CN109790367A - Fiber reinforced polycarbonate resin combination - Google Patents
Fiber reinforced polycarbonate resin combination Download PDFInfo
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- CN109790367A CN109790367A CN201780060576.9A CN201780060576A CN109790367A CN 109790367 A CN109790367 A CN 109790367A CN 201780060576 A CN201780060576 A CN 201780060576A CN 109790367 A CN109790367 A CN 109790367A
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- polycarbonate resin
- weight
- resin combination
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- reinforced polycarbonate
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The purpose of the present invention is to provide a kind of glass fiber-reinforced polycarbonate resin composition composition and the synthetic resin for being molded with the resin combination, excellent mechanical strength and rigidity and release property and excellent heat stability of the resin combination without detriment to glass fiber-reinforced polycarbonate resin composition composition.The present invention relates to a kind of fiber reinforced polycarbonate resin combinations, it is characterized in that, relative to 100 parts by weight of resin combination of the polycarbonate resin (A) comprising 40~80 weight % and the glass fibre (B) of 20~60 weight %, the aliphatic ester (D) of the phosphite ester based compound (C) containing 0.01~0.2 parts by weight and 0.1~2 parts by weight.
Description
Technical field
The present invention relates to a kind of fiber reinforced polycarbonate resin combinations and the tree for being molded with the resin combination
Rouge molded product, the fiber reinforced polycarbonate resin combination can maintain polycarbonate resin it is original possessed by it is excellent heat-resisting
Property and thermal stability, and release property when injection molding is excellent, and the rigidity of obtained molded product is also excellent.
Background technique
Polycarbonate resin is the excellent thermoplastic resins such as mechanical strength, heat resistance, thermal stability, thus industrially
It is widely used in electric and electronic field, automotive field etc..The intensity and rigidity of polycarbonate resin through glass fiber reinforcement
It is excellent, thus in shell for being used for electrical equipment, the shell of electronic equipment or electric tool etc..In recent years, for intelligence
For the portable terminals such as mobile phone, due to carrying the product, thus hope mitigates weight.Shell or the motor electricity of these products
Internal backplane of subassembly etc. is further thinning to realize and carries out injection molding at high temperature.Therefore, seeking
A kind of moulding material of the release property and excellent heat stability of not only mechanical strength and excellent rigidity but also thinner wall section.
But existing glass fiber-reinforced polycarbonate resin composition composition does not carry out sufficiently release property, thermal stability
Research has the undesirable condition for being easy to happen demoulding difficulty or rupture etc in the molded product demoulding that will have thinner wall section
Problem.
In order to improve the mechanical strength and rigidity of glass fiber-reinforced polycarbonate resin composition composition, it is known to a variety of poly-
Contain the method for inorganic filler in carbonate resin.A kind of glass fiber reinforced polycarbonate tree is proposed in patent document 1
Oil/fat composition is made of polycarbonate resin, glass fibre, trialkyl phosphite and polyethylene-based wax, impact resistance, just
Property and excellent in dimensional stability.But the release property of the resin combination, thermal stability are not studied.
A kind of glass fibre reinforced poly carbonate composite is proposed in patent document 2, is specifically to glue equal molecule
In the polycarbonate resin of amount made of the fibrous filler of L/D >=3 of mixed 50~240 parts by weight.In addition, patent document
A kind of less anisotropy high rigidity galss fiber reinforced resin molded product is proposed in 3, it is long by polycarbonate resin sum number
Diameter is than the glass fibre composition for 4~10.But in patent document 2 and patent document 3 not to release property and thermal stability into
Row research.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 57-094039
Patent document 2: Japanese Unexamined Patent Publication 05-287185
Patent document 3: Japanese Unexamined Patent Publication 04-100830
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide a kind of glass fiber-reinforced polycarbonate resin composition composition and by the resin combination
The synthetic resin that object is molded with, the resin combination are excellent without detriment to glass fiber-reinforced polycarbonate resin composition composition
Mechanical strength and rigidity and release property and excellent heat stability.
Means for solving the problems
The present inventor has made intensive studies in order to solve the above problems, as a result, it has been found that, by polycarbonate resin
Phosphite ester based compound and aliphatic ester containing glass fibre, with specific structure can be obtained and increase without detriment to glass fibre
The excellent mechanical strength and rigidity and release property and the glass fibre of excellent heat stability of strong poly carbonate resin composition increase
Strong poly carbonate resin composition, so as to complete the present invention.
That is, the present invention relates to a kind of fiber reinforced polycarbonate resin combinations, which is characterized in that relative to comprising 40~
100 parts by weight of resin combination of the glass fibre (B) of the polycarbonate resin (A) and 20~60 weight % of 80 weight %, contain
There are the phosphite ester based compound (C) of 0.01~0.2 parts by weight and the aliphatic ester (D) of 0.1~2 parts by weight.
The viscosity average molecular weigh of polycarbonate resin (A) is preferably 16000~30000.
It is preferred that: glass fibre (B) is handled using epoxy size or carbamate system size, fibre section
Average diameter be 6~20 μm.
Glass fibre (B) preferably has flat cross section, and in the flat cross section, the average value of the major diameter of fibre section is 10~
50 μm, the average value of the ratio between major diameter and minor axis (major diameter/minor axis) is 2~8.
Phosphite ester based compound (C) is preferably that compound represented by the following general formula (1) or the following general formula (2) are represented
Compound.
General formula (1)
[changing 1]
(in formula, R1And R2Each independently represent carbon atom number be 1~20 alkyl or can be by alkyl-substituted virtue
Base, a and b each independently represent 0~3 integer)
General formula (2)
[changing 2]
(in general formula (2), R3Indicate the alkyl or can indicate 0 by alkyl-substituted aryl, c that carbon atom number is 1~20
~3 integer.)
Phosphite ester based compound (C) represented by general formula (1) is preferably the bis- (2,6- di-t-butyl -4- methylbenzenes of 3,9-
Oxygroup) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5,5] hendecane or the bis- (2,6- di-t-butyl -4- methylenedioxy phenoxies of 3,9-
Base) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [5,5] hendecane.
Phosphite ester based compound (C) represented by general formula (2) is preferably phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
Aliphatic ester (D) is preferably pentaerythritol tetrastearate.
Fiber reinforced polycarbonate resin combination of the invention preferably further includes thermoplastic elastomer (TPE) (E), relatively
In 100 parts by weight of polycarbonate resin (A) and glass fibre (B), thermoplastic elastomer (TPE) (E) is 0.2~20 parts by weight.
Thermoplastic elastomer (TPE) (E) is preferably hydrogenated styrene based thermoplastic elastomer or Polyester thermoplastic elastomer (TPE).
The invention further relates to a kind of synthetic resin, be by above-mentioned fiber reinforced polycarbonate resin combination molding and
It obtains.
The effect of invention
Glass fiber-reinforced polycarbonate resin composition composition of the invention is without detriment to glass fiber-reinforced polycarbonate resin composition
The excellent mechanical strength and rigidity and release property and excellent heat stability of composition, thus the utility value in its industry is high.
Such as it can be used as replacing for the thin-wall case used in electrical equipment or electronic equipment or the metal product of internal backplane
Dai Pin, it can be achieved that product lightweight.In addition, the case where applying external force to the molded product obtained by such resin combination
Under, the molded product can be inhibited to bend as much as possible, damage etc is brought to the electronic component being accommodated in inside molded product
The generation of undesirable condition.
Specific embodiment
The present invention is described in detail for embodiment and illustrative material described below etc., but the present invention is not limited to following institutes
Embodiment and illustrative material for showing etc. can carry out without departing from the gist of the present invention random variation to implement.
Fiber reinforced polycarbonate resin combination of the invention is characterized in that, relative to including 40~80 weight %'s
100 parts by weight of resin combination of the glass fibre (B) of polycarbonate resin (A) and 20~60 weight % contain 0.01~0.2
The phosphite ester based compound (C) of parts by weight and the aliphatic ester (D) of 0.1~2 parts by weight.
Polycarbonate resin used in the present invention (A) is by making various dihydroxy diaryl compounds and phosgene reaction
Phosgenation or make what the ester-interchange method of the carbonate reactions such as dihydroxy diaryl compound and diphenyl carbonate obtained to polymerize
Object can be enumerated as object is represented by the polycarbonate resin of bis- (4- hydroxy phenyl) propane (the being commonly referred to as bisphenol-A) manufactures of 2,2-
Rouge.
As above-mentioned dihydroxy diaryl compound, other than bisphenol-A, bis- (4- hydroxy phenyl) first can also be enumerated
Bis- (4- hydroxy phenyl) ethane of alkane, 1,1-, bis- (4- hydroxy phenyl) butane of 2,2-, bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4-
Hydroxy phenyl) phenylmethane, bis- (4- hydroxy phenyl -3- aminomethyl phenyl) propane of 2,2-, the bis- (4- hydroxyl -3- tert-butyl benzenes of 1,1-
Base) propane, bis- (4- hydroxyl -3- bromophenyl) propane of 2,2-, 2,2- bis- (4- hydroxyl -3,5- dibromo phenyl) propane, the bis- (4- of 2,2-
Hydroxyl -3,5- dichlorophenyl) propane etc bis- (hydroxyaryl) alkanes, 1,1- bis- (4- hydroxy phenyl) pentamethylene, 1,1-
Bis- (hydroxyaryl) cycloalkanes, the 4,4 '-dihydroxydiphenyl ethers, 4,4 '-dihydroxies of bis(4-hydroxyphenyl)cyclohexane etc
The dihydroxy of the dihydroxy diaryl ethers of base -3,3 '-dimethyl diphenyl ether etc, 4,4 '-dihydroxy diphenyl sulfides etc
The two of diaryl sulfide class, 4,4 '-dihydroxydiphenyl sulfoxides, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfoxide etc
The dihydroxy of diarylsulfoxide class, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxy -3,3 '-diphenylsulfone dimethyl etc
Diaryl sulfone class.
These compounds are used alone or mixed use of two or more, in addition to these, can also be used in mixed way piperazine,
Dipiperidino quinhydrones, resorcinol, 4,4 '-dihydroxybiphenyls etc..
Further, it is also possible to which above-mentioned dihydroxy aryl compound is mixed with 3 yuan or more of phenolic compounds as shown below
It uses.As 3 yuan or more of phenol, 1,3,5-trihydroxybenzene, 4,6- dimethyl -2,4 can be enumerated, 6- tri- (4- hydroxy phenyl) heptene, 2,
4,6- dimethyl -2,4,6- three (4- hydroxy phenyl) heptane, 1,3,5- tri- (4- hydroxy phenyl) benzene, (the 4- hydroxy benzenes of 1,1,1- tri-
Base) ethane and bis- [4,4- (4,4 '-dihydroxydiphenyl) cyclohexyl] propane of 2,2- etc..
The viscosity average molecular weigh of polycarbonate resin (A) is not particularly limited, from molding processibility, intensity aspect,
Usually 10000~100000, more preferably 16000~30000, further preferably 19000~26000.In addition, manufacturing
When the polycarbonate resin, it can according to need using molecular weight regulator, catalyst etc..
The blend amount of polycarbonate resin (A) is 40~80 weight %, preferably 50~70 weight %.If more than 80 weights
% is measured, then poor rigidity；If generating the molded product of thermal stability difference less than 40 weight %.
Glass fibre used in the present invention (B) is not particularly limited, and can be the ratio between major diameter and minor axis of fibre section
The average value of (major diameter/minor axis) is 1~1.5 and section is generally circular circular cross-section glass fibre, be also possible to major diameter with
The flat cross section glass fibre that the average value of the ratio between minor axis (major diameter/minor axis) is 2~8.
The long equal fiber of the number of glass fibre (B) is preferably 1~8mm, more preferably 2~5mm.Glass fibre is according to existing public affairs
Any means manufacture known.When a length of 1mm or less of the equal fiber of number, the improvement of mechanical strength is insufficient；It is long in the manufacture equal fiber of number
When polycarbonate resin greater than 8mm, bad dispersibility of the glass fibre in polycarbonate resin, thus glass fibre is from resin
It falls off, productivity is easily reduced.
The ratio between major diameter and the minor axis that glass fibre (B) is fibre section (major diameter/minor axis) average value be 1~1.5 and
In the case that section is generally circular circular cross-section glass fibre, the diameter of glass fibre is preferably 6~20 μm.Glass fibre
Diameter less than 6 μm in the case where, bad mechanical strength；The diameter of glass fibre is if more than 20 μm, then appearance is easily reduced.Glass
The diameter of fiber is more preferably 7~18 μm, further preferably 8~15 μm.
As can the average value of the ratio between major diameter through the fibre section of commercially available acquisition and minor axis (major diameter/minor axis) be 1~1.5
And section is generally circular circular cross-section glass fibre, there is 10 μm and 13 μm of diameter of a fiber, the equal length of their number for 2~
6mm.As can through the glass fibre of commercially available acquisition, it can be cited for example that KCC company manufacture CS321, CS311, Owens
The CS03MAFT737 etc. of Corning Japan company manufacture.
The average value of the ratio between major diameter and the minor axis that glass fibre (B) is fibre section (major diameter/minor axis) be 2~8 it is flat
In the case where plane section glass fibre, the average value of major diameter is 10~50 μm, preferably 15~40 μm, more preferably 25~30 μ
m.In addition, the average value of the ratio between major diameter and minor axis (major diameter/minor axis) is 2~8, preferably 2~7, more preferably 2.5~5.These
Fiber is manufactured according to conventionally known any means.
When the major diameter of flat cross section glass fibre is less than 10 μm, manufacture is difficult；When greater than 50 μm, polycarbonate resin composition
The surface of the molded article appearance of object is damaged sometimes.When the ratio between major diameter and minor axis are less than 2, poor dimensional stability；When greater than 8, sometimes
The case where intensity difference can be generated.
As can the average value of the ratio between major diameter through the fibre section of commercially available acquisition and minor axis (major diameter/minor axis) be 2~8
Flat cross section glass fibre, it can be cited for example that CSG 3PA-820, the CSG 3PA-830 etc. of the manufacture of Nitto Boseki company.
Amino silane, epoxy can use in order to improve the adaptation with polycarbonate resin for glass fibre (B)
Silane coupling agents such as silane etc. are surface-treated.It, can be in addition, in order to improve treatability when handling glass fibre
It is infiltrated using infiltrating materials such as carbamate, epoxy etc..
The blend amount of glass fibre (B) is 20~60 weight % in resin combination.If more than 60 weight %, then generate
The molded product of aesthetic appearance difference.In addition, if less than 20 weight %, intensity, poor rigidity.Preferred blend amount is 30~50 weights
Measure %, most preferably 40~45 weight %.
Mixture has phosphite ester based compound (C) in glass fiber-reinforced polycarbonate resin composition composition of the invention.
By mixed phosphite ester based compound (C), can be obtained without detriment to original possessed mechanical strength of polycarbonate resin (A) etc.
The glass fiber-reinforced polycarbonate resin composition composition of characteristic and excellent heat stability.
As phosphite ester based compound (C), compound represented by particularly preferably above-mentioned general formula (1).
General formula (1)
[changing 3]
(in formula, R1And R2Each independently represent carbon atom number be 1~20 alkyl or can be by alkyl-substituted virtue
Base, a and b each independently represent 0~3 integer)
As compound represented by general formula (1), such as the Adkstab of ADEKA company manufacture can be obtained through commercial sources
The Doverphos S-9228 that PEP-36 (" Adkstab " is registered trademark), Dover Chemical company manufacture.
As phosphite ester based compound (C), other than the compound represented by above-mentioned general formula (1), can also enumerate
Such as compound represented by general formula (2).
General formula (2)
[changing 4]
(in formula, R3Indicate the alkyl or can indicate 0~3 by alkyl-substituted aryl, c that carbon atom number is 1~20
Integer)
In general formula (2), R3It is the alkyl that carbon atom number is 1~20, the alkyl that further preferred carbon atom number is 1~10.
As compound represented by general formula (2), it can be cited for example that triphenyl phosphite, tricresyl phosphite, Asia
Tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester, Wytox 312 etc..Among these, particularly preferred phosphorous acid three (2,
4- di-tert-butyl-phenyl) ester, such as can be used as BASF AG manufacture Irgafos 168 (" Irgafos " is BASF
The registered trademark of Societas Europeae company) it is obtained through commercial sources.
Relative to 100 parts by weight of resin combination comprising polycarbonate resin (A) and glass fibre (B), phosphite ester
The blend amount of based compound (C) is 0.01~0.2 parts by weight.If blend amount is greater than 0.2 parts by weight, thermal stability becomes instead
Difference.If less than 0.01 parts by weight, thermal stability is poor.More preferably 0.02~0.1 parts by weight are most preferably 0.03~0.05 weight
Measure part.
Mixture has aliphatic ester (D) in glass fiber-reinforced polycarbonate resin composition composition of the invention.Pass through mixture
Aliphatic ester (D) can be obtained without detriment to characteristics and release property and heat such as the original possessed mechanical strengths of polycarbonate resin (A)
The glass fiber-reinforced polycarbonate resin composition composition of excellent in stability.
Aliphatic ester (D) used in the present invention, can be used the condensation chemical combination of common aliphatic carboxylic acid and alcohol
Object.
As aliphatic carboxylic acid, saturated or unsaturated monocarboxylic acid, dicarboxylic acids, tricarboxylic acids etc. can be enumerated.It needs to illustrate
, also include ester ring type carboxylic acid in the aliphatic carboxylic acid.Among these, preferably carbon atom number be 6~36 monocarboxylic acid and two
Carboxylic acid, the saturation monocarboxylic acid that further preferred carbon atom number is 6~36.
As the concrete example of aliphatic carboxylic acid, it can be cited for example that palmitinic acid, stearic acid, valeric acid, caproic acid, capric acid, laurel
Acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, melissic acid, gheddic acid, montanic acid, glutaric acid, adipic acid, azelaic acid etc..
As alcohol, saturated or unsaturated monohydric alcohol and polyalcohol can be enumerated, it is former that these alcohol can have fluorine atom, chlorine
The substituent groups such as son, bromine atom, aryl.Among these, preferably carbon atom number is 30 saturated alcohols below, further preferred carbon atom
Number is 30 aliphatic saturated monohydroxy alcohols and aliphatic saturated polyol below.It should be noted that also being wrapped in aliphatic alcohol
Include alicyclic alcohol.
As the concrete example of alcohol, it can be cited for example that octanol, decyl alcohol, dodecanol, tetradecanol, stearyl alcohol, docosyl alcohol,
Ethylene glycol, diethylene glycol (DEG), glycerol, pentaerythrite, 2,2- dihydroxy perfluor propyl alcohol, neopentyl glycol, double trimethylolpropane, two seasons penta
Tetrol etc..
As the concrete example of aliphatic ester (D), it can be cited for example that behenic acid behenyl ester, behenic acid octyldodecyl
It is ester, stearyl stearate, glycerol monopalmitate, glyceryl monostearate, Monoolein, glycerol distearate, sweet
Oily tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol stearate, Ji Wusi
Alcohol tristearate, pentaerythritol tetrastearate etc., these aliphatic esters can be used alone or make two or more combinations
With.Among these, preferably pentaerythritol stearate, such as the Loxiol that can be manufactured through commercial sources acquisition Cognis company
VPG861 etc..
Relative to 100 parts by weight of resin combination comprising polycarbonate resin (A) and glass fibre (B), aliphatic ester
(D) blend amount is 0.1~2 parts by weight.When blend amount is greater than 2 parts by weight, it is difficult to steady production.When less than 0.1 parts by weight, take off
Mould is poor.More preferably 0.3~1.5 parts by weight are most preferably 0.5~1.0 parts by weight.
It is preferred that the mixed thermoplastic elastomer (TPE) (E) in glass fiber-reinforced polycarbonate resin composition composition of the invention.It is logical
Mixed thermoplastic elastomer (TPE) (E) is crossed, the cementability raising of polycarbonate resin (A) and glass fibre (B) can be obtained without detriment to poly-
The glass fiber reinforced polyester of the characteristics such as mechanical strength possessed by carbonate resin (A) is original and the excellent appearance of molded product
Polycarbonate resin composition.
It is not particularly limited as thermoplastic elastomer (TPE) (E), olefin series thermoplastic elastomer, polystyrene heat can be enumerated
Thermoplastic elastic, hydrogenated styrene based thermoplastic elastomer, Polyester thermoplastic elastomer (TPE), acrylic acid series thermoplastic elastomer (TPE),
Polyurethane series thermoplastic elastomer (TPE), Thermoplastic polyamide elastomer etc..Wherein preferred hydrogenated styrene based thermoplastic elastomer,
Polyester thermoplastic elastomer (TPE).
Hydrogenated styrene based thermoplastic elastomer is polystyrene-poly (ethylene/propene) block copolymer, polystyrene-
Poly- (ethylene/propene) block-polystyrene copolymer, gathers polystyrene-poly (ethylene/butylene) block-polystyrene copolymer
Poly- (ethylene-vinyl/propylene) block-polystyrene copolymer of styrene-etc..In addition, these hydrogenated styrene based thermoplastic bullets
Property body also can be used utilize maleic anhydride, amine etc. modified made of modifier.In addition, they can be used alone or by two kinds
Combination of the above uses.Among these, preferred polystyrene-poly (ethylene/butylene) block-polystyrene copolymer, such as can be through
Commercial sources obtain the manufacture of Kuraray company Septon 8004,8007, Tuftec H1062 of Asahi Kasei Corporation's manufacture,
H1051, H1043 etc..
It is preferred from the styrene units content of the appearance aspect of molded product, hydrogenated styrene based thermoplastic elastomer
For 55 weight % or more.The hydrogenated styrene based thermoplastic elastomer for being 55 weight % or more as styrene units content, example
The Septon 8104 of Kuraray company manufacture, the Tuftec H1043 of Asahi Kasei Corporation's manufacture can be such as obtained through commercial sources
Deng.
Polyester thermoplastic elastomer (TPE) is the segmented copolymer that is made of hard segment and soft chain segment (by aromatic polyester
It combines on the hard segment of composition selected from one or more of the group being made of aliphatic polyether, aliphatic polyester and polycarbonate
Block copolymer made of soft chain segment).As above-mentioned hard segment, optimization aromatic polyester can enumerate poly- pair as concrete example
Benzene dicarboxylic acid butanediol ester, polybutylene naphthalate etc..These can be used alone or are used in combination of two or more.
As soft chain segment, preferred aliphat polyethers, aliphatic polyester and polycarbonate etc. can be enumerated as concrete example
Poly- (6-caprolactone), polytetramethylene glycol, polyalkylene carbonate etc..These can be used alone or by two or more combinations
It uses.As such block copolymer (copolyer), it is preferably selected from by polyester-polyester copolymer, polyester-polyether copolymerization
The copolymer etc. of one or more of the group of object and polyester-polycarbonate copolymer composition.
As can be through the Polyester thermoplastic elastomer (TPE) (E) of commercially available acquisition, it can be cited for example that Dong Li E.I.Du Pont Company system
Hytrel, Pelprene of Dongyang spinning company manufacture for making etc..
It, can also be by hydrogenated styrene based thermoplastic elastomer and Polyester thermoplastic elastomer (TPE) as thermoplastic elastomer (TPE)
It shares.By sharing the two, the glass that the cementability of polycarbonate resin (A) and glass fibre (B) further increases can be obtained
Glass fiber reinforced polycarbonate resin combination.
Relative to the glass fibre (B) of the polycarbonate resin (A) comprising 40~80 weight % and 20~60 weight %
100 parts by weight of resin combination, the present invention used in Polyester thermoplastic elastomer (TPE) (E) blend amount be 0.2~20 weight
Part.When blend amount is greater than 20 parts by weight, it is difficult to steady production, it is thus not preferred.When less than 0.2 parts by weight, polycarbonate resin
(A) poor with the cementability of glass fibre (B), it is thus not preferred.More preferably 0.3~15 parts by weight are most preferably 0.4~10 weight
Measure part.
About glass fiber-reinforced polycarbonate resin composition composition of the invention, for example, can by polycarbonate resin from
First feeder (raw material supply mouth) is supplied in extruder barrel, and after resin is sufficiently melted, glass fibre is added from second
Glassware (filler supply mouth) is supplied in extruder barrel, applies typically available disk in being kneaded screw rod used later
(such as kneading disc) etc., by using multiple spiral shell disks that disk is constituted or suitably changed as screw rod using well known method
Configuration etc. is kneaded being adjusted.Also can be used make while drawn glass fiber polycarbonate resin infiltrate to
The drawing method of forming in the fiber.
In addition, within the scope of the effect of the invention, it can also be in poly carbonate resin composition of the invention
The various resins of middle mixture, antioxidant, fluorescent whitening agent, pigment, dyestuff, carbon black, packing material, release agent, ultraviolet radiation absorption
Agent, antistatic agent, rubber, softener material, spreader (atoleine, epoxidised soybean oil etc.), fire retardant, organic metal salt etc.
Additive, anti-drip polyflon etc..
As various resins, it can be cited for example that high impact polystyrene, ABS, AES, AAS, AS, acrylic resin,
Polyamide, polyethylene terephthalate, polybutylene terephthalate (PBT), polyarylate, polysulfones, polyphenylene sulfide etc.,
These can be used one kind or share two or more.
As antioxidant, phosphorous antioxidant, phenolic antioxidant etc. can be enumerated.Wherein it is preferable to use half hindered phenols
It is antioxidant and hindered phenolic antioxidant.As semi-hindered phenol series antioxidant, sumitomo chemical company manufacture can be enumerated
Sumilizer GA-80 etc. can enumerate the Irganox 1076 of BASF AG's manufacture as hindered phenolic antioxidant
Deng these can be used one kind or share two or more.
In addition, synthetic resin of the invention is characterized in that, it is by above-mentioned fiber reinforced polycarbonate resin combination
Obtained from object molding.About the forming method of fiber-reinforced resin molded product of the invention, using extrusion molding or it is molded into
Type method.About extrusion molding, using the molding of the sheet material or abnormity extrusion etc that use extruder, in addition, injection molding makes
With the injection moulding machine of the mold that can mold the molded product and 100~200 Т ranks.Processing and forming temperature is preferably 230
~260 DEG C.The excellent appearance of the formed body, it is thus possible to be preferably applied to the shell of camera, smart phone etc..
Embodiment
The present invention is further specifically described below by embodiment.But the present invention is not limited to embodiment below,
It can arbitrarily implement to change without departing from the spirit and scope of the present invention or change.As long as it should be noted that not special sound
Bright, " % " and " part " in embodiment respectively indicates " weight % " and " parts by weight " based on weight basis.
The details of used raw material is as described below.
1. polycarbonate resin (A):
1-1. by bisphenol-A and optical self-encoding polycarbonate resin
(Sumika Styron Polycarbonate company manufacture Calibre 200-20, viscosity average molecular weigh 19000, under
In text referred to as " PC1 ")
1-2. by bisphenol-A and optical self-encoding polycarbonate resin
(Sumika Styron Polycarbonate company manufacture Calibre 200-13, viscosity average molecular weigh 21000, under
In text referred to as " PC2 ")
1-3. by bisphenol-A and optical self-encoding polycarbonate resin
(Sumika Styron Polycarbonate company manufacture Calibre 200-3, viscosity average molecular weigh 28000, under
In text referred to as " PC3 ")
2. glass fibre (B):
2-1. circular cross-section glass fibre
(KCC company manufacture CS321,10 μm of fiber footpath, the long 3mm of fiber,
Epoxy size is hereinafter referred to as " GF1 ")
2-2. circular cross-section glass fibre
(KCC company manufacture CS311,10 μm of fiber footpath, the long 3mm of fiber,
Carbamate system size is hereinafter referred to as " GF2 ")
2-3. flat cross section glass fibre
(Nitto Boseki company manufactures CSG 3PA-830,28 μm of major diameter, 7 μm of minor axis, the long 3mm of fiber, epoxy/amino
Formic acid esters system size is hereinafter referred to as " GF3 ")
3. phosphite ester based compound (C):
Bis- four oxa- -3 (2,6- di-t-butyl -4- methylphenoxy) -2,4,8,10- 3,9- represented by 3-1. following formula,
9- bis- phospha spiral shell [5,5] hendecane
[changing 5]
Adkstab PEP-36 (trade name, is hereinafter referred to " compound C1 " at the manufacture of ADEKA company)
Phosphorous acid three represented by 3-2. following formula (2,4- di-tert-butyl-phenyl) ester
[changing 6]
Irgafos 168 (trade name, is hereinafter referred to " compound C2 " at BASF AG's manufacture)
Bis- four oxa-s of [bis- (bis (alpha, alpha-dimethylbenzyl) base) phenoxy groups of 2,4-] -2,4,8,10--of 3,9- represented by 3-3. following formula
3,9- bis- phospha spiral shell [5.5] hendecane)
[changing 7]
Doverphos S-9228 (trade name, is hereinafter referred to as " C3 " at the manufacture of Dover Chemical company)
4. aliphatic ester (D):
Pentaerythritol stearate
Loxiol VPG861 (trade name, is hereinafter referred to as " D1 " at the manufacture of Cognis company)
5. thermoplastic elastomer (TPE) (E):
5-1. hydrogenated styrene based thermoplastic elastomer
5-1-1. polystyrene-poly (ethylene/butylene) block-polystyrene copolymer
Septon 8104 (trade name, 60 weight % of styrene units content, is referred to as " E1 " at the manufacture of Kuraray company)
5-1-2. polystyrene-poly (ethylene/butylene) block-polystyrene copolymer
(trade name, 30 weight % of styrene units content, is referred to as the manufacture of Kuraray company Septon 8007L
“E2”)
5.2. Polyester thermoplastic elastomer (TPE)
5-2-1. polyester-polyester copolymer
Pelprene S-3001 (trade name, is referred to as " E3 " at Dongyang spinning company manufacture)
Hard segment: polybutylene terephthalate (PBT)
Soft chain segment: poly- (6-caprolactone)
5-2-2. polyester-polyether copolymers
Pelprene P-150B (trade name, is referred to as " E4 " at Dongyang spinning company manufacture)
Hard segment: polybutylene terephthalate (PBT)
Soft chain segment: polytetramethylene glycol
5-2-3. polyester-polyether copolymers
Pelprene EN-3000 (trade name, is referred to as " E5 " at Dongyang spinning company manufacture)
Hard segment: polybutylene naphthalate
Soft chain segment: polytetramethylene glycol
5-2-4. polyester-polycarbonate copolymer
Pelprene C-2003 (trade name, is referred to as " E6 " at Dongyang spinning company manufacture)
Hard segment: polybutylene terephthalate (PBT)
Soft chain segment: polyalkylene carbonate
Examples 1 to 67 and comparative example 1~32 (production of pellet)
Using double screw extruder (Toshiba Machine Co. Ltd manufacture TEM-37SS), will above-mentioned various formula components press table 1~
Formula rate shown in 10 is kneaded at 300 DEG C of melting temperature, obtains glass fiber-reinforced polycarbonate resin composition composition.It closes
In glass fiber-reinforced polycarbonate resin composition, by polycarbonate resin, phosphite ester based compound, aliphatic ester and thermoplastic elastomehc
Property body is supplied in extruder barrel from the first feeder (raw material supply mouth), after resin combination is sufficiently melted, by glass
Fiber is supplied in extruder barrel from the second feeder (filler supply mouth), is kneaded later, and glass fibre increasing is obtained
Strong poly carbonate resin composition pellet.
<bending modulus of molded product>
The pellet of various resin combinations obtained above is 4 hours dry at 125 DEG C respectively, injection molding is used later
Machine (manufacture of Fanuc company, Roboshot S2000i100B) makes foundation at 300 DEG C of set temperature, injection pressure 100MPa
The test film with a thickness of 4mm of ISO test method(s) is measured (rigid according to the bending modulus of ISO178 using obtained test film
Property).It is 6000MPa or more as good by bending modulus.
<thermal stability>
Test film after the pellet of various resin combinations obtained above and measurement bending modulus (rigidity) is dissolved in
In methylene chloride, the insoluble matter in lysate is filtered out using NO.1 filter paper.The filtrate is thoroughly dried, by obtained polymerization
A certain amount of (0.25g) in object is dissolved in methylene chloride 50ml.Using Cannon-Fenske viscosimeter in 23 DEG C of measurement dichloros
The viscosity of methane weak solution finds out the viscosity average molecular weigh of each test film using Schnell formula.
(Schnell formula) [η]=1.23 × 10-4·M0.83
[η]: inherent viscosity, M: viscosity average molecular weigh
It should be noted that the molecular weight about the index as thermal stability reduces, it will be by the viscosity average molecular weigh of pellet
Value (Δ Mv) obtained from the viscosity average molecular weigh of test film is subtracted less than 2000 as good.
<release property>
The pellet of various resin combinations obtained above is 4 hours dry at 125 DEG C respectively, injection molding is used later
Machine (manufacture of Fanuc company, Roboshot S2000i100B) is in 300 DEG C of barrels set temperature, 50 DEG C of mold temperature, cooling
Between evaluate release property under conditions of 20 seconds.Mold uses the ejection resistance mold (shape of molded product: diameter 70mm, height of cup type
Spend 20mm, thickness 4mm), the ejection load being applied on knock pin when molding cup type molded product is measured, ejection resistance is found out
Value.As the benchmark of evaluation, ejection resistance value is less than 800N as good.
<appearance of molded articles>
For the test film after measurement bending modulus (rigidity), by visual observation to because of the surface of the molded article caused by glass fibre
Degree of roughness observed, there will be no the coarse situations because of the surface of the molded article caused by glass fibre as good.
<cementability of polycarbonate resin and glass fibre>
Using scanning electron microscope (Hitachi, Ltd manufacture, S-3400N) with 500 times to measurement bending modulus (rigidity) after
The section of test film observed, the case where glass fibre that will be attached with resin is more than half whole, is as poly- carbonic acid
The cementability of ester resin and glass fibre is good, is indicated in table with "○"；Bad situation is indicated in table with "×".It needs
Illustrate, golden vapor deposition has been carried out to test film section using ion sputtering instrument (Hitachi, Ltd's manufacture, E-1010) before observation.
[table 2]
As shown in embodiment 1~13, the example for meeting structure condition of the invention meets required performance.
On the other hand, as shown in comparative example 1~6, the example for being unsatisfactory for structure condition of the invention is respectively provided with following lack
Point.Comparative example 1 is the case where blend amount of glass fibre (B) is less than specified amount, and bending modulus is poor.Comparative example 2 is glass fibre
(B) blend amount is more than the case where specified amount, can not carry out the production of pellet.Comparative example 3 is phosphite ester based compound (C's)
Blend amount is less than the case where specified amount, and thermal stability is poor.Comparative example 4 is the blend amount of phosphite ester based compound (C) more than rule
Quantitative situation, thermal stability are poor.Comparative example 5 is the case where blend amount of aliphatic ester (D) is less than specified amount, and release property is poor.
Comparative example 6 is the case where blend amount of aliphatic ester (D) is more than specified amount, can not carry out the production of pellet.
As shown in embodiment 14~29, the example for meeting structure condition of the invention meets required performance.
On the other hand, as shown in comparative example 7~14, the example for being unsatisfactory for structure condition of the invention is respectively provided with following lack
Point.Comparative example 7 is the case where blend amount of glass fibre (B) is less than specified amount, and bending modulus is poor.Comparative example 8 is glass fibre
(B) blend amount is more than the case where specified amount, can not carry out the production of pellet.Comparative example 9 is phosphite ester based compound (C's)
Blend amount is less than the case where specified amount, and thermal stability is poor.Comparative example 10 is the blend amount of phosphite ester based compound (C) more than rule
Quantitative situation, thermal stability are poor.Comparative example 11 is the case where blend amount of aliphatic ester (D) is less than specified amount, and release property is poor.
Comparative example 12 is the case where blend amount of aliphatic ester (D) is more than specified amount, can not carry out the production of pellet.Comparative example 13 is hydrogen
The case where blend amount of change styrene series thermoplastic elastomer (E) is less than specified amount, polycarbonate resin and glass fibre glue
Connecing property is poor.Comparative example 14 is the case where blend amount of hydrogenated styrene based thermoplastic elastomer (E) is more than specified amount, molded product
Poor appearance.
As shown in embodiment 30~48, the example for meeting structure condition of the invention meets required performance.
On the other hand, as shown in comparative example 15~23, be unsatisfactory for structure condition of the invention example be respectively provided with it is following
Disadvantage.Comparative example 15 is the case where blend amount of glass fibre (B) is less than specified amount, and bending modulus is poor.Comparative example 16 is glass
The blend amount of fiber (B) is more than the case where specified amount, can not carry out the production of pellet.Comparative example 17 is phosphite ester based compound
(C) blend amount is less than the case where specified amount, and thermal stability is poor.Comparative example 18 is the blend amount of phosphite ester based compound (C)
The case where more than specified amount, thermal stability is poor.Comparative example 19 is the case where blend amount of aliphatic ester (D) is less than specified amount, is taken off
Mould is poor.Comparative example 20 is the case where blend amount of aliphatic ester (D) is more than specified amount, can not carry out the production of pellet.Compare
The case where example 21 is less than specified amount for the blend amount of Polyester thermoplastic elastomer (TPE) (E), polycarbonate resin and glass fibre
Cementability is poor.Comparative example 22 is the case where blend amount of Polyester thermoplastic elastomer (TPE) (E) is more than specified amount, can not carry out pellet
Production.Comparative example 23 is the case where blend amount of hydrogenated styrene based thermoplastic elastomer (F) is more than specified amount, molded product
Poor appearance.
As shown in embodiment 49~67, the example for meeting structure condition of the invention meets required performance.
On the other hand, as shown in comparative example 24~32, be unsatisfactory for structure condition of the invention example be respectively provided with it is following
Disadvantage.Comparative example 24 is the case where blend amount of glass fibre (B) is less than specified amount, and bending modulus is poor.Comparative example 25 is glass
The blend amount of fiber (B) is more than the case where specified amount, can not carry out the production of pellet.Comparative example 26 is phosphite ester based compound
(C) blend amount is less than the case where specified amount, and thermal stability is poor.Comparative example 27 is the blend amount of phosphite ester based compound (C)
The case where more than specified amount, thermal stability is poor.Comparative example 28 is the case where blend amount of aliphatic ester (D) is less than specified amount, is taken off
Mould is poor.Comparative example 29 is the case where blend amount of aliphatic ester (D) is more than specified amount, can not carry out the production of pellet.Compare
The case where example 30 is less than specified amount for the blend amount of Polyester thermoplastic elastomer (TPE) (E), polycarbonate resin and glass fibre
Cementability is poor.Comparative example 31 is the case where blend amount of Polyester thermoplastic elastomer (TPE) (E) is more than specified amount, can not carry out pellet
Production.Comparative example 32 is the case where blend amount of hydrogenated styrene based thermoplastic elastomer (F) is more than specified amount, molded product
Poor appearance.
Industrial applicibility
Glass fiber-reinforced polycarbonate resin composition composition of the invention is without detriment to glass fiber-reinforced polycarbonate resin composition
The excellent mechanical strength and rigidity and release property and excellent heat stability of composition, thus the utility value in its industry is high.
Such as it can be used as replacing for the thin-wall case used in electrical equipment or electronic equipment or the metal product of internal backplane
Dai Pin, it can be achieved that product lightweight.In addition, in the feelings for applying external force for the molded product obtained by such resin combination
Under condition, the molded product can be inhibited to bend as much as possible, damage etc is brought to the electronic component being accommodated in inside molded product
Undesirable condition generation.
Claims (11)
1. a kind of fiber reinforced polycarbonate resin combination, which is characterized in that relative to including 40 weight of weight %~80 %
Polycarbonate resin (A) and 20 weight of weight %~60 % glass fibre (B) 100 parts by weight of resin combination, contain
0.01 parts by weight~0.2 parts by weight phosphite ester based compound (C) and 0.1 parts by weight~2 parts by weight aliphatic ester (D).
2. fiber reinforced polycarbonate resin combination as described in claim 1, wherein polycarbonate resin (A) it is viscous
Molecular weight is 16000~30000.
3. fiber reinforced polycarbonate resin combination as claimed in claim 1 or 2, wherein glass fibre (B) utilizes epoxy
It is that size or carbamate system size are handled, the average diameter of fibre section is 6 μm~20 μm.
4. fiber reinforced polycarbonate resin combination as claimed in claim 3, wherein glass fibre (B) has flat section
Face, in the flat cross section, the average value of the major diameter of fibre section is 10 μm~50 μm, the ratio between major diameter and minor axis i.e. major diameter/minor axis
Average value be 2~8.
5. fiber reinforced polycarbonate resin combination as described in any one of claims 1 to 4, wherein phosphite ester system
Compound (C) is compound represented by compound represented by the following general formula (1) or the following general formula (2),
General formula (1)
[changing 1]
In formula, R1And R2Each independently represent the alkyl or replaced or unsubstituted virtue by alkyl that carbon atom number is 1~20
Base, a and b each independently represent 0~3 integer；
General formula (2)
[changing 2]
In general formula (2), R3Indicate the alkyl or is replaced or unsubstituted aryl by alkyl that carbon atom number is 1~20, c expression 0
~3 integer.
6. fiber reinforced polycarbonate resin combination as claimed in claim 5, wherein phosphorous acid represented by general formula (1)
Ester based compound (C) is the bis- two phospha spiral shells of (2,6- di-t-butyl -4- methylphenoxy) four oxa- -3,9- of -2,4,8,10- of 3,9-
[5,5] hendecane or the bis- two phospha spiral shells of (2,6- di-t-butyl -4- methylphenoxy) four oxa- -3,9- of -2,4,8,10- of 3,9-
[5,5] hendecane.
7. fiber reinforced polycarbonate resin combination as claimed in claim 5, wherein phosphorous acid represented by general formula (2)
Ester based compound (C) is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
8. such as fiber reinforced polycarbonate resin combination according to any one of claims 1 to 7, wherein aliphatic ester (D)
For pentaerythritol tetrastearate.
9. such as fiber reinforced polycarbonate resin combination according to any one of claims 1 to 8, wherein further include
Thermoplastic elastomer (TPE) (E), relative to 100 parts by weight of polycarbonate resin (A) and glass fibre (B), the thermoplastic elastomer (TPE) (E)
For 0.2 parts by weight~20 parts by weight.
10. fiber reinforced polycarbonate resin combination as claimed in claim 9, wherein thermoplastic elastomer (TPE) (E) is hydrogenation
Styrene series thermoplastic elastomer or Polyester thermoplastic elastomer (TPE).
11. a kind of synthetic resin is by fiber reinforced polycarbonate resin group according to any one of claims 1 to 10
It closes obtained from object molding.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
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| JP2016206482 | 2016-10-21 | ||
| JP2016-206482 | 2016-10-21 | ||
| JP2016206477 | 2016-10-21 | ||
| JP2016-206477 | 2016-10-21 | ||
| JP2017-088482 | 2017-04-27 | ||
| JP2017088482 | 2017-04-27 | ||
| JP2017-088493 | 2017-04-27 | ||
| JP2017088493 | 2017-04-27 | ||
| JP2017125892 | 2017-06-28 | ||
| JP2017-125892 | 2017-06-28 | ||
| JP2017132343 | 2017-07-06 | ||
| JP2017-132343 | 2017-07-06 | ||
| PCT/JP2017/030778 WO2018074066A1 (en) | 2016-10-21 | 2017-08-28 | Fiber-reinforced polycarbonate resin composition |
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| KR (1) | KR102414203B1 (en) |
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| CN115818985A (en) * | 2022-12-27 | 2023-03-21 | 巨石集团有限公司 | Impregnating compound for chopped glass fibers, and preparation method, product and application thereof |
| CN116568744A (en) * | 2020-12-09 | 2023-08-08 | 三菱化学株式会社 | Resin composition, pellet, molded article, and method for producing resin composition |
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| JP7257408B2 (en) * | 2018-09-10 | 2023-04-13 | 住化ポリカーボネート株式会社 | Fiber-reinforced polycarbonate resin composition |
| JP2021017533A (en) * | 2019-07-23 | 2021-02-15 | 住化ポリカーボネート株式会社 | Fiber-reinforced polycarbonate resin composition |
| TWI757886B (en) * | 2020-09-23 | 2022-03-11 | 大陸商漢達精密電子（昆山）有限公司 | High performance glass fiber reinforced pc material and the products thereof |
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| CN109790367B (en) | 2022-06-03 |
| JP6956045B2 (en) | 2021-10-27 |
| TWI813544B (en) | 2023-09-01 |
| JP6364572B1 (en) | 2018-07-25 |
| TW201817793A (en) | 2018-05-16 |
| WO2018074066A1 (en) | 2018-04-26 |
| KR20190070321A (en) | 2019-06-20 |
| JP2019011459A (en) | 2019-01-24 |
| JPWO2018074066A1 (en) | 2018-10-18 |
| KR102414203B1 (en) | 2022-06-27 |
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