KR101795143B1 - Polycarbonate resin composition with good transparent and impatct - Google Patents
Polycarbonate resin composition with good transparent and impatct Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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Abstract
The polycarbonate resin composition of the present invention comprises a polycarbonate resin; An inorganic filler having a refractive index difference of 0 to 0.01 with the polycarbonate resin; A siloxane copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And a glass transition temperature adjusting agent containing phosphorus. The polycarbonate resin composition and the molded article formed therefrom are excellent in transparency, impact resistance, flexural elasticity, and appearance.
[Chemical Formula 1]
(2)
R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 3 and R < 4 > is an aryl group.
Description
The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition excellent in transparency, impact resistance, flexural elasticity, and external appearance, and a molded article formed from the polycarbonate resin composition.
When the thermoplastic resin composition contains an inorganic filler as a reinforcing material, rigidity such as flexural strength is improved and can be applied to parts such as automobiles and electronic devices. However, when an inorganic filler is added to a thermoplastic resin composition, the impact resistance can be greatly reduced, which is difficult to apply to products requiring high impact strength, and the fluidity is significantly lowered, Problems may arise.
Specifically, the polycarbonate resin composition containing glass fibers as a reinforcing material can improve the tensile strength, flexural strength and the like while maintaining excellent moldability of the polycarbonate resin. Such a polycarbonate resin composition is excellent in bending elasticity, heat resistance, and the like, and can be applied to parts that must withstand continuous load and / or heat, such as exterior materials for electronic devices such as mobile phones.
However, in the resin composition to which the glass fiber is applied, the glass fiber may protrude from the surface of the molded product during injection molding, thereby decreasing the transparency and appearance characteristics. To improve this, an additive such as a surfactant may be used. , Flexural elasticity, impact resistance and the like may be lowered.
In addition, a method of improving the flowability and impact resistance of a polycarbonate resin composition by adding a modified polyolefin or the like together with glass fiber has been developed. However, the degree of improvement of fluidity is insufficient, the appearance of the article is deteriorated, Etc. may be required.
Therefore, there is a need to develop a polycarbonate resin composition capable of realizing excellent transparency, impact resistance, flexural elasticity, appearance, balance of physical properties, and the like.
The background art of the present invention is disclosed in Korean Patent Publication No. 10-2009-0018569.
An object of the present invention is to provide a polycarbonate resin composition excellent in transparency, impact resistance, flexural elasticity, and external appearance.
Another object of the present invention is to provide a molded article formed from the polycarbonate resin composition.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to a polycarbonate resin composition. The resin composition may include a polycarbonate resin; An inorganic filler having a refractive index difference of 0 to 0.01 with the polycarbonate resin; A siloxane copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And a glass transition temperature adjusting agent containing phosphorus:
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms;
(2)
In Formula 2, R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and at least one of R 3 and R 4 is an aryl group.
In an embodiment, the polycarbonate resin composition comprises 0.1 to 5 parts by weight of the siloxane copolymer and 100 to 5 parts by weight of the siloxane copolymer, based on 100 parts by weight of the base resin containing 60 to 95% by weight of the polycarbonate resin and 5 to 40% And 1 to 10 parts by weight of a glass transition temperature adjusting agent.
In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol.
In an embodiment, the inorganic filler may include at least one of glass fiber, carbon fiber, ceramic fiber, calcium carbonate, silica, alumina, aluminum hydroxide, talc, clay, mica, barium sulfate and whiskers.
In an embodiment, the inorganic filler may be in the form of fibers.
In embodiments, the siloxane copolymer may have an aryl group content of 30 to 50 mole percent of the total substituent group in 100 mole percent.
In embodiments, the siloxane copolymer may comprise at least one of poly (dialkylsiloxane-co-arylalkylsiloxane) and poly (dialkylsiloxane-co-diarylsiloxane).
In embodiments, the viscosity of the siloxane copolymer may be from 1 to 1,000 cst at 25 占 폚.
In an embodiment, the glass transition temperature modifier may be a compound represented by the following formula:
(3)
In Formula 3, R 5 to R 10 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted Substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or a hydroxy group.
In an embodiment, the glass transition temperature adjusting agent may include at least one of a compound represented by the following formula (3a), a compound represented by the following formula (3b) and a compound represented by the following formula (3c)
[Chemical Formula 3]
(3b)
[Chemical Formula 3c]
In Formula 3c, R 11 , R 12 , R 13 , R 14 , R 15, and R 16 may each independently be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group.
In an embodiment, the polycarbonate resin composition may further include an ester compound.
In an embodiment of the present invention, the polycarbonate resin composition is used in combination with at least one of an antimicrobial agent, a thermal stabilizer, an antioxidant, a releasing agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, a compatibilizing agent, a lubricant, an antistatic agent, a colorant, a flame retardant, Ultraviolet light absorber, ultraviolet light absorber, ultraviolet light absorber, ultraviolet light absorber and ultraviolet light absorber.
In the specific examples, the polycarbonate resin composition had a flexural modulus of a specimen of 6.4 mm thickness measured at a speed of 2.8 mm / min according to ASTM D790 of 30,000 To 45,000 kgf / cm < 2 >, and the notched Izod impact strength of the 1/8 "specimen measured according to ASTM D256 may be 18 to 30 kgf / cm / cm.
Another aspect of the present invention relates to a molded article formed from the polycarbonate resin composition.
INDUSTRIAL APPLICABILITY The present invention has the effect of providing a polycarbonate resin composition excellent in transparency, impact resistance, flexural elasticity, appearance and the like, and a molded article formed therefrom. The molded product can secure mechanical properties required for a thinner and larger portable electronic device exterior material, and is excellent in transparency and appearance, and can be used as an exterior material without additional process for application of exterior materials.
Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) an inorganic filler; (C) a siloxane copolymer; And (D) a glass transition temperature adjusting agent.
(A) Polycarbonate resin
The above-mentioned polycarbonate resin can be used without limitation in a polycarbonate resin such as an aromatic polycarbonate resin used in a conventional polycarbonate resin composition. For example, the polycarbonate resin may be prepared by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene, halogenformate or carbonic acid diester in the presence of a catalyst according to a known production method.
In an embodiment, the aromatic dihydroxy compound may be selected from the group consisting of bis (hydroxyaryl) alkane, bis (hydroxyaryl) cycloalkane, bis (hydroxyaryl) ether, bis (hydroxyaryl) sulfoxide, bis Aryl) sulfide, bis (hydroxyaryl) sulfone, biphenyl compounds, dihydroxybenzene compounds, combinations thereof and the like.
Specific examples of the bis (hydroxyaryl) alkane include bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- 3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (2-tertiary- (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, Bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methane, 2,2-bis Bis (4-hydroxy-3-bromophenyl) propane, 2, (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy- Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2 Bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Butyl-4-hydroxyphenyl) butane, 1,1-bis (2-tertiary- Butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tertiary- Bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-phenyl) 2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, , But is not limited thereto.
Specific examples of the bis (hydroxyaryl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, Hexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, and the like, but are not limited thereto.
Specific examples of the bis (hydroxyaryl) ether include bis (4-hydroxyphenyl) ether and bis (4-hydroxy-3-methylphenyl) Examples of the bis (hydroxyaryl) sulfoxide include bis (hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide. (3-methyl-4-hydroxyphenyl) sulfoxide and bis (3-phenyl-4-hydroxyphenyl) sulfoxide. Examples of the bis (hydroxyaryl) sulfone include bis 4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone and bis Dihydroxybiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 3,3-di Fluoro-4,4'-dihydroxybiphenyl , But are not limited thereto.
Specifically, the dihydroxybenzene compounds include resorcinol, 3-methylresorcinol, 3-ethyl resorcinol, 3-propyrazolesynol, 3-butyl resorcinol, Resorcinol, 3-phenylresorcinol, 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromorezolicol, catechol, hydroquinone, 3-methyl Hydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tertiary-butylhydroquinone, 3-phenylhydroquinone, 3-silylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-tertiary-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6- 6-tetrabromohydroquinone, and the like, but the present invention is not limited thereto.
In an embodiment, the carbonate precursor is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , Carbonyl chloride (phosgene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, and the like. These may be used alone or in combination of two or more.
In an embodiment, the polycarbonate resin may be prepared by reacting the aromatic dihydroxy compound and the carbonate precursor in a molar ratio of 1: 0.9 to 1: 1.5.
In an embodiment, the polycarbonate resin may be partially or wholly substituted with an aliphatic polycarbonate resin, an aromatic and aliphatic copolycarbonate resin, a polyester carbonate resin, a polycarbonate-polysiloxane copolymer resin, etc., in addition to the aromatic polycarbonate resin It is also possible to do.
The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a mixture of linear and branched polycarbonate resins. For example, the branched polycarbonate resin may be used in an amount of 0.05 to 2 mol% of a trifunctional or more polyfunctional compound with respect to the (aromatic) dihydroxy compound used in the polymerization, specifically, Group in the compound of formula (I).
In embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, such as 15,000 to 80,000 g / mol. Within the above range, the polycarbonate resin composition may have excellent mechanical properties and processability. In the present invention, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then measuring it by Gel Permeation Chromatography (GPC). At this time, a column was Shodex LF-804 (8.0.1.D. × 300 mm), and a standard sample was polystyrene.
In an embodiment, the polycarbonate resin may have a refractive index of 1.58 to 1.59, such as 1.581 to 1.587. The transparency and the like of the polycarbonate resin composition within the above range can be excellent.
In an embodiment, the polycarbonate resin is used in an amount of 60 to 95% by weight, based on 100% by weight of the polycarbonate resin (A) and the base resin (A) + (B) containing the inorganic filler (B) 70 to 90% by weight. Within the above range, the polycarbonate resin composition may have excellent impact resistance, thermal stability, moldability and the like.
(B) inorganic filler
The inorganic filler can improve the rigidity and the like of the polycarbonate resin composition without lowering the transparency of the polycarbonate resin. The difference in refractive index between the polycarbonate resin and the polycarbonate resin may be 0 to 0.1, for example, 0 to 0.002. If the refractive index difference between the polycarbonate resin and the inorganic filler exceeds 0.01, the transparency of the polycarbonate resin composition may be significantly lowered. As the inorganic filler, those having a difference in refractive index from the polycarbonate resin satisfying the above range can be used without limitation of the form and the type, and those known in the art can be used. For example, fibrous inorganic fillers may be used, but are not limited thereto.
In an embodiment, the inorganic filler may include at least one of glass fiber, carbon fiber, ceramic fiber, metal fiber, calcium carbonate, silica, alumina, aluminum hydroxide, talc, clay, mica, barium sulfate and whiskers. Such an inorganic filler may have various cross-sectional shapes such as a circle, an ellipse, and a rectangle.
The inorganic filler according to one embodiment of the present invention may be glass fiber. The type and form of the glass fiber are not limited, but may be a cylindrical cross-section glass fiber or a plate-shaped glass fiber. For example, the cylindrical cross-section glass fibers may have a cross-sectional diameter of 5 to 20 탆 and a length of 2 to 5 mm before processing, wherein the cross-sectional aspect ratio of the glass fibers is 1.5 to 10, To 5 mm. Within the above range, the polycarbonate resin composition can have excellent processability, and mechanical properties such as tensile strength, impact strength and flexural modulus of the molded article as well as appearance properties can be improved.
In an embodiment, the inorganic filler may be a surface treatment agent coated on the surface of the inorganic filler in order to increase the bonding strength with the polycarbonate resin. Examples of the surface treatment agent include, but are not limited to, silane compounds, urethane compounds, and epoxy compounds.
In an embodiment, the inorganic filler is contained in an amount of 5 to 40% by weight, for example, 10 to 100% by weight, based on 100% by weight of the base resin (A) + (B) containing the polycarbonate resin (A) To 30% by weight. Within the above range, the polycarbonate resin composition can be excellent in transparency, impact resistance, heat resistance, molding processability, appearance and the like.
(C) a siloxane copolymer
The siloxane copolymer is obtained by substituting a part of an alkyl group of a polydialkylsiloxane with an aryl group, and includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group and the like.
(2)
R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a tert-butyl group, an aryl group having 6 to 12 carbon atoms, For example, a phenyl group, a benzyl group, a tolyl group, an o-xylyl group, an m-xylyl group and the like, and at least one of R 3 and R 4 is an aryl group .
Generally, polydialkylsiloxane such as polydimethylsiloxane has a low glass transition temperature (Tg) and is used as an impact modifier for improving the low-temperature impact strength of a thermoplastic resin composition. However, since the refractive index difference from the polycarbonate resin is large, There is a problem that the transparency is largely lowered. Accordingly, the present invention provides a polycarbonate resin composition having a reduced refractive index difference with a polycarbonate resin and having excellent transparency, impact resistance, etc., by using a siloxane copolymer containing an aryl group instead of a polydialkylsiloxane.
In embodiments, the siloxane copolymer may have from 30 to 50 mole percent, such as from 35 to 45 mole percent, of the total substituent groups (R 1 , R 2 , R 3, and R 4 ) . Within the above range, transparency, appearance, (low temperature) impact resistance and the like of the polycarbonate resin composition can be excellent.
In embodiments, the siloxane copolymer is a poly (dialkylsiloxane-co-arylalkylsiloxane) such as poly (dimethylsiloxane-co-phenylmethylsiloxane); Poly (dialkylsiloxane-co-diarylsiloxanes) such as poly (dimethylsiloxane-co-diphenylsiloxane); Combinations thereof, and the like. Specifically, the poly (dialkylsiloxane-co-arylalkylsiloxane) may be a siloxane copolymer wherein R 1 and R 2 in Formula 1 are alkyl groups, R 3 in Formula 2 is an aryl group, and R 4 is an alkyl group And the poly (dialkylsiloxane-co-diarylsiloxane) may be a siloxane copolymer in which R 1 and R 2 in Formula 1 are alkyl groups, and R 3 and R 4 in Formula 2 are aryl groups.
In embodiments, the siloxane copolymer may have a viscosity of from 1 to 1,000 cSt (centistokes), for example from 4 to 500 cSt, as measured using a Ubbelohde viscometer. Within the above range, the polycarbonate resin composition may be excellent in impact resistance, transparency, physical properties and the like.
In embodiments, the siloxane copolymer may have a refractive index of 1.57 to 1.59, such as 1.575 to 1.585, and the difference in refractive index from the polycarbonate resin may be 0.01 or less, such as 0.001 to 0.01, have. The transparency and the like of the polycarbonate resin composition within the above range can be excellent.
In an embodiment, the siloxane copolymer may be included in an amount of 0.1 to 5 parts by weight, for example, 0.5 to 2 parts by weight, based on 100 parts by weight of the base resin. Within the above range, the polycarbonate resin composition may have excellent mechanical properties, transparency, and appearance characteristics.
(D) Glass transition temperature adjusting agent
The glass transition temperature regulator can lower the glass transition temperature (Tg) of the polycarbonate resin to improve the flowability (workability) and the like without deteriorating the mechanical properties etc. of the polycarbonate resin composition. , And cyclic phosphazene can be used.
In an embodiment, the glass transition temperature adjusting agent may be a compound represented by the following formula (3) (cyclic phosphazene).
(3)
In Formula 3, R 5 to R 10 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted Substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or a hydroxy group.
Here, the "substitution" means that the hydrogen atom is an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A heterocycloalkyl group, a heteroaryl group having 4 to 10 carbon atoms, a combination of these, and the like.
Also, the substituents comprising the above "alkyl", "alkoxy" and other "alkyl" moieties include both linear and branched forms, "alkenyl" means a straight or branched chain containing from 2 to 8 carbon atoms and containing at least one double bond Quot; cycloalkyl "includes both saturated monocyclic or saturated bicyclic ring structure forms having 3 to 20 carbon atoms. Refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom and is a single or fused ring system containing in each ring suitably 4 to 7, preferably 5 or 6, ring atoms . Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, tolyl, and the like.
Said "heterocycloalkyl" is a saturated cyclic hydrocarbon skeletal atom containing 1 to 3 heteroatoms selected from N, O and S, and the remaining saturated monocyclic or bicyclic ring skeletal atoms are carbon, Means pyridinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, Oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyril Naphthyl, decyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, azepanyl and the like.
The "heteroaryl" refers to an aryl group having 1 to 3 heteroatoms selected from N, O, and S as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms being carbon, wherein the heteroaryl group is heteroaryl The atoms include divalent aryl groups that are oxidized or capped, for example forming an N-oxide or quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tri But are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like.
In an embodiment, the glass transition temperature regulator may include at least one compound represented by the following formula (3a), a compound represented by the following formula (3b), and a compound represented by the following formula (3c).
[Chemical Formula 3]
(3b)
[Chemical Formula 3c]
In Formula 3c, R 11 , R 12 , R 13 , R 14 , R 15, and R 16 may each independently be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group.
In an embodiment, the glass transition temperature adjuster may be included in an amount of 1 to 10 parts by weight, for example, 1 to 5 parts by weight, and more preferably 1 to 3 parts by weight, based on 100 parts by weight of the base resin. Within the above range, the polycarbonate resin composition may be excellent in mechanical properties, processability, appearance, physical properties, and the like.
In a specific example, the weight ratio (C) :( D) of the siloxane copolymer (C) and the glass transition temperature adjuster (D) is from 1: 1 to 1:10, for example from 1: 2 to 1: Lt; / RTI > Within the above range, the polycarbonate resin composition may have better mechanical properties, processability, transparency, appearance, and balance of physical properties thereof.
The polycarbonate resin composition according to one embodiment of the present invention may further include an ester compound. The ester compound can be used in combination with other components of the polycarbonate resin composition to stabilize the synergistic effect of transparency and appearance over a long period of time without deteriorating the mechanical properties and improve discoloration resistance.
In an embodiment, the ester compound includes glycerin, pentaerythritol or an ester compound of a polyhydric alcohol and a fatty acid; Ester compounds of glycol compounds and fatty acids such as ethylene glycol, polyethylene glycol, and polypropylene glycol; And combinations thereof. For example, ester compounds containing a pentaerythritol structure in a molecular structure such as a long chain ester of pentaerythritol, monoglycerides of fatty acids, diglycerides of fatty acids and triglycerides of fatty acids An ester compound of fatty acid and glycerin, an ester compound of fatty acid and polyethylene glycol, an ester compound of fatty acid and polyglycol such as ester compound of fatty acid and polypropylene glycol, an ester compound of fatty acid and ethylene glycol, an ester compound of fatty acid and polyhydric alcohol For example.
In an embodiment, the ester compound may be included in an amount of 0.1 to 5 parts by weight, for example, 0.5 to 2 parts by weight, based on 100 parts by weight of the base resin. Within the above range, the synergistic effect of transparency, appearance, etc. of the polycarbonate resin composition can be stabilized.
The polycarbonate resin composition according to one embodiment of the present invention may further contain various additives depending on the application within a range not hindering the object of the present invention.
In an embodiment, the additive is selected from the group consisting of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, a colorant, a flame retardant, Ultraviolet absorber, ultraviolet absorber, combination of these, and the like. The content of the additive can be easily determined by those skilled in the art.
The polycarbonate resin composition of the present invention can be prepared by a known method. For example, the additives may be mixed with a Henschel mixer, a V blender, a tumbler blender, a ribbon blender or the like and melt-extruded at a temperature of 150 to 300 ° C using a single screw extruder or a twin screw extruder, . ≪ / RTI > At this time, the components other than the inorganic filler can be fed into the main feeder and the inorganic filler can be fed into the side feeder. Specifically, extrusion molding was carried out at 230 to 280 占 폚 using a twin-screw extruder with L / D = 29 and? = 45 mm at a screw rotation speed of 300 to 600 rpm and a self-feed rate of 60 to 600 kg / To prepare a polycarbonate resin composition (pellet). The produced pellets can be used for the production (injection molding) of molded products and specimens after drying at 80 ° C or more for 1 hour or more.
In an embodiment, the polycarbonate resin composition has a transmittance of 85% or more, for example, 86 to 95%, of a 2 mm-thick specimen measured according to ASTM D1003 and measured at 2.8 mm / min according to ASTM D790 the flexural elastic modulus of the specimen thickness is from 30,000 to 45,000 kgf / cm 2, for example 31,000 to 44,000 is kgf / cm 2, a notched Izod impact strength of a 1/8 "specimen, measured according to ASTM D256 15 to 30 kgf · cm / cm, for example, 18 to 30 kgf · cm / cm.
The molded article according to the present invention is formed from the resin composition containing the polyester carbonate resin. For example, the resin composition can be used to produce a molded article by a known molding method such as injection molding, double injection molding, blow molding, extrusion molding, and thermoforming. The molded article can be easily formed by a person having ordinary skill in the art to which the present invention belongs.
The molded article can be applied to various fields to which the polycarbonate resin composition is applied, and is particularly useful as a covering material for portable electronic devices because it is excellent in transparency, impact resistance, flexural elasticity, and appearance.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
Example
The specifications of each component used in the following examples and comparative examples are as follows.
(A) Polycarbonate resin
Bisphenol A polycarbonate resin having a refractive index of 1.583 (weight average molecular weight (Mw): 24,000 g / mol and melt flow index (300 DEG C, 1.2 kg): 20 g / 10 min) was used.
(B) inorganic filler
(B1) A transparent glass fiber having a refractive index of 1.575 (trade name: Idemitsu, product name: G-1930T) was used.
(B2) Glass fiber having a refractive index of 1.53 (manufacturer: Owens Corning, product name: 183F) was used.
(C) a siloxane copolymer
(Dimethylsiloxane-co-diphenylsiloxane) (manufacturer: Momentive product name: TSF-433) having a refractive index of 1.575 was used.
(D) Glass transition temperature adjusting agent
Hexaphenoxycyclotriphosphazene (manufacturer: Fushimi, product name: Rabite FP-110) was used.
(E) ester compound
The long chain ester of pentaerythritol (manufactured by Emery Oleochemicals, product name: LOXIOL P861) was used.
Examples 2 to 4 and Comparative Examples 1 to 5
The components were dry blended and then extruded at 230 to 250 ° C. using a twin-screw extruder having L / D = 29 and Φ = 45 mm according to the composition and content of the following Table 1 to obtain pellet-shaped poly Carbonate resin composition was prepared. The prepared pellets were dried at 90 ° C for 3 hours and then injection molded at an extruder (manufactured by Dongshin Hydraulic Co., Ltd., DHC 120WD) at a molding temperature of 270 and a mold temperature of 70 to prepare specimens. The prepared specimens were measured for permeability, flexural modulus and notched Izod impact strength by the following physical property measuring methods, and the results are shown in Table 1 below.
Property evaluation method
(1) Permeability (unit:%): Measured according to ASTM D1003 on a 2 mm thick specimen using a Haze Meter (YDP02-0D) manufactured by Nippon Denshoku.
(2) Flexural modulus (FM, unit: kgf / cm 2 ): Measured according to the evaluation method specified in ASTM D790 for a 6.4 mm thick specimen at 2.8 mm / min.
(3) Notch Izod Impact Strength (Unit: kgf · cm / cm): Evaluation was made on 1/8 "thick specimens according to the evaluation method specified in ASTM D256.
(weight%)
Parts by weight based on 100 parts by weight of the base resin ((A) + (B))
From the above results, it can be seen that the polycarbonate resin compositions of the present invention (Examples 2 to 4) are excellent in flexural modulus, impact strength, transparency (transparency), and physical properties thereof.
On the other hand, when the inorganic filler and the glass transition temperature regulator were not used (Comparative Example 1), the flexural modulus was largely lowered and the inorganic filler having a refractive index difference of more than 0.01 with the polycarbonate resin was used (Comparative Examples 2 and 3) , The transparency is largely lowered, and when the glass transition temperature adjuster or the siloxane copolymer is not used (Comparative Examples 4 and 5), the impact strength is lowered and the overall physical property balance is lowered.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (14)
An inorganic filler having a refractive index difference of 0 to 0.01 with the polycarbonate resin;
A siloxane copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2);
A glass transition temperature adjusting agent containing phosphorus; And
An ester compound,
The ester compound may be an ester compound of glycerin, pentaerythritol or a polyhydric alcohol and a fatty acid; Ester compounds of glycol compounds and fatty acids; Or a combination thereof. The polycarbonate resin composition according to claim 1,
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms;
(2)
In Formula 2, R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and at least one of R 3 and R 4 is an aryl group.
(3)
In Formula 3, R 5 to R 10 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted Substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or a hydroxy group.
[Chemical Formula 3]
(3b)
[Chemical Formula 3c]
In Formula 3c, R 11 , R 12 , R 13 , R 14 , R 15, and R 16 may each independently be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group.
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| KR20190082429A (en) * | 2017-12-31 | 2019-07-10 | 롯데첨단소재(주) | Lens barrel member |
| KR102141727B1 (en) * | 2017-12-31 | 2020-08-05 | 롯데첨단소재(주) | Lens barrel member |
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