unsubstituted or phenyl Beach - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO.

[Claim 8]

According to claim 7,

The repeating unit represented by the formula (1) is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide ， Bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, Bisphenol A, 2,2-bis (4-hydroxyphenyl) Butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid, 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-hydroxyspecial-3-chlorophenyl) propane, 2, 2- Bis (4-hydroxy ᅳ 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, and a, ω-bis [3- (0 -hydroxyphenyl) propyl] poly At least one aromatic di selected from the group consisting of dimethylsiloxane derived from the compound,

Copolycarbonate composition. [Claim 9]

The method of claim 7, wherein

Formula 1 is represented by the following formula 1-1 Copolycarbonate

-One]

[Claim 10]

The method of claim 1,

The second repeating unit is characterized in that it comprises a repeating unit represented by the repeating unit formula 3 represented by the following formula (2),

Copolycarbonate Compositions:

[Formula ² ]

In Chemical Formula 2,

¾ are each independently d-) alkylene,

Each R ₅ is independently hydrogen; Unsubstituted or oxiranyl group, a d- ₁₀ alkoxy substituted by oxiranyl group, or a C ₆ - ₂₀ 'reel substituted d

halogen; d- ₁₀ alkoxy; Allyl; d-) haloalkyl; And also C ₆ -20 aryl,

n is an integer of 10 to 200,

[Formula 3]

In Chemical Formula 3,

¾ are each independently d— ₁₀ alkylene,

[Claim 14]

The method of claim 1,

The UV stabilizer is a copolycarbonate composition, characterized in that represented by the formula (4).

In Chemical Formula 4,

R ₇ to Rio are each independently hydrogen, hydroxy, halogen, or a hydrocarbon group having 1 to 12 carbon atoms,

Y ₂ and X ₃ are each independently hydrogen; A hydrocarbon group having 1 to 40 carbon atoms; Herein, the hydrocarbon group may further include a nitrogen atom or an oxygen atom.