WO2021085867A1 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Thermoplastic resin composition and molded product manufactured therefrom Download PDF

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Publication number
WO2021085867A1
WO2021085867A1 PCT/KR2020/013017 KR2020013017W WO2021085867A1 WO 2021085867 A1 WO2021085867 A1 WO 2021085867A1 KR 2020013017 W KR2020013017 W KR 2020013017W WO 2021085867 A1 WO2021085867 A1 WO 2021085867A1
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weight
parts
thermoplastic resin
cross
resin composition
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PCT/KR2020/013017
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French (fr)
Korean (ko)
Inventor
양성우
최기홍
하동인
강태곤
강미성
신동엽
Original Assignee
롯데케미칼 주식회사
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Priority to CN202080075403.6A priority Critical patent/CN114641535B/en
Publication of WO2021085867A1 publication Critical patent/WO2021085867A1/en

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    • 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
    • C08K3/34—Silicon-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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like, and a molded article manufactured therefrom.
  • polycarbonate resin is excellent in impact resistance, heat resistance, dimensional stability, weather resistance, flame resistance, and electrical properties, and has the advantage of being transparent. useful. In addition, it has a feature that can enhance various physical properties by applying various fillers.
  • fillers such as glass fiber, talc, and wollastonite, which are applied to improve the dimensional stability of polycarbonate resin, may differ in physical properties depending on the type. It is very difficult to implement a level of dimensional stability.
  • thermoplastic resin composition that can implement metal-level dimensional stability and has excellent flame retardancy and impact resistance.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a polycarbonate resin; About 1 to about 20 parts by weight of a polyester resin; About 30 to about 80 parts by weight of glass fiber; About 5 to about 33 parts by weight of mica; And about 5 to about 25 parts by weight of a phosphazene-based flame retardant, wherein the glass fiber has a cross-sectional diameter of about 5 to about 20 ⁇ m, and a circular cross-section of about 1 to about 15 mm in length before processing, and One of the rectangular cross-section glass fibers having an aspect ratio of the cross section (long diameter of the cross section/short diameter of the cross section) of about 1.5 to about 10, the short diameter of the cross section of about 2 to about 10 ⁇ m, and the length before processing is about 1 to about 15 mm Including more than a species, the mica has an aspect ratio of a cross-section (long diameter of a cross-section / short diameter of a cross-section) of about 90 to
  • the polyester resin may include one or more of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene terephthalate.
  • the polyester resin may include one or more of polyethylene terephthalate and polybutylene terephthalate.
  • the weight ratio of the polyester resin and the glass fiber may be about 1: 2 to about 1: 40.
  • the weight ratio of the polyester resin and the mica may be about 1: 1 to about 1: 15.
  • the thermoplastic resin composition is a 10 mm ⁇ 10 mm ⁇ 6.4 mm size of the injection specimen measured by raising the temperature from 0 °C to 90 °C at a rate of 5 °C / min according to ASTM D696
  • the coefficient of linear expansion may be about 20 to about 45 ⁇ m/m ⁇ °C.
  • thermoplastic resin composition may have a flame retardancy of V-0 of a 0.8 mm-thick injection specimen measured by the UL-94 vertical test method.
  • the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 from about 9 to about 17 kgf ⁇ cm/cm.
  • Another aspect of the present invention relates to a molded article.
  • the molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 8.
  • the molded article may be an injection molded article having a width of about 100 to about 300 cm, a length of about 50 to about 150 cm, and a thickness of about 0.1 to about 10 mm.
  • the present invention has the effect of the invention of providing a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like, and a molded article formed therefrom.
  • thermoplastic resin composition includes (A) a polycarbonate resin; (B) polyester resin; (C) glass fibers; (D) mica; And (E) a phosphazene-based flame retardant.
  • a polycarbonate resin used in a conventional thermoplastic resin composition may be used.
  • an aromatic polycarbonate resin prepared by reacting diphenols (aromatic diol compounds) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.
  • the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like may be exemplified, but are not limited thereto.
  • the polycarbonate resin may be used having a branched chain, for example, about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound with respect to the total diphenols used for polymerization, specifically , A branched polycarbonate resin prepared by adding a compound having a trivalent or higher phenol group may be used.
  • the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof.
  • the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor, such as a bifunctional carboxylic acid.
  • the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 200,000 g/mol, for example, about 15,000 to about 80,000 g/mol. In the above range, the fluidity (processability) of the thermoplastic resin composition may be excellent.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the polyester resin of the present invention is applied together with glass fiber, mica, etc., and can realize metal-level dimensional stability without deteriorating physical properties such as impact resistance and flame retardancy.
  • the polyester resin is a dicarboxylic acid component, terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid.
  • Aromatic dicarboxylic acids such as carboxylic acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl- 1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate, dimethyl-2,3-na
  • diol components such as aromatic dicarboxylate such as phthalate, dimethyl-2,6-naphthalate, dimethyl-2,7-naphthalate, etc., ethylene glycol, 1,2-propylene
  • the polyester resin is one of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), and polycyclohexylene terephthalate It may include more than one.
  • the polyester resin may be polyethylene terephthalate, polybutylene terephthalate, a combination thereof, or the like.
  • the polyester resin of the present invention is dissolved in an o-chlorophenol solution (concentration: 0.5 g/dl) and the intrinsic viscosity measured using a Ubbelohde viscometer (capillary viscometer) at 25° C. is about 0.6 to about 1.5 dl/ g, for example about 0.7 to about 1.3 dl/g. Within the above range, the processability and dimensional stability of the thermoplastic resin composition may be excellent.
  • the polyester resin may be included in about 1 to about 20 parts by weight, for example, about 1.5 to about 15 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the polyester resin is less than about 1 part by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 20 parts by weight, the thermoplastic resin composition There is a fear that the flame retardancy, impact resistance, etc. may be deteriorated.
  • the glass fiber of the present invention is applied together with the polyester resin, mica, and the like, so as to realize metal-level dimensional stability without deteriorating physical properties such as flame retardancy and impact resistance.
  • the glass fibers may be in the form of fibers, and may have a circular (including oval) and/or rectangular cross-section.
  • the circular cross-section of the glass fiber has a cross-sectional diameter of about 5 to about 20 ⁇ m, for example, about 10 to about 20 ⁇ m, and a length before processing of about 1 to about 15 mm, for example, about 2 to about 8 mm
  • the rectangular cross-section of the glass fiber may have an aspect ratio of the cross-section (long diameter of the cross-section / short diameter of the cross-section) of about 1.5 to about 10, for example, about 2 to about 8, and the short diameter of the cross-section of about 2 to It may be about 10 ⁇ m, for example, about 4 to about 8 ⁇ m, and the length before processing may be about 1 to about 15 mm, for example, about 2 to about 8 mm. If it is out of the above range, there is a concern that the dimensional stability, rigidity, and processability of the thermoplastic resin composition may be deteriorated.
  • the glass fibers may be treated with a conventional surface treatment agent.
  • the glass fiber may be included in about 30 to about 80 parts by weight, for example, about 40 to about 80 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the glass fiber is less than about 30 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 80 parts by weight, the thermoplastic resin composition There is a concern that impact resistance, flame retardancy, etc. may be deteriorated.
  • the weight ratio (B:C) of the polyester resin and the glass fiber may be about 1: 2 to about 1: 40, for example, about 1: 4 to about 1: 40.
  • the dimensional stability and impact resistance of the thermoplastic resin composition may be more excellent.
  • the mica of the present invention is applied together with the polyester resin, glass fiber, and the like, and can realize metal-level dimensional stability without deteriorating physical properties such as flame retardancy and impact resistance.
  • the mica is a plate-shaped filler
  • the aspect ratio of the cross section (long diameter of the cross section / short diameter of the cross section) may be about 90 to about 300, for example, about 100 to about 250
  • a laser particle size analyzer manufactured by Beckman Coulter , Equipment name: LS 13 320
  • the average particle size (D50) may be about 200 to about 550 ⁇ m, for example, about 250 to about 450 ⁇ m. If it is out of the above range, there is a concern that the dimensional stability, rigidity, and processability of the thermoplastic resin composition may be deteriorated.
  • the mica may be included in about 5 to about 33 parts by weight, for example, about 10 to about 30 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the mica is less than about 5 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 33 parts by weight, the internal content of the thermoplastic resin composition There is a risk of deterioration in impact resistance and flame retardancy.
  • the weight ratio (B:D) of the polyester resin and the mica may be about 1:1 to about 1:15, for example, about 1:1 to about 1:14.
  • the dimensional stability and impact resistance of the thermoplastic resin composition may be more excellent.
  • the weight ratio (C:D) of the glass fiber and the mica may be about 1.5:1 to about 7:1, for example, about 2:1 to about 6:1.
  • the weight ratio of the glass fiber and the mica is less than about 1.5:1, the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 7:1, the dimensional stability, flame retardancy, and impact resistance of the thermoplastic resin composition There is a risk of lowering the back.
  • the phosphazene-based flame retardant according to an embodiment of the present invention is capable of improving the flame retardancy of the thermoplastic resin composition, and a phosphazene compound used in a conventional flame retardant thermoplastic resin composition may be used.
  • the phosphazene-based flame retardant may include a phosphazene compound represented by the following formula (1).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently 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, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, 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 Or an aryloxy group, a C5 to C20 heteroaryl group, a substituted or unsubstituted C3 to C20 alkoxycarbonylalkyl group, a substituted or unsubstituted C2 to C10 carbonylalkyl group, an amino group or a hydroxy group.
  • 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 hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and It means substituted with a substituent such as a heterocycloalkyl group, a C4-10 heteroaryl group, and a combination thereof.
  • substituents including the "alkyl”, “alkoxy” and other “alkyl” moieties include both straight-chain or branched forms, and “alkenyl” has 2 to 8 carbon atoms and contains one or more double bonds. It includes all of the linear or branched forms, and the “cycloalkyl” includes all of the saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms.
  • the "aryl” is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and suitably represents a single or fused ring system containing 4 to 7, preferably 5 or 6 ring atoms in each ring. Includes. Specifically, phenyl, naphthyl, biphenyl, tolyl, and the like can be illustrated.
  • heterocycloalkyl refers to a cycloalkyl group in which 1 to 3 heteroatoms selected from N, O, S are included as a saturated cyclic hydrocarbon skeleton atom, and the remaining saturated monocyclic or bicyclic ring skeleton atoms are carbon.
  • heteroaryl refers to an aryl group including 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon, and the heteroaryl group is hetero Atoms include divalent aryl groups that are oxidized or quaternized to form, for example, N-oxides or quaternary salts.
  • furyl, thienyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tria Zolyl, tetrazolyl, furazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like can be exemplified.
  • the phosphazene-based flame retardant may be included in an amount of about 5 to about 25 parts by weight, for example, about 7 to about 25 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the content of the phosphazene-based flame retardant is less than about 5 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a risk that the flame retardancy and fluidity of the thermoplastic resin composition may be deteriorated, and when it exceeds about 25 parts by weight, thermoplastic There is a fear that the impact resistance and the like of the resin composition may be deteriorated.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additives include antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto.
  • the content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • thermoplastic resin composition according to an embodiment of the present invention is in the form of a pellet melt-extruded at about 200 to about 280°C, for example about 220 to about 270°C, by mixing the constituents and using a conventional twin screw extruder. I can.
  • the coefficient of linear expansion of an injection specimen of 10 mm ⁇ 10 mm ⁇ 6.4 mm measured by heating from 0°C to 90°C at a rate of 5°C/min with a thermo-mechanical analyzer May be about 20 to about 45 ⁇ m/m ⁇ °C, for example, about 30 to about 40 ⁇ m/m ⁇ °C.
  • thermoplastic resin composition may have a flame retardancy of V-0 of a 0.8 mm-thick injection specimen measured by UL-94 vertical test method.
  • the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256, from about 9 to about 17 kgf ⁇ cm/cm, for example, from about 10 to about 16 kgf ⁇ cm May be /cm.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the antimicrobial thermoplastic resin composition may be prepared in the form of pellets, and the prepared pellets may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the field to which the present invention belongs.
  • the molded article is excellent in dimensional stability, flame retardancy, impact resistance, and balance of physical properties thereof, and thus is useful as an interior/exterior material of an electric and electronic product, a thin film sheet, and the like.
  • the molded article has a coefficient of linear expansion of about 20 to about 45 of an injection specimen of 10 mm ⁇ 10 mm ⁇ 6.4 mm measured by heating from 0° C. to 90° C. at a rate of 5° C./min according to ASTM D696.
  • the flame retardancy of the 0.8 mm-thick injection specimen measured by the UL-94 vertical test method is V-0
  • the notched Izod impact strength of the 1/8" thick specimen measured according to ASTM D256 is about 9 to about 17 kgf ⁇ cm/cm, it is suitable as a large injection molded article having a width of about 100 to about 300 cm, a length of about 50 to about 150 cm, and a thickness of about 0.1 to about 10 mm.
  • a bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 25,000 g/mol was used.
  • B2 Polybutylene terephthalate (PBT, manufacturer: Shinkong, product name: Shinite K006, intrinsic viscosity: 1.3 dl/g) was used.
  • (C1) A rectangular cross-section glass fiber (manufacturer: Nittobo, product name: FF45y11) having an aspect ratio of the cross section (long diameter of the cross section/short diameter of the cross section) is 4, the short diameter is 7 ⁇ m, and the length before processing is 3 mm was used.
  • C2 A glass fiber (manufacturer: Owen Corning, product name: CS 183F-4P) having a circular cross-section with a diameter of 13 ⁇ m and a length of 4 mm before processing was used.
  • C3 A glass fiber (manufacturer: Sungjin Fiber, product name: MF75W-NL) having a diameter of a cross section of 10 ⁇ m and a length of 50 ⁇ m before processing was used.
  • a mica manufactured by IMERYS, product name: SUZORITE 60-S having an aspect ratio of a cross section (long axis of a cross section/short axis of a cross section) of 100 and an average particle size (D50) of 280 ⁇ m was used.
  • a mica manufactured by IMERYS, product name: SUZORITE 200-HK having an aspect ratio of a cross section (longer diameter of a cross section/shorter diameter of a cross section) is 55 and an average particle size (D50) of 60 ⁇ m was used.
  • a mica manufactured by IMERYS, product name: SUZORITE 150-S having an aspect ratio of a cross section (long diameter of a cross section/short diameter of a cross section) is 90 and an average particle size (D50) of 150 ⁇ m was used.
  • a mica manufactured by IMERYS, product name: SUZORITE 30-S having an aspect ratio of a cross section (long diameter of a cross section/short diameter of a cross section) is 100 and an average particle size (D50) of 600 ⁇ m was used.
  • Example One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 (B1) (parts by weight) 1.5 4 15 - 4 4 (B2) (parts by weight) - - - 4 - - (C1) (parts by weight) 60 60 60 60 40 80 (C2) (parts by weight) - - - - - - (C3) (parts by weight) - - - - - - - (D1) (parts by weight) 20 20 20 20 20 20 20 20 20 20 (D2) (parts by weight) - - - - - - - (D3) (parts by weight) - - - - - - - (D4) (parts by weight) - - - - - - (D5) (parts by weight) - - - - - - - (E1) (parts by weight) 15 15 15 15 15 15 (E2) (parts by weight)
  • Example 7 8 9 10 11 (A) (parts by weight) 100 100 100 100 100 100 100 (B1) (parts by weight) 4 4 4 4 4 4 4 (B2) (parts by weight) - - - - - (C1) (parts by weight) 60 60 60 60 - (C2) (parts by weight) - - - - 60 (C3) (parts by weight) - - - - (D1) (parts by weight) 10 30 20 20 20 20 (D2) (parts by weight) - - - - - (D3) (parts by weight) - - - - - (D4) (parts by weight) - - - - - - (D5) (parts by weight) - - - - - - (E1) (parts by weight) 15 15 7 25 15 (E2) (parts by weight) - - - Coefficient of linear expansion 37.5 32.0 35.1 36.2 38.4 Flame retardancy V-0 V
  • thermoplastic resin composition of the present invention has excellent dimensional stability, flame retardancy, impact resistance, and the like.
  • thermoplastic resin composition decreases, and when mica (D3) is applied (comparative Example 9), it can be seen that the dimensional stability and impact resistance of the thermoplastic resin composition are deteriorated, and when mica (D4) is applied (Comparative Example 10), the dimensional stability, flame retardancy, impact resistance, etc. of the thermoplastic resin composition are deteriorated. It can be seen, and when talc (D5) is applied (Comparative Example 11), it can be seen that the dimensional stability, flame retardancy, impact resistance, and the like of the thermoplastic resin composition are deteriorated.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

A thermoplastic resin composition according to the present invention comprises: about 100 parts by weight of a polycarbonate resin; about 1 to about 20 parts by weight of a polyester resin; about 30 to about 80 parts by weight of glass fibers; about 5 to about 33 parts by weight of mica; and about 5 to about 25 parts by weight of a phosphagen-based flame retardant. The glass fibers comprise at least one of: a circular cross-section glass fiber having a sectional diameter of about 5 to about 20 ㎛ and a pre-processing length of about 1 to about 15 mm; and a rectangular cross-section glass fiber having a cross-sectional aspect ratio of about 1.5 to about 1.0, a cross sectional minor diameter of about 2 to about 10 ㎛, and a pre-processing length of about 1 to about 15 mm. The mica has a cross-sectional aspect ratio of about 90 to about 300 and a mean particle size (D50) of about 200 to about 550 ㎛. The weight ratio of the glass fibers and the mica is about 1.5 : 1 to about 7 : 1. The thermoplastic resin composition is excellent in terms of dimensional stability, flame retardancy, impact resistance, and the like.

Description

열가소성 수지 조성물 및 이로부터 제조된 성형품Thermoplastic resin composition and molded article manufactured therefrom
본 발명은 열가소성 수지 조성물 및 이로부터 제조된 성형품에 관한 것이다. 보다 구체적으로 본 발명은 치수 안정성, 난연성, 내충격성 등이 우수한 열가소성 수지 조성물 및 이로부터 제조된 성형품에 관한 것이다.The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like, and a molded article manufactured therefrom.
엔지니어링 플라스틱으로서, 폴리카보네이트 수지는 내충격성, 내열성, 치수 안정성, 내후성, 난연성, 전기 특성 등이 우수하며, 투명하다는 장점을 가지고 있어, 전기/전자 제품의 하우징, 기타 사무용 기기의 내/외장재 등으로 유용하다. 또한, 다양한 필러(filler)의 적용으로 다양한 물성을 강화시킬 수 있는 특징을 가지고 있다.As an engineering plastic, polycarbonate resin is excellent in impact resistance, heat resistance, dimensional stability, weather resistance, flame resistance, and electrical properties, and has the advantage of being transparent. useful. In addition, it has a feature that can enhance various physical properties by applying various fillers.
그러나, 폴리카보네이트 수지의 치수 안정성을 향상시키기 위하여 적용되는 유리 섬유, 탈크, 규회석 등의 필러는 종류에 따라 물성에 차이가 발생하기도 하고, 일정 이상의 함량을 투입 시, 오히려 물성 저하가 발생하므로, 금속 수준의 치수 안정성 구현이 매우 어렵다.However, fillers such as glass fiber, talc, and wollastonite, which are applied to improve the dimensional stability of polycarbonate resin, may differ in physical properties depending on the type. It is very difficult to implement a level of dimensional stability.
따라서, 금속 수준의 치수 안정성을 구현할 수 있고, 난연성, 내충격성 등이 우수한 열가소성 수지 조성물의 개발이 필요한 실정이다.Accordingly, there is a need to develop a thermoplastic resin composition that can implement metal-level dimensional stability and has excellent flame retardancy and impact resistance.
본 발명의 배경기술은 대한민국 공개특허 10-2011-0059886호 등에 개시되어 있다.Background art of the present invention is disclosed in Korean Patent Application Laid-Open No. 10-2011-0059886 and the like.
본 발명의 목적은 치수 안정성, 난연성, 내충격성 등이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like.
본 발명의 다른 목적은 상기 열가소성 수지 조성물로부터 형성된 성형품을 제공하기 위한 것이다.Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.All of the above and other objects of the present invention can be achieved by the present invention described below.
1. 본 발명의 하나의 관점은 열가소성 수지 조성물에 관한 것이다. 상기 열가소성 수지 조성물은 폴리카보네이트 수지 약 100 중량부; 폴리에스테르 수지 약 1 내지 약 20 중량부; 유리 섬유 약 30 내지 약 80 중량부; 마이카 약 5 내지 약 33 중량부; 및 포스파젠계 난연제 약 5 내지 약 25 중량부;를 포함하며, 상기 유리 섬유는 단면 직경이 약 5 내지 약 20 ㎛이고, 가공 전 길이가 약 1 내지 약 15 mm인 원형 단면의 유리 섬유, 및 단면의 종횡비(단면의 장경/단면의 단경)가 약 1.5 내지 약 10이고, 단면의 단경이 약 2 내지 약 10 ㎛이며, 가공 전 길이가 약 1 내지 약 15 mm인 직사각형 단면의 유리 섬유 중 1종 이상을 포함하고, 상기 마이카는 단면의 종횡비(단면의 장경/단면의 단경)가 약 90 내지 약 300이고, 평균 입자 크기(D50)가 약 200 내지 약 550 ㎛이며, 상기 유리 섬유 및 상기 마이카의 중량비는 약 1.5 : 1 내지 약 7 : 1인 것을 특징으로 한다.1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a polycarbonate resin; About 1 to about 20 parts by weight of a polyester resin; About 30 to about 80 parts by weight of glass fiber; About 5 to about 33 parts by weight of mica; And about 5 to about 25 parts by weight of a phosphazene-based flame retardant, wherein the glass fiber has a cross-sectional diameter of about 5 to about 20 μm, and a circular cross-section of about 1 to about 15 mm in length before processing, and One of the rectangular cross-section glass fibers having an aspect ratio of the cross section (long diameter of the cross section/short diameter of the cross section) of about 1.5 to about 10, the short diameter of the cross section of about 2 to about 10 μm, and the length before processing is about 1 to about 15 mm Including more than a species, the mica has an aspect ratio of a cross-section (long diameter of a cross-section / short diameter of a cross-section) of about 90 to about 300, an average particle size (D50) of about 200 to about 550 µm, and the glass fiber and the mica The weight ratio of is characterized in that from about 1.5: 1 to about 7: 1.
2. 상기 1 구체예에서, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리트리메틸렌테레프탈레이트 및 폴리시클로헥실렌테레프탈레이트 중 1종 이상을 포함할 수 있다.2. In the above 1 embodiment, the polyester resin may include one or more of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene terephthalate.
3. 상기 1 또는 2 구체예에서, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 중 1종 이상을 포함할 수 있다.3. In the above 1 or 2 embodiments, the polyester resin may include one or more of polyethylene terephthalate and polybutylene terephthalate.
4. 상기 1 내지 3 구체예에서, 상기 폴리에스테르 수지 및 상기 유리 섬유의 중량비는 약 1 : 2 내지 약 1 : 40일 수 있다.4. In the above 1 to 3 embodiments, the weight ratio of the polyester resin and the glass fiber may be about 1: 2 to about 1: 40.
5. 상기 1 내지 4 구체예에서, 상기 폴리에스테르 수지 및 상기 마이카의 중량비는 약 1 : 1 내지 약 1 : 15일 수 있다.5. In the above 1 to 4 embodiments, the weight ratio of the polyester resin and the mica may be about 1: 1 to about 1: 15.
6. 상기 1 내지 5 구체예에서, 상기 열가소성 수지 조성물은 ASTM D696에 의거하여, 0℃에서 90℃까지 5℃/min 속도로 승온하며 측정한 10 mm × 10 mm × 6.4 mm 크기의 사출 시편의 선팽창계수가 약 20 내지 약 45 ㎛/m·℃일 수 있다.6. In the above 1 to 5 embodiments, the thermoplastic resin composition is a 10 mm × 10 mm × 6.4 mm size of the injection specimen measured by raising the temperature from 0 ℃ to 90 ℃ at a rate of 5 ℃ / min according to ASTM D696 The coefficient of linear expansion may be about 20 to about 45 µm/m·°C.
7. 상기 1 내지 6 구체예에서, 상기 열가소성 수지 조성물은 UL-94 vertical test 방법으로 측정한 0.8 mm 두께 사출 시편의 난연도가 V-0일 수 있다.7. In the above embodiments 1 to 6, the thermoplastic resin composition may have a flame retardancy of V-0 of a 0.8 mm-thick injection specimen measured by the UL-94 vertical test method.
8. 상기 1 내지 7 구체예에서, 상기 열가소성 수지 조성물은 ASTM D256에 의거하여 측정한 두께 1/8" 시편의 노치 아이조드 충격강도가 약 9 내지 약 17 kgf·cm/cm일 수 있다.8. In the above 1 to 7 embodiments, the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 from about 9 to about 17 kgf·cm/cm.
9. 본 발명의 다른 관점은 성형품에 관한 것이다. 상기 성형품은 상기 1 내지 8 중 어느 하나에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 한다.9. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 8.
10. 상기 9 구체예에서, 상기 성형품은 가로 약 100 내지 약 300 cm, 세로 약 50 내지 약 150 cm 및 두께 약 0.1 내지 약 10 mm의 사출 성형품일 수 있다.10. In the 9 embodiments, the molded article may be an injection molded article having a width of about 100 to about 300 cm, a length of about 50 to about 150 cm, and a thickness of about 0.1 to about 10 mm.
본 발명은 치수 안정성, 난연성, 내충격성 등이 우수한 열가소성 수지 조성물 및 이로부터 형성된 성형품을 제공하는 발명의 효과를 갖는다.The present invention has the effect of the invention of providing a thermoplastic resin composition excellent in dimensional stability, flame retardancy, impact resistance, and the like, and a molded article formed therefrom.
이하, 본 발명을 상세히 설명하면, 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 열가소성 수지 조성물은 (A) 폴리카보네이트 수지; (B) 폴리에스테르 수지; (C) 유리 섬유; (D) 마이카; 및 (E) 포스파젠계 난연제;를 포함한다.The thermoplastic resin composition according to the present invention includes (A) a polycarbonate resin; (B) polyester resin; (C) glass fibers; (D) mica; And (E) a phosphazene-based flame retardant.
본 명세서에서, 수치범위를 나타내는 "a 내지 b"는 "≥a 이고 ≤b"으로 정의한다.In the present specification, "a to b" representing a numerical range is defined as "≥a and ≤b".
(A) 폴리카보네이트 수지(A) Polycarbonate resin
본 발명의 일 구체예에 따른 폴리카보네이트 수지로는 통상의 열가소성 수지 조성물에 사용되는 폴리카보네이트 수지를 사용할 수 있다. 예를 들면, 디페놀류(방향족 디올 화합물)를 포스겐, 할로겐 포르메이트, 탄산 디에스테르 등의 전구체와 반응시킴으로써 제조되는 방향족 폴리카보네이트 수지를 사용할 수 있다.As the polycarbonate resin according to an embodiment of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin prepared by reacting diphenols (aromatic diol compounds) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.
구체예에서, 상기 디페놀류로는 4,4'-비페놀, 2,2-비스(4-히드록시페닐)프로판, 2,4-비스(4-히드록시페닐)-2-메틸부탄, 1,1-비스(4-히드록시페닐)시클로헥산, 2,2-비스(3-클로로-4-히드록시페닐)프로판, 2,2-비스(3,5-디클로로-4-히드록시페닐)프로판 등을 예시할 수 있으나, 이에 제한되지 않는다. 예를 들면, 2,2-비스(4-히드록시페닐)프로판, 2,2-비스(3,5-디클로로-4-히드록시페닐)프로판, 또는 1,1-비스(4-히드록시페닐)시클로헥산을 사용할 수 있고, 구체적으로, 비스페놀-A 라고 불리는 2,2-비스(4-히드록시페닐)프로판을 사용할 수 있다.In a specific embodiment, the diphenols include 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like may be exemplified, but are not limited thereto. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl) ) Cyclohexane can be used, specifically, 2,2-bis(4-hydroxyphenyl)propane called bisphenol-A can be used.
구체예에서, 상기 폴리카보네이트 수지는 분지쇄가 있는 것이 사용될 수 있으며, 예를 들면 중합에 사용되는 디페놀류 전체에 대하여, 약 0.05 내지 약 2 몰%의 3가 또는 그 이상의 다관능 화합물, 구체적으로, 3가 또는 그 이상의 페놀기를 가진 화합물을 첨가하여 제조한 분지형 폴리카보네이트 수지를 사용할 수도 있다.In a specific embodiment, the polycarbonate resin may be used having a branched chain, for example, about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound with respect to the total diphenols used for polymerization, specifically , A branched polycarbonate resin prepared by adding a compound having a trivalent or higher phenol group may be used.
구체예에서, 상기 폴리카보네이트 수지는 호모 폴리카보네이트 수지, 코폴리카보네이트 수지 또는 이들의 블렌드 형태로 사용할 수 있다. 또한, 상기 폴리카보네이트 수지는 에스테르 전구체(precursor), 예컨대 2관능 카르복실산의 존재 하에서 중합 반응시켜 얻어진 방향족 폴리에스테르-카보네이트 수지로 일부 또는 전량 대체하는 것도 가능하다.In a specific embodiment, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor, such as a bifunctional carboxylic acid.
구체예에서, 상기 폴리카보네이트 수지는 GPC(gel permeation chromatography)로 측정한 중량평균분자량(Mw)이 약 10,000 내지 약 200,000 g/mol, 예를 들면 약 15,000 내지 약 80,000 g/mol일 수 있다. 상기 범위에서 열가소성 수지 조성물의 유동성(가공성) 등이 우수할 수 있다.In a specific embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 200,000 g/mol, for example, about 15,000 to about 80,000 g/mol. In the above range, the fluidity (processability) of the thermoplastic resin composition may be excellent.
(B) 폴리에스테르 수지(B) polyester resin
본 발명의 폴리에스테르 수지는 유리 섬유, 마이카 등과 함께 적용되어, 내충격성, 난연성 등의 물성 저하 없이, 금속 수준의 치수 안정성을 구현할 수 있는 것으로서, 통상의 열가소성 수지 조성물에 사용되는 폴리에스테르 수지를 사용할 수 있다. 예를 들면, 상기 폴리에스테르 수지는 디카르복실산 성분으로서, 테레프탈산(terephthalic acid, TPA), 이소프탈산(isophthalic acid, IPA), 1,2-나프탈렌 디카르복실산, 1,4-나프탈렌 디카르복실산, 1,5-나프탈렌 디카르복실산, 1,6-나프탈렌 디카르복실산, 1,7-나프탈렌 디카르복실산, 1,8-나프탈렌 디카르복실산, 2,3-나프탈렌 디카르복실산, 2,6-나프탈렌 디카르복실산, 2,7-나프탈렌 디카르복실산 등의 방향족 디카르복실산, 디메틸 테레프탈레이트(dimethyl terephthalate, DMT), 디메틸 이소프탈레이트(dimethyl isophthalate), 디메틸-1,2-나프탈레이트, 디메틸-1,5-나프탈레이트, 디메틸-1,7-나프탈레이트, 디메틸-1,7-나프탈레이트, 디메틸-1,8-나프탈레이트, 디메틸-2,3-나프탈레이트, 디메틸-2,6-나프탈레이트, 디메틸-2,7-나프탈레이트 등의 방향족 디카르복실레이트(aromatic dicarboxylate) 등과 디올 성분으로서, 에틸렌 글리콜, 1,2-프로필렌 글리콜, 1,3-프로필렌 글리콜, 2,2-디메틸-1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 1,5-펜탄디올, 1,5-펜탄디올, 1,6-헥산디올, 환형알킬렌디올 등을 중축합하여 얻을 수 있다.The polyester resin of the present invention is applied together with glass fiber, mica, etc., and can realize metal-level dimensional stability without deteriorating physical properties such as impact resistance and flame retardancy. I can. For example, the polyester resin is a dicarboxylic acid component, terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid. Acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as carboxylic acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl- 1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate, dimethyl-2,3-na As diol components such as aromatic dicarboxylate such as phthalate, dimethyl-2,6-naphthalate, dimethyl-2,7-naphthalate, etc., ethylene glycol, 1,2-propylene glycol, 1,3-propylene Glycol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, cyclic alkyl It can be obtained by polycondensing rendiol or the like.
구체예에서, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트(PBT), 폴리에틸렌나프탈레이트(PEN) 및 폴리트리메틸렌테레프탈레이트(PTT), 폴리시클로헥실렌테레프탈레이트 중 1종 이상을 포함할 수 있다. 예를 들면, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 이들의 조합 등일 수 있다.In a specific embodiment, the polyester resin is one of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), and polycyclohexylene terephthalate It may include more than one. For example, the polyester resin may be polyethylene terephthalate, polybutylene terephthalate, a combination thereof, or the like.
구체예에서, 본 발명의 폴리에스테르 수지는 o-클로로페놀 용액(농도: 0.5 g/dl)에 녹여 25℃에서 Ubbelohde viscometer(capillary viscometer)를 이용하여 측정한 고유점도가 약 0.6 내지 약 1.5 dl/g, 예를 들면 약 0.7 내지 약 1.3 dl/g일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 가공성, 치수 안정성 등이 우수할 수 있다.In a specific embodiment, the polyester resin of the present invention is dissolved in an o-chlorophenol solution (concentration: 0.5 g/dl) and the intrinsic viscosity measured using a Ubbelohde viscometer (capillary viscometer) at 25° C. is about 0.6 to about 1.5 dl/ g, for example about 0.7 to about 1.3 dl/g. Within the above range, the processability and dimensional stability of the thermoplastic resin composition may be excellent.
구체예에서, 상기 폴리에스테르 수지는 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 1 내지 약 20 중량부, 예를 들면 약 1.5 내지 약 15 중량부로 포함될 수 있다. 상기 폴리에스테르 수지의 함량이 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 1 중량부 미만일 경우, 열가소성 수지 조성물의 치수 안정성 등이 저하될 우려가 있고, 약 20 중량부를 초과할 경우, 열가소성 수지 조성물의 난연성, 내충격성 등이 저하될 우려가 있다.In an embodiment, the polyester resin may be included in about 1 to about 20 parts by weight, for example, about 1.5 to about 15 parts by weight, based on about 100 parts by weight of the polycarbonate resin. When the content of the polyester resin is less than about 1 part by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 20 parts by weight, the thermoplastic resin composition There is a fear that the flame retardancy, impact resistance, etc. may be deteriorated.
(C) 유리 섬유(C) glass fiber
본 발명의 유리 섬유는 상기 폴리에스테르 수지, 마이카 등과 함께 적용되어, 난연성, 내충격성 등의 물성 저하 없이, 금속 수준의 치수 안정성을 구현할 수 있는 것이다.The glass fiber of the present invention is applied together with the polyester resin, mica, and the like, so as to realize metal-level dimensional stability without deteriorating physical properties such as flame retardancy and impact resistance.
구체예에서, 상기 유리 섬유는 섬유 형태일 수 있고, 원형(타원형 포함) 및/또는 직사각형의 단면을 가질 수 있다.In embodiments, the glass fibers may be in the form of fibers, and may have a circular (including oval) and/or rectangular cross-section.
구체예에서, 상기 원형 단면의 유리 섬유는 단면 직경이 약 5 내지 약 20 ㎛, 예를 들면 약 10 내지 약 20 ㎛, 가공 전 길이가 약 1 내지 약 15 mm, 예를 들면 약 2 내지 약 8 mm일 수 있고, 상기 직사각형 단면의 유리 섬유는 단면의 종횡비(단면의 장경/단면의 단경)가 약 1.5 내지 약 10, 예를 들면 약 2 내지 약 8일 수 있고, 단면의 단경이 약 2 내지 약 10 ㎛, 예를 들면 약 4 내지 약 8 ㎛일 수 있으며, 가공 전 길이가 약 1 내지 약 15 mm, 예를 들면 약 2 내지 약 8 mm일 수 있다. 상기 범위를 벗어날 경우, 열가소성 수지 조성물의 치수 안정성, 강성, 가공성 등이 저하될 우려가 있다.In an embodiment, the circular cross-section of the glass fiber has a cross-sectional diameter of about 5 to about 20 μm, for example, about 10 to about 20 μm, and a length before processing of about 1 to about 15 mm, for example, about 2 to about 8 mm, and the rectangular cross-section of the glass fiber may have an aspect ratio of the cross-section (long diameter of the cross-section / short diameter of the cross-section) of about 1.5 to about 10, for example, about 2 to about 8, and the short diameter of the cross-section of about 2 to It may be about 10 μm, for example, about 4 to about 8 μm, and the length before processing may be about 1 to about 15 mm, for example, about 2 to about 8 mm. If it is out of the above range, there is a concern that the dimensional stability, rigidity, and processability of the thermoplastic resin composition may be deteriorated.
구체예에서, 상기 유리 섬유는 통상의 표면 처리제로 처리된 것일 수 있다.In embodiments, the glass fibers may be treated with a conventional surface treatment agent.
구체예에서, 상기 유리 섬유는 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 30 내지 약 80 중량부, 예를 들면 약 40 내지 약 80 중량부로 포함될 수 있다. 상기 유리 섬유의 함량이 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 30 중량부 미만일 경우, 열가소성 수지 조성물의 치수 안정성 등이 저하될 우려가 있고, 약 80 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 난연성 등이 저하될 우려가 있다.In an embodiment, the glass fiber may be included in about 30 to about 80 parts by weight, for example, about 40 to about 80 parts by weight, based on about 100 parts by weight of the polycarbonate resin. When the content of the glass fiber is less than about 30 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 80 parts by weight, the thermoplastic resin composition There is a concern that impact resistance, flame retardancy, etc. may be deteriorated.
구체예에서, 상기 폴리에스테르 수지 및 상기 유리 섬유의 중량비(B:C)는 약 1 : 2 내지 약 1 : 40, 예를 들면 약 1 : 4 내지 약 1 : 40일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 치수 안정성, 내충격성 등이 더 우수할 수 있다.In a specific embodiment, the weight ratio (B:C) of the polyester resin and the glass fiber may be about 1: 2 to about 1: 40, for example, about 1: 4 to about 1: 40. Within the above range, the dimensional stability and impact resistance of the thermoplastic resin composition may be more excellent.
(D) 마이카(D) mica
본 발명의 마이카는 상기 폴리에스테르 수지, 유리 섬유 등과 함께 적용되어, 난연성, 내충격성 등의 물성 저하 없이, 금속 수준의 치수 안정성을 구현할 수 있는 것이다.The mica of the present invention is applied together with the polyester resin, glass fiber, and the like, and can realize metal-level dimensional stability without deteriorating physical properties such as flame retardancy and impact resistance.
구체예에서, 상기 마이카는 판상형 충전제로서, 단면의 종횡비(단면의 장경/단면의 단경)가 약 90 내지 약 300, 예를 들면 약 100 내지 약 250일 수 있고, 레이저 입도 분석기(제조사 : Beckman Coulter, 장비명 : LS 13 320)로 측정한 평균 입자 크기(D50)는 약 200 내지 약 550 ㎛, 예를 들면 약 250 내지 약 450 ㎛일 수 있다. 상기 범위를 벗어날 경우, 열가소성 수지 조성물의 치수 안정성, 강성, 가공성 등이 저하될 우려가 있다.In a specific embodiment, the mica is a plate-shaped filler, and the aspect ratio of the cross section (long diameter of the cross section / short diameter of the cross section) may be about 90 to about 300, for example, about 100 to about 250, and a laser particle size analyzer (manufacturer: Beckman Coulter , Equipment name: LS 13 320), the average particle size (D50) may be about 200 to about 550 μm, for example, about 250 to about 450 μm. If it is out of the above range, there is a concern that the dimensional stability, rigidity, and processability of the thermoplastic resin composition may be deteriorated.
구체예에서, 상기 마이카는 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 5 내지 약 33 중량부, 예를 들면 약 10 내지 약 30 중량부로 포함될 수 있다. 상기 마이카의 함량이 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 5 중량부 미만일 경우, 열가소성 수지 조성물의 치수 안정성 등이 저하될 우려가 있고, 약 33 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 난연성 등이 저하될 우려가 있다.In an embodiment, the mica may be included in about 5 to about 33 parts by weight, for example, about 10 to about 30 parts by weight, based on about 100 parts by weight of the polycarbonate resin. When the content of the mica is less than about 5 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a concern that the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 33 parts by weight, the internal content of the thermoplastic resin composition There is a risk of deterioration in impact resistance and flame retardancy.
구체예에서, 상기 폴리에스테르 수지 및 상기 마이카의 중량비(B:D)는 약 1 : 1 내지 약 1 : 15, 예를 들면 약 1 : 1 내지 약 1 : 14일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 치수 안정성, 내충격성 등이 더 우수할 수 있다.In a specific embodiment, the weight ratio (B:D) of the polyester resin and the mica may be about 1:1 to about 1:15, for example, about 1:1 to about 1:14. Within the above range, the dimensional stability and impact resistance of the thermoplastic resin composition may be more excellent.
구체예에서, 상기 유리 섬유 및 상기 마이카의 중량비(C:D)는 약 1.5 : 1 내지 약 7 : 1, 예를 들면 약 2 : 1 내지 약 6 : 1일 수 있다. 상기 유리 섬유 및 상기 마이카의 중량비가 약 1.5 : 1 미만일 경우, 열가소성 수지 조성물의 치수 안정성 등이 저하될 우려가 있고, 약 7 : 1를 초과할 경우, 열가소성 수지 조성물의 치수 안정성, 난연성, 내충격성 등이 저하될 우려가 있다.In an embodiment, the weight ratio (C:D) of the glass fiber and the mica may be about 1.5:1 to about 7:1, for example, about 2:1 to about 6:1. When the weight ratio of the glass fiber and the mica is less than about 1.5:1, the dimensional stability of the thermoplastic resin composition may be deteriorated, and when it exceeds about 7:1, the dimensional stability, flame retardancy, and impact resistance of the thermoplastic resin composition There is a risk of lowering the back.
(E) 포스파젠계 난연제(E) phosphazene-based flame retardant
본 발명의 일 구체예에 따른 포스파젠계 난연제는 열가소성 수지 조성물의 난연성 등을 향상시킬 수 있는 것으로서, 통상적인 난연성 열가소성 수지 조성물에 사용되는 포스파젠(phosphazene) 화합물 등을 사용할 수 있다.The phosphazene-based flame retardant according to an embodiment of the present invention is capable of improving the flame retardancy of the thermoplastic resin composition, and a phosphazene compound used in a conventional flame retardant thermoplastic resin composition may be used.
구체예에서, 상기 포스파젠계 난연제는 하기 화학식 1로 표시되는 포스파젠 화합물을 포함할 수 있다.In a specific embodiment, the phosphazene-based flame retardant may include a phosphazene compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2020013017-appb-I000001
Figure PCTKR2020013017-appb-I000001
상기 화학식 1에서, R1, R2, R3, R4, R5 및 R6는 각각 독립적으로, 수소 원자, 할로겐 원자, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 2 내지 7의 알케닐기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 헤테로시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴기 또는 아릴옥시기, 탄소수 5 내지 20의 헤테로아릴기, 치환 또는 비치환된 탄소수 3 내지 20의 알콕시카보닐알킬기, 치환 또는 비치환된 탄소수 2 내지 10의 카보닐알킬기, 아미노기 또는 히드록시기이다.In Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently 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, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, 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 Or an aryloxy group, a C5 to C20 heteroaryl group, a substituted or unsubstituted C3 to C20 alkoxycarbonylalkyl group, a substituted or unsubstituted C2 to C10 carbonylalkyl group, an amino group or a hydroxy group.
여기서, 상기 "치환"은 수소 원자가 탄소수 1 내지 10의 알킬기, 할로겐 원자, 니트로기, 시아노기, 히드록시기, 아미노기, 탄소수 6 내지 10의 아릴기, 탄소수 3 내지 10의 시클로알킬기, 탄소수 3 내지 10의 헤테로시클로알킬기, 탄소수 4 내지 10의 헤테로아릴기, 이들의 조합 등의 치환기로 치환되는 것을 의미한다.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 hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and It means substituted with a substituent such as a heterocycloalkyl group, a C4-10 heteroaryl group, and a combination thereof.
또한, 상기 "알킬", "알콕시" 및 그 외 "알킬" 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하고, "알케닐"은 2 내지 8개의 탄소 원자를 갖고 하나 이상의 이중결합을 함유하는 직쇄 또는 분쇄 형태를 모두 포함하며, 상기 "시클로알킬"은 탄소 원자수가 3 내지 20개인 포화모노시클릭 또는 포화바이시클릭 고리 구조형태를 모두 포함한다. 상기 "아릴"은 하나의 수소 원자 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함한다. 구체적으로, 페닐, 나프틸, 비페닐, 톨릴 등을 예시할 수 있다.In addition, the substituents including the "alkyl", "alkoxy" and other "alkyl" moieties include both straight-chain or branched forms, and "alkenyl" has 2 to 8 carbon atoms and contains one or more double bonds. It includes all of the linear or branched forms, and the "cycloalkyl" includes all of the saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms. The "aryl" is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and suitably represents a single or fused ring system containing 4 to 7, preferably 5 or 6 ring atoms in each ring. Includes. Specifically, phenyl, naphthyl, biphenyl, tolyl, and the like can be illustrated.
상기 "헤테로시클로알킬"은 포화시클릭 탄화수소 골격 원자로서 N, O, S로부터 선택되는 1 내지 3개의 헤테로원자를 포함하고, 나머지 포화모노시클릭 또는 바이시클릭 고리 골격 원자가 탄소인 시클로알킬 그룹을 의미하는 것으로, 피롤리디닐, 아제티디닐, 피라졸리디닐, 옥사졸리디닐, 피페리디닐, 피페라지닐, 모르폴리닐, 티오모르폴리닐, 티아졸리디닐, 히단토이닐, 발레로락타밀, 옥시라닐, 옥세타닐, 디옥솔라닐, 디옥사닐, 옥사티올라닐, 옥사티아닐, 디티아닐, 디히드로푸라닐, 테트라히드로푸라닐, 디히드로피라닐, 테트라히드로피라닐, 테트라히드로피리디닐, 테트라히드로피리미디닐, 테트라히드로티오페닐, 테트라히드로티오피라닐, 디아제파닐, 아제파닐 등을 예시할 수 있다.The "heterocycloalkyl" refers to a cycloalkyl group in which 1 to 3 heteroatoms selected from N, O, S are included as a saturated cyclic hydrocarbon skeleton atom, and the remaining saturated monocyclic or bicyclic ring skeleton atoms are carbon. As meant, pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, Oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxatianil, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyranyl Denyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, azepanyl, and the like can be exemplified.
상기 "헤테로아릴"은 방향족 고리 골격 원자로서 N, O, S로부터 선택되는 1 내지 3개의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 상기 헤테로아릴기는 고리 내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적으로, 퓨릴, 티에닐, 피롤릴, 피란일, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아지닐, 테트라지닐, 트리아졸릴, 테트라졸릴, 퓨라자닐, 피리딜, 피라지닐, 피리미딘일, 피리다지닐 등을 예시할 수 있다.The "heteroaryl" refers to an aryl group including 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon, and the heteroaryl group is hetero Atoms include divalent aryl groups that are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specifically, furyl, thienyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tria Zolyl, tetrazolyl, furazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like can be exemplified.
구체예에서, 상기 포스파젠계 난연제는 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 5 내지 약 25 중량부, 예를 들면 약 7 내지 약 25 중량부로 포함될 수 있다. 상기 포스파젠계 난연제의 함량이 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 5 중량부 미만일 경우, 열가소성 수지 조성물의 난연성, 유동성 등이 저하될 우려가 있고, 약 25 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성 등이 저하될 우려가 있다.In embodiments, the phosphazene-based flame retardant may be included in an amount of about 5 to about 25 parts by weight, for example, about 7 to about 25 parts by weight, based on about 100 parts by weight of the polycarbonate resin. When the content of the phosphazene-based flame retardant is less than about 5 parts by weight, based on about 100 parts by weight of the polycarbonate resin, there is a risk that the flame retardancy and fluidity of the thermoplastic resin composition may be deteriorated, and when it exceeds about 25 parts by weight, thermoplastic There is a fear that the impact resistance and the like of the resin composition may be deteriorated.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 통상의 열가소성 수지 조성물에 포함되는 첨가제를 더욱 포함할 수 있다. 상기 첨가제로는 산화 방지제, 적하 방지제, 활제, 이형제, 핵제, 대전방지제, 안정제, 안료, 염료, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다. 상기 첨가제 사용 시, 그 함량은 상기 폴리카보네이트 수지 약 100 중량부에 대하여, 약 0.001 내지 약 40 중량부, 예를 들면 약 0.1 내지 약 10 중량부일 수 있다.The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additives include antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 상기 구성 성분을 혼합하고, 통상의 이축 압출기를 사용하여, 약 200 내지 약 280℃, 예를 들면 약 220 내지 약 270℃에서 용융 압출한 펠렛 형태일 수 있다.The thermoplastic resin composition according to an embodiment of the present invention is in the form of a pellet melt-extruded at about 200 to about 280°C, for example about 220 to about 270°C, by mixing the constituents and using a conventional twin screw extruder. I can.
구체예에서, ASTM D696에 의거하여, 열기계분석기(thermo mechanical analyzer)로 0℃에서 90℃까지 5℃/min 속도로 승온하며 측정한 10 mm × 10 mm × 6.4 mm 크기의 사출 시편의 선팽창계수가 약 20 내지 약 45 ㎛/m·℃, 예를 들면 약 30 내지 약 40 ㎛/m·℃일 수 있다.In a specific example, according to ASTM D696, the coefficient of linear expansion of an injection specimen of 10 mm × 10 mm × 6.4 mm measured by heating from 0°C to 90°C at a rate of 5°C/min with a thermo-mechanical analyzer May be about 20 to about 45 μm/m·°C, for example, about 30 to about 40 μm/m·°C.
구체예에서, 상기 열가소성 수지 조성물은 UL-94 vertical test 방법으로 측정한 0.8 mm 두께 사출 시편의 난연도가 V-0일 수 있다.In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 of a 0.8 mm-thick injection specimen measured by UL-94 vertical test method.
구체예에서, 상기 열가소성 수지 조성물은 ASTM D256에 의거하여 측정한 두께 1/8" 시편의 노치 아이조드 충격강도가 약 9 내지 약 17 kgf·cm/cm, 예를 들면 약 10 내지 약 16 kgf·cm/cm일 수 있다.In a specific embodiment, the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256, from about 9 to about 17 kgf·cm/cm, for example, from about 10 to about 16 kgf·cm May be /cm.
본 발명에 따른 성형품은 상기 열가소성 수지 조성물로부터 형성된다. 상기 항균성 열가소성 수지 조성물은 펠렛 형태로 제조될 수 있으며, 제조된 펠렛은 사출성형, 압출성형, 진공성형, 캐스팅성형 등의 다양한 성형방법을 통해 다양한 성형품(제품)으로 제조될 수 있다. 이러한 성형방법은 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 잘 알려져 있다. 상기 성형품은 치수 안정성, 난연성, 내충격성 이들의 물성 발란스 등이 우수하므로, 전기 전자 제품의 내/외장재, 박막 시트 등으로 유용하다.The molded article according to the present invention is formed from the thermoplastic resin composition. The antimicrobial thermoplastic resin composition may be prepared in the form of pellets, and the prepared pellets may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the field to which the present invention belongs. The molded article is excellent in dimensional stability, flame retardancy, impact resistance, and balance of physical properties thereof, and thus is useful as an interior/exterior material of an electric and electronic product, a thin film sheet, and the like.
구체예에서, 상기 성형품은 ASTM D696에 의거하여, 0℃에서 90℃까지 5℃/min 속도로 승온하며 측정한 10 mm × 10 mm × 6.4 mm 크기의 사출 시편의 선팽창계수가 약 20 내지 약 45 ㎛/m·℃이고, UL-94 vertical test 방법으로 측정한 0.8 mm 두께 사출 시편의 난연도가 V-0이며, ASTM D256에 의거하여 측정한 두께 1/8" 시편의 노치 아이조드 충격강도가 약 9 내지 약 17 kgf·cm/cm인 것으로, 가로 약 100 내지 약 300 cm, 세로 약 50 내지 약 150 cm, 및 두께 약 0.1 내지 약 10 mm의 대형 사출 성형품으로 적합하다.In an embodiment, the molded article has a coefficient of linear expansion of about 20 to about 45 of an injection specimen of 10 mm × 10 mm × 6.4 mm measured by heating from 0° C. to 90° C. at a rate of 5° C./min according to ASTM D696. ㎛/m·℃, the flame retardancy of the 0.8 mm-thick injection specimen measured by the UL-94 vertical test method is V-0, and the notched Izod impact strength of the 1/8" thick specimen measured according to ASTM D256 is about 9 to about 17 kgf·cm/cm, it is suitable as a large injection molded article having a width of about 100 to about 300 cm, a length of about 50 to about 150 cm, and a thickness of about 0.1 to about 10 mm.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로, 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail through examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예Example
이하, 실시예 및 비교예에서 사용된 각 성분의 사양은 다음과 같다.Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.
(A) 폴리카보네이트 수지(A) Polycarbonate resin
중량평균분자량(Mw)이 25,000 g/mol인 비스페놀-A형 폴리카보네이트 수지를 사용하였다. A bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 25,000 g/mol was used.
(B) 폴리에스테르 수지(B) polyester resin
(B1) 폴리에틸렌테레프탈레이트(PET, 제조사: SK Chemical, 제품명: SKYPET 1100, 고유점도: 0.8 dl/g)를 사용하였다.(B1) Polyethylene terephthalate (PET, manufacturer: SK Chemical, product name: SKYPET 1100, intrinsic viscosity: 0.8 dl/g) was used.
(B2) 폴리부틸렌테레프탈레이트(PBT, 제조사: Shinkong, 제품명: Shinite K006, 고유점도: 1.3 dl/g)를 사용하였다.(B2) Polybutylene terephthalate (PBT, manufacturer: Shinkong, product name: Shinite K006, intrinsic viscosity: 1.3 dl/g) was used.
(C) 유리 섬유(C) glass fiber
(C1) 단면의 종횡비(단면의 장경/단면의 단경)가 4이고, 단경이 7 ㎛이며, 가공 전 길이가 3 mm인 직사각형 단면의 유리 섬유(제조사: Nittobo, 제품명: FF45y11)를 사용하였다.(C1) A rectangular cross-section glass fiber (manufacturer: Nittobo, product name: FF45y11) having an aspect ratio of the cross section (long diameter of the cross section/short diameter of the cross section) is 4, the short diameter is 7 μm, and the length before processing is 3 mm was used.
(C2) 단면의 직경이 13 ㎛이고, 가공 전 길이가 4 mm인 원형 단면의 유리 섬유(제조사: 오웬스코닝, 제품명: CS 183F-4P )를 사용하였다.(C2) A glass fiber (manufacturer: Owen Corning, product name: CS 183F-4P) having a circular cross-section with a diameter of 13 µm and a length of 4 mm before processing was used.
(C3) 단면의 직경이 10 ㎛이고, 가공 전 길이가 50 ㎛인 원형 단면의 유리 섬유(제조사: 성진화이버, 제품명: MF75W-NL)를 사용하였다.(C3) A glass fiber (manufacturer: Sungjin Fiber, product name: MF75W-NL) having a diameter of a cross section of 10 µm and a length of 50 µm before processing was used.
(D) 무기 충전제(D) inorganic filler
(D1) 단면의 종횡비(단면의 장경/단면의 단경)가 100이고, 평균 입자 크기(D50)가 280 ㎛인 마이카(제조사: IMERYS, 제품명: SUZORITE 60-S)를 사용하였다.(D1) A mica (manufacturer: IMERYS, product name: SUZORITE 60-S) having an aspect ratio of a cross section (long axis of a cross section/short axis of a cross section) of 100 and an average particle size (D50) of 280 μm was used.
(D2) 단면의 종횡비(단면의 장경/단면의 단경)가 55이고, 평균 입자 크기(D50)가 60 ㎛인 마이카(제조사: IMERYS, 제품명: SUZORITE 200-HK)를 사용하였다.(D2) A mica (manufacturer: IMERYS, product name: SUZORITE 200-HK) having an aspect ratio of a cross section (longer diameter of a cross section/shorter diameter of a cross section) is 55 and an average particle size (D50) of 60 μm was used.
(D3) 단면의 종횡비(단면의 장경/단면의 단경)가 90이고, 평균 입자 크기(D50)가 150 ㎛인 마이카(제조사: IMERYS, 제품명: SUZORITE 150-S)를 사용하였다.(D3) A mica (manufacturer: IMERYS, product name: SUZORITE 150-S) having an aspect ratio of a cross section (long diameter of a cross section/short diameter of a cross section) is 90 and an average particle size (D50) of 150 μm was used.
(D4) 단면의 종횡비(단면의 장경/단면의 단경)가 100이고, 평균 입자 크기(D50)가 600 ㎛인 마이카(제조사: IMERYS, 제품명: SUZORITE 30-S)를 사용하였다.(D4) A mica (manufacturer: IMERYS, product name: SUZORITE 30-S) having an aspect ratio of a cross section (long diameter of a cross section/short diameter of a cross section) is 100 and an average particle size (D50) of 600 μm was used.
(D5) 탈크(제조사: KOCH, 제품명: KCP-04)를 사용하였다.(D5) Talc (manufacturer: KOCH, product name: KCP-04) was used.
(E) 인계 난연제(E) Phosphorus flame retardant
(E1) 포스파젠 화합물(제조사: Fushimi Pharmaceutical, 제품명: FP-110)을 사용하였다.(E1) A phosphazene compound (manufacturer: Fushimi Pharmaceutical, product name: FP-110) was used.
(E2) 비스페놀-A 디포스페이트(bisphenol-A diphosphate, 제조사: Yoke Chemical, 제품명: YOKE BDP)를 사용하였다.(E2) Bisphenol-A diphosphate (manufacturer: Yoke Chemical, product name: YOKE BDP) was used.
실시예 1 내지 11 및 비교예 1 내지 16Examples 1 to 11 and Comparative Examples 1 to 16
상기 각 구성 성분을 하기 표 1, 2, 3 및 4에 기재된 바와 같은 함량으로 첨가한 후, 260℃에서 압출하여 펠렛을 제조하였다. 압출은 L/D=36, 직경 45 mm인 이축 압출기를 사용하였으며, 제조된 펠렛은 80℃에서 4시간 이상 건조 후, 6 Oz 사출기(성형 온도 260℃, 금형 온도: 60℃)에서 사출하여 시편을 제조하였다. 제조된 시편에 대하여 하기의 방법으로 물성을 평가하고, 그 결과를 하기 표 1, 2, 3 및 4에 나타내었다.Each of the above constituents was added in an amount as described in Tables 1, 2, 3 and 4 below, and then extruded at 260°C to prepare a pellet. Extrusion was performed using a twin-screw extruder with L/D=36 and diameter of 45 mm, and the produced pellets were dried at 80°C for 4 hours or more, and then injected from a 6 Oz injection machine (molding temperature 260°C, mold temperature: 60°C) to test specimens. Was prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2, 3, and 4 below.
물성 측정 방법How to measure physical properties
(1) 치수 안정성 평가: ASTM D696에 의거하여, 열기계분석기(thermo mechanical analyzer)로 0℃에서 90℃까지 5℃/min 속도로 승온하며 10 mm × 10 mm × 6.4 mm 크기의 사출 시편의 선팽창계수(단위: ㎛/m·℃)를 측정하였다.(1) Dimensional stability evaluation: In accordance with ASTM D696, the temperature was raised from 0℃ to 90℃ at a rate of 5℃/min with a thermomechanical analyzer, and linear expansion of the 10 mm × 10 mm × 6.4 mm sized injection specimen The coefficient (unit: µm/m·°C) was measured.
(2) 난연성 평가: UL-94 vertical test 방법으로 0.8 mm 두께 사출 시편의 난연도를 측정하였다.(2) Flame retardancy evaluation: The flame retardancy of the 0.8 mm-thick injection specimen was measured by the UL-94 vertical test method.
(3) 내충격성 평가: ASTM D256에 의거하여, 두께 1/8" 시편의 노치 아이조드 충격강도(단위: kgf·cm/cm)를 측정하였다.(3) Impact resistance evaluation: Based on ASTM D256, the notched Izod impact strength (unit: kgf·cm/cm) of a 1/8" thick specimen was measured.
실시예Example
1One 22 33 44 55 66
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100
(B1) (중량부)(B1) (parts by weight) 1.51.5 44 1515 -- 44 44
(B2) (중량부)(B2) (parts by weight) -- -- -- 44 -- --
(C1) (중량부)(C1) (parts by weight) 6060 6060 6060 6060 4040 8080
(C2) (중량부)(C2) (parts by weight) -- -- -- -- -- --
(C3) (중량부)(C3) (parts by weight) -- -- -- -- -- --
(D1) (중량부)(D1) (parts by weight) 2020 2020 2020 2020 2020 2020
(D2) (중량부)(D2) (parts by weight) -- -- -- -- -- --
(D3) (중량부)(D3) (parts by weight) -- -- -- -- -- --
(D4) (중량부)(D4) (parts by weight) -- -- -- -- -- --
(D5) (중량부)(D5) (parts by weight) -- -- -- -- -- --
(E1) (중량부)(E1) (parts by weight) 1515 1515 1515 1515 1515 1515
(E2) (중량부)(E2) (parts by weight) -- -- -- -- -- --
선팽창계수Coefficient of linear expansion 36.336.3 35.235.2 32.732.7 33.733.7 39.739.7 29.129.1
난연도Flame retardancy V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0
노치 아이조드 충격강도Notch Izod impact strength 13.113.1 12.312.3 11.011.0 11.211.2 15.815.8 10.210.2
실시예Example
77 88 99 1010 1111
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100
(B1) (중량부)(B1) (parts by weight) 44 44 44 44 44
(B2) (중량부)(B2) (parts by weight) -- -- -- -- --
(C1) (중량부)(C1) (parts by weight) 6060 6060 6060 6060 --
(C2) (중량부)(C2) (parts by weight) -- -- -- -- 6060
(C3) (중량부)(C3) (parts by weight) -- -- -- --
(D1) (중량부)(D1) (parts by weight) 1010 3030 2020 2020 2020
(D2) (중량부)(D2) (parts by weight) -- -- -- -- --
(D3) (중량부)(D3) (parts by weight) -- -- -- -- --
(D4) (중량부)(D4) (parts by weight) -- -- -- -- --
(D5) (중량부)(D5) (parts by weight) -- -- -- -- --
(E1) (중량부)(E1) (parts by weight) 1515 1515 77 2525 1515
(E2) (중량부)(E2) (parts by weight) -- -- --
선팽창계수Coefficient of linear expansion 37.537.5 32.032.0 35.135.1 36.236.2 38.438.4
난연도Flame retardancy V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0
노치 아이조드 충격강도Notch Izod impact strength 13.413.4 10.510.5 15.815.8 10.510.5 11.511.5
비교예Comparative example
1One 22 33 44 55 66 77 88
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100 100100
(B1) (중량부)(B1) (parts by weight) 0.80.8 2121 44 44 44 44 44 44
(B2) (중량부)(B2) (parts by weight) -- -- -- -- -- -- -- --
(C1) (중량부)(C1) (parts by weight) 6060 6060 2525 8585 -- 6060 6060 6060
(C2) (중량부)(C2) (parts by weight) -- -- -- -- -- -- -- --
(C3) (중량부)(C3) (parts by weight) -- -- -- -- 6060 -- -- --
(D1) (중량부)(D1) (parts by weight) 2020 2020 2020 2020 2020 33 3535 --
(D2) (중량부)(D2) (parts by weight) -- -- -- -- -- -- -- 2020
(D3) (중량부)(D3) (parts by weight) -- -- -- -- -- -- -- --
(D4) (중량부)(D4) (parts by weight) -- -- -- -- -- -- -- --
(D5) (중량부)(D5) (parts by weight) -- -- -- -- -- -- -- --
(E1) (중량부)(E1) (parts by weight) 1515 1515 1515 1515 1515 1515 1515 1515
(E2) (중량부)(E2) (parts by weight) -- -- -- -- -- -- -- --
선팽창계수Coefficient of linear expansion 46.946.9 31.931.9 64.364.3 24.524.5 34.634.6 52.252.2 30.330.3 46.646.6
난연도Flame retardancy V-0V-0 V-1V-1 V-0V-0 V-2V-2 V-1V-1 V-0V-0 V-1V-1 V-1V-1
노치 아이조드 충격강도Notch Izod impact strength 13.913.9 7.77.7 16.916.9 6.66.6 6.36.3 14.314.3 6.36.3 7.67.6
비교예Comparative example
99 1010 1111 1212 1313 1414 1515 1616
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100 100100
(B1) (중량부)(B1) (parts by weight) 44 44 44 44 44 44 44 44
(B2) (중량부)(B2) (parts by weight) -- -- -- -- -- -- -- --
(C1) (중량부)(C1) (parts by weight) 6060 6060 6060 6060 6060 6060 3030 8080
(C2) (중량부)(C2) (parts by weight) -- -- -- -- -- -- -- --
(C3) (중량부)(C3) (parts by weight) -- -- -- -- -- -- -- --
(D1) (중량부)(D1) (parts by weight) -- -- -- 2020 2020 2020 2525 1010
(D2) (중량부)(D2) (parts by weight) -- -- -- -- -- -- -- --
(D3) (중량부)(D3) (parts by weight) 2020 -- -- -- -- -- -- --
(D4) (중량부)(D4) (parts by weight) -- 2020 -- -- -- -- --
(D5) (중량부)(D5) (parts by weight) -- -- 2020 -- -- -- -- --
(E1) (중량부)(E1) (parts by weight) 1515 1515 1515 44 2828 -- 1515 1515
(E2) (중량부)(E2) (parts by weight) -- -- -- -- -- 1515 -- --
선팽창계수Coefficient of linear expansion 47.347.3 48.148.1 48.348.3 32.832.8 40.240.2 34.534.5 54.154.1 47.747.7
난연도Flame retardancy V-0V-0 V-1V-1 V-1V-1 V-1V-1 V-0V-0 V-1V-1 V-0V-0 V-1V-1
노치 아이조드 충격강도Notch Izod impact strength 8.18.1 5.55.5 6.36.3 15.315.3 8.18.1 8.38.3 14.814.8 7.27.2
상기 결과로부터, 본 발명의 열가소성 수지 조성물은 치수 안정성, 난연성, 내충격성 등이 모두 우수함을 알 수 있다.From the above results, it can be seen that the thermoplastic resin composition of the present invention has excellent dimensional stability, flame retardancy, impact resistance, and the like.
반면, 폴리에스테르 수지를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 1), 열가소성 수지 조성물의 치수 안정성 등이 저하됨을 알 수 있고, 폴리에스테르 수지를 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 2), 열가소성 수지 조성물의 난연성, 내충격성 등이 저하됨을 알 수 있으며, 유리 섬유를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 3), 열가소성 수지 조성물의 치수 안정성 등이 저하됨을 알 수 있고, 유리 섬유를 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 4), 열가소성 수지 조성물의 난연성, 내충격성 등이 저하됨을 알 수 있다. 본 발명의 유리 섬유 대신에, 유리 섬유 (C3)를 적용할 경우(비교예 5), 열가소성 수지 조성물의 난연성, 내충격성 등이 저하됨을 알 수 있고, 마이카를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 6), 열가소성 수지 조성물의 치수 안정성 등이 저하됨을 알 수 있고, 마이카를 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 7), 열가소성 수지 조성물의 난연성, 내충격성 등이 저하됨을 알 수 있다. 본 발명의 마이카 대신에, 마이카 (D2)를 적용할 경우(비교예 8), 열가소성 수지 조성물의 치수 안정성, 난연성, 내충격성 등이 저하됨을 알 수 있고, 마이카 (D3)를 적용할 경우(비교예 9), 열가소성 수지 조성물의 치수 안정성, 내충격성 등이 저하됨을 알 수 있고, 마이카 (D4)를 적용할 경우(비교예 10), 열가소성 수지 조성물의 치수 안정성, 난연성, 내충격성 등이 저하됨을 알 수 있으며, 탈크 (D5)를 적용할 경우(비교예 11), 열가소성 수지 조성물의 치수 안정성, 난연성, 내충격성 등이 저하됨을 알 수 있다. 또한, 포스파젠계 난연제를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 12), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 포스파젠계 난연제를 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 13), 열가소성 수지 조성물의 내충격성 등이 저하됨을 알 수 있으며, 본 발명의 포스파젠계 난연제 대신에, BSP (E2)를 적용할 경우(비교예 14), 열가소성 수지 조성물의 난연성, 내충격성 등이 저하됨을 알 수 있다. 또한, 유리 섬유 및 마이카의 함량이 본 발명의 범위에 포함되더라도, 중량비가 본 발명의 범위 미만(1.2:1)일 경우(비교예 15), 열가소성 수지 조성물의 치수 안정성 등이 저하됨을 알 수 있으며, 중량비가 본 발명의 범위를 초과(8:1)할 경우(비교예 16), 열가소성 수지 조성물의 치수 안정성, 난연성, 내충격성 등이 저하됨을 알 수 있다.On the other hand, when the polyester resin is applied in the content range of the present invention (Comparative Example 1), it can be seen that the dimensional stability of the thermoplastic resin composition is lowered, and the polyester resin is applied in excess of the content range of the present invention. In the case (Comparative Example 2), it can be seen that the flame retardancy and impact resistance of the thermoplastic resin composition are deteriorated, and when the glass fiber is applied below the content range of the present invention (Comparative Example 3), the dimensional stability of the thermoplastic resin composition, etc. It can be seen that it is degraded, and when the glass fiber is applied in excess of the content range of the present invention (Comparative Example 4), it can be seen that the flame retardancy and impact resistance of the thermoplastic resin composition are deteriorated. In the case of applying glass fiber (C3) instead of the glass fiber of the present invention (Comparative Example 5), it can be seen that the flame retardancy, impact resistance, etc. of the thermoplastic resin composition are lowered, and mica can be applied in the content range of the present invention. In the case (Comparative Example 6), it can be seen that the dimensional stability of the thermoplastic resin composition is deteriorated, and when mica is applied beyond the content range of the present invention (Comparative Example 7), the flame retardancy and impact resistance of the thermoplastic resin composition are It can be seen that it is lowered. In the case of applying mica (D2) instead of the mica of the present invention (Comparative Example 8), it can be seen that the dimensional stability, flame retardancy, impact resistance, etc. of the thermoplastic resin composition decrease, and when mica (D3) is applied (comparative Example 9), it can be seen that the dimensional stability and impact resistance of the thermoplastic resin composition are deteriorated, and when mica (D4) is applied (Comparative Example 10), the dimensional stability, flame retardancy, impact resistance, etc. of the thermoplastic resin composition are deteriorated. It can be seen, and when talc (D5) is applied (Comparative Example 11), it can be seen that the dimensional stability, flame retardancy, impact resistance, and the like of the thermoplastic resin composition are deteriorated. In addition, when the phosphazene-based flame retardant is applied below the content range of the present invention (Comparative Example 12), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and the phosphazene-based flame retardant is applied in excess of the content range of the present invention. In the case of (Comparative Example 13), it can be seen that the impact resistance of the thermoplastic resin composition is lowered, and when BSP (E2) is applied instead of the phosphazene-based flame retardant of the present invention (Comparative Example 14), the thermoplastic resin composition It can be seen that flame retardancy, impact resistance, etc. are deteriorated. In addition, even if the contents of the glass fiber and mica are included in the scope of the present invention, when the weight ratio is less than the scope of the present invention (1.2:1) (Comparative Example 15), it can be seen that the dimensional stability of the thermoplastic resin composition is lowered. , When the weight ratio exceeds the range of the present invention (8:1) (Comparative Example 16), it can be seen that the dimensional stability, flame retardancy, impact resistance, and the like of the thermoplastic resin composition are deteriorated.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (8)

  1. 폴리카보네이트 수지 약 100 중량부;About 100 parts by weight of a polycarbonate resin;
    폴리에스테르 수지 약 1 내지 약 20 중량부;About 1 to about 20 parts by weight of a polyester resin;
    유리 섬유 약 30 내지 약 80 중량부;About 30 to about 80 parts by weight of glass fiber;
    마이카 약 5 내지 약 33 중량부; 및About 5 to about 33 parts by weight of mica; And
    포스파젠계 난연제 약 5 내지 약 25 중량부;를 포함하며,Including about 5 to about 25 parts by weight of a phosphazene-based flame retardant,
    상기 유리 섬유는 단면 직경이 약 5 내지 약 20 ㎛이고, 가공 전 길이가 약 1 내지 약 15 mm인 원형 단면의 유리 섬유, 및 단면의 종횡비(단면의 장경/단면의 단경)가 약 1.5 내지 약 10이고, 단면의 단경이 약 2 내지 약 10 ㎛이며, 가공 전 길이가 약 1 내지 약 15 mm인 직사각형 단면의 유리 섬유 중 1종 이상을 포함하고,The glass fiber has a cross-sectional diameter of about 5 to about 20 µm, a circular cross-section of about 1 to about 15 mm in length before processing, and an aspect ratio of the cross-section (long diameter of the cross-section / short diameter of the cross-section) of about 1.5 to about 10, the short diameter of the cross section is about 2 to about 10 μm, and the length before processing includes at least one of glass fibers having a rectangular cross section of about 1 to about 15 mm,
    상기 마이카는 단면의 종횡비(단면의 장경/단면의 단경)가 약 90 내지 약 300이고, 평균 입자 크기(D50)가 약 200 내지 약 550 ㎛이며,The mica has an aspect ratio of a cross section (long diameter of a cross section/short diameter of a cross section) of about 90 to about 300, and an average particle size (D50) of about 200 to about 550 μm,
    상기 유리 섬유 및 상기 마이카의 중량비는 약 1.5 : 1 내지 약 7 : 1인 것을 특징으로 하는 열가소성 수지 조성물.The weight ratio of the glass fiber and the mica is about 1.5:1 to about 7:1, characterized in that the thermoplastic resin composition.
  2. 제1항에 있어서, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리트리메틸렌테레프탈레이트 및 폴리시클로헥실렌테레프탈레이트 중 1종 이상을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin of claim 1, wherein the polyester resin comprises at least one of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, and polycyclohexylene terephthalate. Composition.
  3. 제1항 또는 제2항에 있어서, 상기 폴리에스테르 수지는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 중 1종 이상을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 1 or 2, wherein the polyester resin contains at least one of polyethylene terephthalate and polybutylene terephthalate.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, 상기 폴리에스테르 수지 및 상기 유리 섬유의 중량비는 약 1 : 2 내지 약 1 : 40인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 3, wherein a weight ratio of the polyester resin and the glass fiber is about 1:2 to about 1:40.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 폴리에스테르 수지 및 상기 마이카의 중량비는 약 1 : 1 내지 약 1 : 15인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 4, wherein a weight ratio of the polyester resin and the mica is about 1:1 to about 1:15.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 ASTM D696에 의거하여, 0℃에서 90℃까지 5℃/min 속도로 승온하며 측정한 10 mm × 10 mm × 6.4 mm 크기의 사출 시편의 선팽창계수가 약 20 내지 약 45 ㎛/m·℃이고, UL-94 vertical test 방법으로 측정한 0.8 mm 두께 사출 시편의 난연도가 V-0이며, ASTM D256에 의거하여 측정한 두께 1/8" 시편의 노치 아이조드 충격강도가 약 9 내지 약 17 kgf·cm/cm인 것을 특징으로 하는 열가소성 수지 조성물.The method of any one of claims 1 to 5, wherein the thermoplastic resin composition is 10 mm × 10 mm × 6.4 mm in size measured by heating from 0°C to 90°C at a rate of 5°C/min according to ASTM D696. The coefficient of linear expansion of the injection specimen of is about 20 to about 45 µm/m·℃, and the flame retardancy of the 0.8 mm-thick injection specimen measured by the UL-94 vertical test method is V-0, and the thickness measured according to ASTM D256 A thermoplastic resin composition, characterized in that the notched Izod impact strength of the 1/8" specimen is about 9 to about 17 kgf·cm/cm.
  7. 제1항에 내지 제6항 중 어느 한 항에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 하는 성형품.A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 6.
  8. 제7항에 있어서, 상기 성형품은 상기 성형품은 가로 약 100 내지 약 300 cm, 세로 약 50 내지 약 150 cm 및 두께 약 0.1 내지 약 10 mm의 사출 성형품인 것을 특징으로 하는 성형품.The molded article of claim 7, wherein the molded article is an injection molded article having a width of about 100 to about 300 cm, a length of about 50 to about 150 cm, and a thickness of about 0.1 to about 10 mm.
PCT/KR2020/013017 2019-10-31 2020-09-24 Thermoplastic resin composition and molded product manufactured therefrom WO2021085867A1 (en)

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