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WO2015170803A1 - Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci - Google Patents

Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci Download PDF

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Publication number
WO2015170803A1
WO2015170803A1 PCT/KR2014/008296 KR2014008296W WO2015170803A1 WO 2015170803 A1 WO2015170803 A1 WO 2015170803A1 KR 2014008296 W KR2014008296 W KR 2014008296W WO 2015170803 A1 WO2015170803 A1 WO 2015170803A1
Authority
WO
WIPO (PCT)
Prior art keywords
polycarbonate resin
resin composition
weight
antimony
ion exchanger
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/008296
Other languages
English (en)
Korean (ko)
Inventor
이현호
신승식
최성헌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of WO2015170803A1 publication Critical patent/WO2015170803A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/59—Arsenic- or antimony-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium

Definitions

  • the present invention relates to a polycarbonate resin composition and a molded article prepared therefrom, and more particularly, to a polycarbonate resin composition having excellent thermal decomposition resistance, which can exhibit excellent physical properties by preventing thermal decomposition of polycarbonate, and a molded article prepared therefrom. will be.
  • Polycarbonate is one of engineering plastics and is widely used in the plastics industry.
  • Polycarbonate has a glass transition temperature (Tg) of about 150 ° C. due to a bulky molecular structure such as bisphenol-A, and thus exhibits high heat resistance.
  • Tg glass transition temperature
  • the carbonyl group of the carbonate group has high rotational motility, thereby providing flexibility and rigidity to the polycarbonate. To give.
  • the amorphous polymer has excellent transparency.
  • an organic acid and / or a silane coupling agent such as maleic acid or acetic acid were mixed with a polycarbonate to form a resin composition.
  • the addition of an organic acid or a silane coupling agent has the effect of inhibiting thermal decomposition of the polycarbonate, but causes a problem of poor physical properties such as mechanical strength.
  • the organic acid may cause the decomposition of the polymer in a high temperature processing process to lower physical properties, and the boiling point may be low to generate gas during processing.
  • an object of the present invention is to solve such a conventional problem, and to provide a polycarbonate resin composition excellent in mechanical strength and a molded article prepared therefrom by adding an inorganic filler capable of realizing high rigidity.
  • the present invention provides a polycarbonate resin composition and a molded article prepared therefrom, which can realize excellent physical properties by reducing thermal decomposition of polycarbonate by adding an ion exchanger capable of preventing thermal decomposition of polycarbonate accelerated by an inorganic filler. For the purpose.
  • the polycarbonate resin composition (a) polycarbonate resin; (b) needle reinforcement; And (c) an antimony ion exchanger, and 0.01 to 2 parts by weight of the antimony ion exchanger (c) based on 100 parts by weight of the total of the polycarbonate resin (a) and the needle-shaped reinforcement (b). It may include.
  • the polycarbonate resin (a) and the needle-shaped reinforcement (b) may be made of 60 to 95% by weight of the polycarbonate resin (a) and 5 to 40% by weight of the needle-shaped reinforcement (b).
  • the needle-shaped reinforcing material (b) may be potassium titanate whisker.
  • the potassium titanate whisker may have a length of 10 to 20 ⁇ m and a diameter of 0.3 to 0.6 ⁇ m.
  • the potassium titanate whisker may have a pH of 8 to 11.
  • the antimony-based ion exchanger (c) may include antimonic acid.
  • the antimony-based ion exchanger (c) may have an average particle diameter of 0.01 to 3 ⁇ m.
  • Molded article according to an embodiment of the present invention can be prepared from the polycarbonate resin composition described above.
  • the molded article may have a melt index of 23 to 40 g / 10 min, measured according to ASTM D1238.
  • the molded article may have a flexural strength of 500 to 1,400 kgf / cm 2 measured according to ASTM D790.
  • the polycarbonate resin composition of the present invention is excellent in mechanical strength by adding a needle-like reinforcement, due to the fine size of the needle-shaped reinforcement is superior to conventional inorganic fillers in the processing of moldings requiring excellent dimensional stability and require dimensional stability There is an advantage.
  • the polycarbonate resin composition according to the present invention includes a polycarbonate resin, acicular reinforcing material and antimony-based ion exchanger.
  • the polycarbonate resin (a) is a polyester having a carbonate bond, and the kind thereof is not particularly limited, and any polycarbonate available in the resin composition field may be used.
  • the polycarbonate resin may be prepared by reacting diphenols with phosgene, halogen acid esters, carbonate esters, or a combination thereof.
  • Two or more kinds of diphenols may be combined to constitute a repeating unit of the polycarbonate resin.
  • diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also called 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether and the like.
  • diphenols preferably 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxy Oxyphenyl) cyclohexane can be used.
  • 2, 2-bis (4-hydroxyphenyl) propane can be used.
  • the polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.
  • polycarbonate resin a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like can be used.
  • linear polycarbonate resin may be bisphenol-A polycarbonate resin.
  • branched polycarbonate resin may be a polymer prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with diphenols and carbonates.
  • the polyester carbonate copolymer may be prepared by reacting a bifunctional carboxylic acid with diphenols and carbonates, and the carbonate used herein may be a diaryl carbonate such as diphenyl carbonate or ethylene carbonate.
  • the polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, preferably 14,000 to 40,000 g / mol.
  • the polycarbonate resin may be 60 to 95% by weight, preferably 75 to 90% by weight, based on 100% by weight of the sum with the needle-shaped reinforcement (b) to be described later. If the polycarbonate resin is less than 60% by weight, the appearance characteristics are not good, and if the polycarbonate resin is more than 95% by weight may lower the mechanical strength.
  • Needle-shaped reinforcing material (b) serves to improve the mechanical strength of the polycarbonate resin composition.
  • the potassium titanate whisker may be used as the needle-shaped reinforcing material (b), and the potassium titanate whisker may be fibrous potassium titanate.
  • glass fiber is mainly used as a needle-shaped reinforcing material, but the polycarbonate resin composition to which the glass fiber is added may increase mechanical strength, but the appearance property may be degraded due to the protrusion of the glass fiber.
  • polycarbonate resin composition to which the glass fiber is added may increase mechanical strength, but the appearance property may be degraded due to the protrusion of the glass fiber.
  • injection molding There is a limitation of injection molding.
  • the potassium titanate whisker has inherent high stiffness, abrasion resistance, and chemical resistance, and due to the fine size of the whisker, the complex structure and moldability of the existing fillers such as glass fibers can be overcome, thereby preventing polycarbonate resins. By using it, it can improve mechanical strength and an external appearance characteristic simultaneously.
  • the potassium titanate whisker may specifically use potassium hexatitanate (K 2 Ti 6 O 13 ) whisker, and the potassium hexatitanate has strong properties in heat resistance and chemical resistance in potassium titanate as a molded article. May be advantageous for processing.
  • the potassium titanate whisker may have a length of 10 to 20 ⁇ m, the diameter may be 0.3 to 0.6 ⁇ m.
  • length means the length corresponding to the longitudinal direction of a potassium titanate whisker
  • a diameter means the diameter of a potassium titanate whisker cross section.
  • the potassium titanate whisker may have a pH of 8 to 11, preferably a pH of 9 to 10.
  • the needle-shaped reinforcing material may be 5 to 40% by weight, preferably 10 to 25% by weight, based on 100% by weight of the polycarbonate resin. If the needle-shaped reinforcing material is less than 5% by weight, the mechanical strength may be lowered, and when the needle-shaped reinforcement is more than 40% by weight, the appearance characteristics and workability may be reduced.
  • the antimony-based ion exchanger (c) is an anion exchanger capable of trapping cations, and serves to suppress thermal decomposition of the polycarbonate resin.
  • the antimony-based ion exchanger traps the needle reinforcement, particularly potassium ions (K + ) of the potassium titanate whisker, thereby preventing thermal decomposition of the polycarbonate resin generated by the action of titanium (Ti) in the potassium titanate whisker. You can prevent it.
  • the form of the antimony-based ion exchanger is generally amorphous, and the average particle diameter of the antimony-based ion exchanger used in the present invention may be 0.01 to 3 ⁇ m, and preferably 0.1 to 2 ⁇ m.
  • the average particle diameter refers to the average value of the longitudinal length of the antimony-based ion exchanger, and the average particle diameter can be obtained by measuring through an image enlarged by a microscope or the like.
  • the antimony-based ion exchanger may include antimony oxide, and specifically may include antimony trioxide (Sb 2 O 3 ), antimony tetraoxide (Sb 2 O 4 ) or antimony pentoxide (Sb 2 O 5 ).
  • it may be in the form of a hydrate of antimony trioxide, antimony tetraoxide, or antimony pentoxide, and more preferably, may be an antimonic acid in the form of a hydrate of antimony pentoxide (Sb 2 O 5 .xH 2 O).
  • the antimony-based ion exchanger may be 0.01 to 2 parts by weight, and more preferably 0.25 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin and the needle-shaped reinforcement. If the antimony-based ion exchanger is less than 0.01 part by weight, thermal decomposition of the polycarbonate cannot be effectively suppressed. If the antimony-based ion exchanger is more than 2 parts by weight, the effect of improving the thermal decomposition effect is insignificant and uneconomic.
  • the polycarbonate resin composition may optionally further include an additive according to its use.
  • the additive may further include a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, or a colorant, and may be used by mixing two or more kinds according to the properties of the final molded product.
  • the flame retardant is a material for reducing combustibility, and includes a phosphate compound, a phosphite compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate compound or a melamine compound It may include at least one of, but is not limited thereto.
  • the lubricant is a material that helps the flow or movement of the resin composition by lubricating the metal surface in contact with the polycarbonate resin composition during processing, molding, extrusion, can be used a commonly used material.
  • the plasticizer is a material that increases the flexibility, processing workability, or expandability of the polycarbonate resin composition, and may be a material commonly used.
  • the heat stabilizer is a material that suppresses thermal decomposition of the polycarbonate resin composition when kneading or molding at a high temperature, and may be a material that is commonly used.
  • the antioxidant is a substance that prevents decomposition of the resin composition and loss of intrinsic properties by inhibiting or blocking a chemical reaction between the polycarbonate resin composition and oxygen, and is a phenol type, phosphite type, thioether type or amine type antioxidant. It may include at least one of, but is not limited thereto.
  • the light stabilizer is a material that inhibits or blocks the polycarbonate resin composition from being decomposed from ultraviolet rays and changes color or loses mechanical properties, and preferably titanium oxide may be used.
  • the colorant may be used conventional pigments or dyes.
  • the additive may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polycarbonate resin and the needle-shaped reinforcement.
  • the polycarbonate resin composition described above uses an acicular reinforcing material that is effective for improving mechanical strength as an inorganic filler, and an antimony-based ion exchanger that can effectively control thermal decomposition of the polycarbonate resin generated by the acicular reinforcing material. It has an excellent effect on mechanical strength, appearance properties and thermal decomposition resistance.
  • the polycarbonate resin composition according to the present invention can be prepared by a known method for producing a resin composition.
  • the polycarbonate resin composition according to the present invention may be prepared in the form of pellets by mixing the components of the present invention and other additives at the same time and then melt extrusion in an extruder.
  • Molded article according to an embodiment of the present invention can be prepared from the polycarbonate resin composition described above.
  • the polycarbonate resin composition is prepared from a high molecular weight polycarbonate which can prevent thermal decomposition of the polycarbonate resin and exhibit excellent physical properties, thereby having excellent thermal decomposition resistance and mechanical strength.
  • the molded article may have a melt index of 23 to 40 g / 10 min, and preferably 25 to 36 g / 10 min.
  • the bending strength of the molded article may be 500 to 1,400kgf / cm 2 , preferably 600 to 1,200kgf / cm 2 It can be.
  • the polycarbonate resin composition is excellent in thermal decomposition resistance and mechanical strength, and can be applied without limitation to molded articles requiring such properties.
  • the component used for the polycarbonate resin composition of the following Example and a comparative example is as follows.
  • Otsuka's potassium titanate whisker TISMO-D was used.
  • IXEPLAS-A1 an ion exchanger product mainly composed of zirconium (Zr), magnesium (Mg) and aluminum (Al), manufactured by Toagosei Co., was used.
  • IXEPLAS-A3 an ion exchanger product having an organic coated surface, was used as a main component of Toagosei Co., Ltd., zirconium (Zr), magnesium (Mg) and aluminum (Al).
  • Polycarbonate resin compositions of Examples and Comparative Examples were prepared according to the component content ratios shown in Table 1 below.
  • Table 1 the total amount of the polycarbonate resin (a) and the needle-shaped reinforcement (b) is 100% by weight, and the ion exchanger (c) is based on 100 parts by weight of the total polycarbonate resin (a) and the needle-shaped reinforcement (b). Parts by weight are described.
  • the pelletized polycarbonate resin composition was then dried at about 80 ° C. for about 6 hours, and then injected at about 280 ° C. using an injection machine to prepare a specimen.
  • the weight average molecular weight-1 was determined by gel permeation chromatography on the basis of standard polystyrene.
  • the weight average molecular weight-2 was measured in the same manner with respect to the specimen prepared by injection molding the pelletized polycarbonate resin composition.
  • Table 1 and Table 2 showed that the polycarbonate resin compositions according to Examples 1 to 10 were excellent in both mechanical strength and thermal decomposition resistance.
  • the flexural strength was large, the melt index was small, and the weight average molecular weight was large. It can be seen that the thermal decomposition of the polycarbonate resin is suppressed due to the addition of the antimony-based ion exchanger, thereby improving the physical properties of the polycarbonate resin composition.
  • the polycarbonate resin composition to which the ion exchangers of Comparative Examples 1 and 2 were not added had a lower mechanical strength and a smaller weight average molecular weight.
  • the polycarbonate resin compositions of Comparative Examples 7 and 8 used the same ion exchanger as in the examples, but the content was outside the scope of the present invention, and the flexural strength and the weight average molecular weight were smaller than those of the examples, resulting in a polycarbonate resin composition. It can be seen that the content of the ion exchanger is a major factor in forming.
  • the polycarbonate resin compositions of Comparative Examples 9 and 10 used an organic acid instead of an ion exchanger, and small mechanical strength and weight average molecular weight were observed. This can be expected that the organic acid decomposes the polycarbonate resin.
  • the polycarbonate resin composition is required to have a certain level of fluidity in order to facilitate processing, but low molecular weight polycarbonate resin is produced by thermal decomposition, and the increased fluidity may result in deterioration of the physical properties of the resin composition. have.
  • the polycarbonate resin composition according to the present invention can implement excellent physical properties by preventing thermal decomposition of polycarbonate, it is possible to manufacture a molded article excellent in thermal decomposition resistance and mechanical strength using the polycarbonate resin composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de polycarbonate et un article moulé préparé à partir de celle-ci. La composition de résine de polycarbonate comprend : a) une résine de polycarbonate ; (b) un matériau de renfort en forme d'aiguille ; et (c) un matériau d'échange d'ions à base d'antimoine ; et comprend de 0,01 à 2 parties en poids de l'échangeur d'ions à base d'antimoine (c) par rapport à 100 parties en poids de la somme de la résine de polycarbonate (a) et du matériau de renfort en forme d'aiguille (b).
PCT/KR2014/008296 2014-05-07 2014-09-04 Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci Ceased WO2015170803A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0054363 2014-05-07
KR1020140054363A KR101735883B1 (ko) 2014-05-07 2014-05-07 폴리카보네이트 수지 조성물 및 이로부터 제조된 성형품

Publications (1)

Publication Number Publication Date
WO2015170803A1 true WO2015170803A1 (fr) 2015-11-12

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PCT/KR2014/008296 Ceased WO2015170803A1 (fr) 2014-05-07 2014-09-04 Composition de résine de polycarbonate et articles moulés préparés à partir de celle-ci

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WO (1) WO2015170803A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5055523A (en) * 1989-03-20 1991-10-08 Ce Plastics Japan Limited Aromatic polycarbonate resin composition
KR20000069101A (ko) * 1997-09-25 2000-11-25 야스이 쇼사꾸 강화, 난연화 열가소성 수지 조성물 및 이의 제법
KR20090031869A (ko) * 2006-06-30 2009-03-30 도레이 카부시키가이샤 열가소성 수지 조성물 및 그 성형품
KR20100059980A (ko) * 2007-10-16 2010-06-04 테이진 카세이 가부시키가이샤 방향족 폴리카보네이트 수지 조성물
WO2011052849A1 (fr) * 2009-11-02 2011-05-05 제일모직 주식회사 Composition de résine thermoplastique et pièces moulées utilisant une telle composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003286348A (ja) * 2002-03-28 2003-10-10 Toyota Central Res & Dev Lab Inc 樹脂複合材料の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5055523A (en) * 1989-03-20 1991-10-08 Ce Plastics Japan Limited Aromatic polycarbonate resin composition
KR20000069101A (ko) * 1997-09-25 2000-11-25 야스이 쇼사꾸 강화, 난연화 열가소성 수지 조성물 및 이의 제법
KR20090031869A (ko) * 2006-06-30 2009-03-30 도레이 카부시키가이샤 열가소성 수지 조성물 및 그 성형품
KR20100059980A (ko) * 2007-10-16 2010-06-04 테이진 카세이 가부시키가이샤 방향족 폴리카보네이트 수지 조성물
WO2011052849A1 (fr) * 2009-11-02 2011-05-05 제일모직 주식회사 Composition de résine thermoplastique et pièces moulées utilisant une telle composition

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Publication number Publication date
KR20150127930A (ko) 2015-11-18
KR101735883B1 (ko) 2017-05-30

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