CN106084710B - Thermoplastic resin composition and use its mechanograph - Google Patents
Thermoplastic resin composition and use its mechanograph Download PDFInfo
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- CN106084710B CN106084710B CN201610281314.2A CN201610281314A CN106084710B CN 106084710 B CN106084710 B CN 106084710B CN 201610281314 A CN201610281314 A CN 201610281314A CN 106084710 B CN106084710 B CN 106084710B
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to thermoplastic resin composition and its mechanograph is used, the mechanograph for automotive component more particularly to a kind of poly carbonate resin composition and using its manufacture.The thermoplastic resin composition includes：(A) polycarbonate resin；(B) vinyl graft copolymer of modified rubber includes the vinyl graft copolymer of the second modified rubber of the rubber polymer that the vinyl graft copolymer of the first modified rubber of the rubber polymer of the average grain diameter with 230nm to 380nm and (B 2) include the average grain diameter with 60nm to 200nm including (B 1)；(C) aromatic vinyl vinyl cyan copolymer；And (D) (methyl) acrylic copolymer.The thermoplastic resin composition can have excellent specific property in terms of thermal stability and glossiness.
Description
Technical field
Mechanograph the present invention relates to thermoplastic resin composition and using its manufacture.
Background technology
Makrolon is widely used in the engineering plastics of plastics industry.
Due to huge molecular structure, such as bisphenol-A, makrolon can have 150 DEG C of glass transition temperature (Tg),
So as to show high heat resistance, and the carbonyl group in carbonate group have high rotational mobility so as to
To give makrolon flexibility and rigidity.In addition, makrolon is the amorphous polymer for having excellent transparency, and
In impact resistance and with excellent specific property can be shown in terms of the compatibilities of other resins.
However, makrolon have poor mobility and usually in the form of with the alloy of various resins use with more
Mend workability and rear machinability.
Among this alloy, polycarbonate/acrylonitrile-butadiene-phenylethene copolymer (PC/ABS) alloy is durable
Property, can have excellent specific property in terms of heat resistance and impact resistance, and use it for various fields such as electrical/electronic product,
Optical devices, motor vehicle assemblies, construction material, medical instruments, the material of food containers and other real worlds.For example, PC/
ABS alloy can be readily used for the large part of transmitting amount of heat, such as motor vehicle assemblies, counter body or do
It postulates standby.
As needed, after injection-molded, some mechanographs can be made to be subjected to depositing.In the deposition of plastic material,
Usually deposition process is carried out after the coating of the surface of injection-molded product.
At present, Direct precipitation method is had been developed that, wherein the surface of the mechanograph before saving deposition is applied coated with overcoming
Environmental problem.In this approach, the surface characteristic of injection moulded products becomes the main reason for influence deposition.
Routinely, the light on the surface of injection moulded products is adjusted using for example rapid thermal cycle molding (RHCM) of mechanography
Damp degree.However, due to the longer injection-molded time, this method has limitation in productivity.It, can be in another method
The amount of the rubber polymer in thermoplastic resin composition is reduced to obtain the mechanograph with high-gloss surface.However, by
In the rubber mass of reduction, this method has the problem of deteriorating in characteristic such as impact strength.
Therefore, for the thermoplastic for the inherent characteristic for keeping resin combination simultaneously with excellent glossiness and thermal stability
Property resin combination exist need.
The content of the invention
Illustrative embodiments provide thermoplastic resin composition and using its manufacture for automotive component
Mechanograph, which can show improved thermal stability and glossiness has excellent characteristic such as simultaneously
Impact resistance, transparency and colourability.
In the exemplary embodiment, thermoplastic resin composition includes：(A) polycarbonate resin；(B) modified rubber
Vinyl graft copolymer includes the first rubber of the rubber polymer of the average grain diameter with 230nm to 380nm including (B-1)
Vinyl graft copolymer and (B-2) that glue is modified include the rubber polymer of the average grain diameter with 60nm to 200nm
The vinyl graft copolymer of second modified rubber；(C) aromatic vinyl-vinyl cyan copolymer；And (D) (methyl) propylene
Acid copolymer.
Thermoplastic resin composition can include：Vinyl graft copolymer copolymerization based on polycarbonate resin (A), modified rubber
The total weight of object (B), aromatic vinyl-vinyl cyan copolymer (C) and (methyl) acrylic copolymer (D), 65wt% is extremely
The polycarbonate resin (A) of 85wt%；The vinyl graft copolymer (B) of the modified rubber of 2wt% to 15wt%；2wt% is extremely
Aromatic vinyl-vinyl cyan copolymer (C) of 25wt%；And (methyl) acrylic copolymer of 5wt% to 30wt%
(D)。
It is 1 that the vinyl graft copolymer (B) of modified rubber, which can include weight ratio,:0.25 to 1:4 the first rubber changes
The vinyl graft copolymer (B-1) of property and the vinyl graft copolymer (B-2) of the second modified rubber.
The vinyl graft copolymer (B) of modified rubber can include acrylonitrile-butadiene-phenylethene grafted copolymer
(g-ABS)。
Aromatic vinyl-vinyl cyan copolymer (C) can include styrene-acrylonitrile copolymer.
(methyl) acrylic copolymer (D) can include methylmethacrylate copolymer.
(methyl) acrylic copolymer (D) can include Methyl Methacrylate-Styrene-acrylonitrile copolymer
(MSAN)。
Aromatic vinyl-vinyl cyan copolymer (C) and Methyl Methacrylate-Styrene-acrylonitrile copolymer
(MSAN) weight ratio can be 1:0.25 to 1:In the range of 4.
(methyl) acrylic copolymer (D) can connect comprising methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)
Graft copolymer (g-MABS).
In the exemplary embodiment, using thermoplastic resin composition's manufacture as set forth above for automotive component
Mechanograph.
The mechanograph has the 900ppm measured by the following method or less escaping gas yield：In this method
In, the particle of the 5g prepared by thermoplastic resin composition is placed in petri diss and covers institute with inserts of glass
Culture dish is stated, and at 250 DEG C when heating 3 is small on hot plate, then measuring the weight of inserts of glass increases.
The mechanograph can have according to the 95GU that ASTMD523 is measured under 20 ° of angle of reflection to the glossiness of 110GU
And the glossiness of the 90GU measured under 60 ° of angle of reflection to 105GU.
When mechanograph includes black colorant, which can have through International Commission on Illumination (CIE) Lab colors
Spend the brightness (L) for being less than 29 of systematic survey.
Specific embodiment
By the detailed description of implementation below, above and other aspect, property and advantages of the invention will become apparent
It is visible.It is to be understood that can be included the present invention is not limited to implementation below and in a different manner, and pass through
Those skilled in the art provide the embodiment fully to disclose and thoroughly understand the present invention.The scope of the present invention only by
Claim is defined.
Unless all terms tool for including technical term or scientific terminology defined otherwise herein, used herein
Have as the technical staff as the field belonging to the present invention is commonly understood by identical meaning.In addition it should further be appreciated that
The term of those such as defined in universaling dictionary should not be explained with the meaning for idealizing or excessively formalizing, removed
Non- clear stipulaties herein are so defined.
Hereinafter, embodiments of the present invention be will be described in.
According to illustrative embodiments, thermoplastic resin composition includes：(A) polycarbonate resin；(B) modified rubber
Vinyl graft copolymer；(C) aromatic vinyl-vinyl cyan copolymer；And (D) (methyl) acrylic copolymer.
Now, each component of thermoplastic resin composition according to the present invention will be described in further detail.
(A) polycarbonate resin
Polycarbonate resin (A) can be the polyester and without limitation comprising carbonic acid ester bond, can wrap
It is contained in available any polycarbonate resin in the field of resin combination.
For example, can by will from phosgene, halogen acids ester (halogen acid ester), carbonic ester and they
The compound selected in combination and the one or more dihydric phenols represented by formula 1 react to prepare the polycarbonate resin：
Wherein A1It is singly-bound, the C of substituted or unsubstituted linear chain or branch chain1To C30Alkylidene group, substitution or not
Substituted C2To C5Alkenylene group, substituted or unsubstituted C2To C5Alkyliden group, substituted or unsubstituted straight
The C of chain or branch1To C30Halogeno alkylen group, substituted or unsubstituted C5To C6Cycloalkylene group, substitution or not
Substituted C5To C6Sub- cycloalkenyl groups, substituted or unsubstituted C5To C10Ring alkyliden group, substitution or it is unsubstituted
C6To C30Arylene group, the C of substituted or unsubstituted linear chain or branch chain1To C20Polyoxyalkylene group, halogen acids ester
Group, carbonate group ,-CO- ,-S- and-SO2-；R1And R2Identical or different and independently be substitution or
Unsubstituted C1To C30Alkyl group or substituted or unsubstituted C6To C30Aryl group；And n1And n2It is identical
Or integer that is different and being independently 0 to 4.As used in this article, term " substituted " refers to use halogen
Group, C1To C30Alkyl group, C1To C30Halogenated alkyl group, C6To C30Aryl group, and/or C1To C20Alcoxyl
Hydrogen atom in base group substitution functional group.
At least two dihydric phenols represented by formula 1 can be combined to the repetitive unit for forming polycarbonate resin.
The example of dihydric phenol can include but is not limited to：Hydroquinone, resorcinol, 4,4'- dihydroxy phenyls, 2,2-
Double-(4- hydroxy phenyls)-propane (also known as " bisphenol-A "), 2,4- pairs-(4- hydroxy phenyls) -2- methybutanes, double (4- hydroxyls
Phenyl)-methane, 1,1- be double-and (4- hydroxy phenyls)-hexamethylene, 2,2- be double-and (3- chloro-4-hydroxyls phenyl)-propane, 2,2- be double-
(3- methyl -4- hydroxy phenyls)-propane, 2,2- pairs-(3,5- dimethyl -4- hydroxy phenyls)-propane, 2,2- pairs-(3,5- bis-
Chloro-4-hydroxyl phenyl)-propane, 2,2- be double-and it is (bis- bromo- 4- hydroxy phenyls of 3,5-)-propane, double (4- hydroxy phenyls)-sulfoxides, double
(4- hydroxy phenyls) -one, double (4- hydroxy phenyls)-ethers etc. and combination thereof.In the exemplary embodiment, dihydric phenol can
Be 2,2- it is double-(4- hydroxy phenyls)-propane, 2,2- be double-(3- methyl -4- hydroxy phenyls)-propane, 2,2- be double-(3,5- diformazans
Base -4- hydroxy phenyls)-propane, 2,2- pairs-(bis- chloro- 4- hydroxy phenyls of 3,5-)-propane, and/or 1,1- pairs-(4- hydroxy benzenes
Base)-hexamethylene.For example, dihydric phenol can include 2,2- pairs-(4- hydroxy phenyls)-propane.
Polycarbonate resin can include the mixture of the copolymer prepared by least two different dihydric phenols.
In addition, polycarbonate resin can include the polycarbonate resin of straight chain, the polycarbonate resin of branch and/or gather
Ester carbonate copolymer resin.
The example of the polycarbonate resin of straight chain can include bisphenol A polycarbonate resin.The polycarbonate resin of branch
Example can include by multi-functional aromatic compounds such as trimellitic anhydride and trimellitic acid and one or more dihydric phenols
The resin prepared with carbonate reaction.Can by the reaction of bifunctional carboxylic acid and one or more dihydric phenols and carbonic ester come
Polyester carbonate copolymer resin is prepared, wherein, carbonic ester can be that diaryl carbonate such as diphenyl carbonate and/or carbonic acid are sub-
Ethyl ester.
Polycarbonate resin has 10,000g/mol to 100,000g/mol, such as 14,000g/mol to 40,000g/
The weight average molecular weight of mol.In the range of this of weight average molecular weight, poly carbonate resin composition can have excellent anti-impact
Hitting property and mobility.Further, in order to meet desired mobility, polycarbonate resin can have different Weight-average moleculars
The mixture of at least two polycarbonate resins of amount.
Vinyl graft copolymer (B), aromatic vinyl-vinyl cyanide based on polycarbonate resin (A), modified rubber
The total weight (100wt%) of copolymer (C) and (methyl) acrylic copolymer (D), thermoplastic resin composition can be with
65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%,
The amount bag of 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt% or 85wt%
(A) containing polycarbonate resin exists.In addition, polycarbonate resin (A) can be with any one in more than numerical value to more than numerical value
In another amount exist.For example, based on polycarbonate resin (A), the vinyl graft copolymer (B) of modified rubber, virtue
The total weight (100wt%) of race's ethylene-ethyl vinyl cyanide copolymer (C) and (methyl) acrylic copolymer (D), makrolon
Resin (A) can exist using amounts of the 65wt% to 85wt% and as another example 70wt% to 80wt%.In this scope
Interior, the mechanograph manufactured using resin combination can show excellent specific property in terms of appearance and mechanical strength.
(B) vinyl graft copolymer of modified rubber
The vinyl graft copolymer (B) of modified rubber can have nucleocapsid structure, and it includes formed by rubber polymer
Core and by being grafted the shell formed with the vinyl monomer that skill-copolymerizable is connect around the rubber polymer of core.
The vinyl graft copolymer of modified rubber can include the vinyl graft copolymer of two kinds of modified rubbers, wherein
Rubber polymer have different average grain diameters.
For convenience, the vinyl graft copolymer of two kinds of modified rubbers is referred to as the " second of the first modified rubber
Alkenyl graft copolymer " (B-1) and " vinyl graft copolymer of the second modified rubber " (B-2).
Although grain size can be expressed as by using one group quantitative of average-size of measuring method, the routine of grain size
It represents to include representing the mode diameter (mode diameter) of the maximum of distribution, be equivalent in integral distribution curve
Between be worth median diameter, (number average diameter, length average diameter, area mean diameter, quality are average straight for various average diameters
Footpath, volume mean diameter etc.) etc..Unless otherwise stated, grain size used herein refers to D50 (in 50% distribution
Diameter under rate), it is number average particle size.
Can by by with rubber polymer connect the copolymerizable aromatic vinyl monomer for connecing skill-copolymerizable of skill with and aromatics second
The copolymerizable monomer copolymerizable of alkene monomer prepares the vinyl graft copolymer of modified rubber (B).
In the vinyl graft copolymer of the first modified rubber, rubber polymer can have 230nm to 380nm, example
Such as the average grain diameter of 250nm to 350nm.
The vinyl graft copolymer of first modified rubber can include acrylonitrile-butadiene-phenylethene grafted copolymer
(g-ABS).For example, the can be prepared by the way that styrene and acrylonitrile grafting to polybutadiene rubber polymer core are formed shell
The vinyl graft copolymer of one modified rubber.Here, it can be grafted by emulsion process, resuspension procedure etc..
The each total weight based on acrylonitrile-butadiene-phenylethene grafted copolymer (100wt%), acrylic nitrile-butadiene two
Alkene-phenylethene grafted copolymer can include polybutadiene rubber polymer, the 20wt% to 80wt% of 10wt% to 60wt%
Styrene and 5wt% to 45wt% acrylonitrile, wherein, styrene and acrylonitrile form acrylonitritrile-styrene resin
Repetitive unit.
In some embodiments, the first acrylonitrile-butadiene-phenylethene grafted copolymer can with 10,11,12,13,
14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、
39th, the amount bag of 40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 or 60wt%
Containing butadiene rubber polyirier.In addition, according to certain embodiments of the present invention, butadiene rubber polyirier can be with from above-mentioned
The amount of another in any of amount to above-mentioned amount exists.
In some embodiments, the first acrylonitrile-butadiene-phenylethene grafted copolymer can with 20,21,22,23,
24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、
49、50、51、52、53、54、55、56、57、58、59、60、61、62、63、64、65、66、67、68、69、70、71、72、73、
74th, the amount of 75,76,77,78,79 or 80wt% includes styrene.In addition, according to certain embodiments of the present invention, styrene
It can be with from any of above-mentioned amount, into above-mentioned amount, the amount of another exists.
In some embodiments, the first acrylonitrile-butadiene-phenylethene grafted copolymer can with 5,6,7,8,9,
10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、
35th, the amount of 36,37,38,39,40,41,42,43,44 or 45wt% includes acrylonitrile.In addition, some implementations according to the present invention
Mode, acrylonitrile can be with from any of above-mentioned amount, into above-mentioned amount, the amount of another exists.
In the vinyl graft copolymer of the second modified rubber, rubber polymer can have 60nm to 200nm, such as
The average grain diameter of 80nm to 180nm.
The vinyl graft copolymer of second modified rubber can include acrylonitrile-butadiene-phenylethene grafted copolymer
(g-ABS), and their preparation method is same as described above.
It is 1 that the vinyl graft copolymer of modified rubber, which can include weight ratio,:0.25、1:0.3、1:0.4、1:0.5、1:
0.6、1:0.7、1:0.8、1:0.9、1:1.0、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、
1:1.9、1:2.0、1:2.1、1:2.2、1:2.3、1:2.4、1:2.5、1:2.6、1:2.7、1:2.8、1:2.9、1:3.0、1:
3.1、1:3.2、1:3.3、1:3.4、1:3.5、1:3.6、1:3.7、1:3.8、1:3.9 or 1:The second of 4.0 the first modified rubber
The vinyl graft copolymer of alkenyl graft copolymer and the second modified rubber.In addition, the vinyl graft copolymer copolymerization of modified rubber
Object can have the weight ratio of one with one be greater than or equal in more than numerical value and being less than or equal in more than numerical value
The vinyl graft copolymer of the first modified rubber and the vinyl graft copolymer of the second modified rubber.
For example, it is 1 that the vinyl graft copolymer of modified rubber, which can include weight ratio,:0.25 to 1:4 and as another
One example 1:0.3 to 1:The vinyl graft copolymer of 3 the first modified rubber and the vinyl of the second modified rubber connect
Graft copolymer.
In the weight of the vinyl graft copolymer of the vinyl graft copolymer and the second modified rubber of the first modified rubber
It measures in the range of this of ratio, it can be in surface gloss and thermostabilization by the product of injection-molded manufacture using resin combination
Property aspect show excellent specific property.
Based on polycarbonate resin, the vinyl graft copolymer of modified rubber, aromatic vinyl-vinyl cyanide copolymerization
The total weight (100wt%) of object and (methyl) acrylic copolymer, thermoplastic resin composition can with 2wt%, 3wt%,
4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or
The amount of 15wt% includes the vinyl graft copolymer of modified rubber.In addition, the vinyl graft copolymer of modified rubber can be with
Exist with another the amount in any one in more than numerical value to more than numerical value.For example, changed based on polycarbonate resin, rubber
The total weight of the vinyl graft copolymer of property, aromatic vinyl-vinyl cyan copolymer and (methyl) acrylic copolymer
(100wt%), the vinyl graft copolymer of modified rubber can be using 2wt% to 15wt% and as another example
The amount of 3wt% to 12wt% exists.The vinyl graft copolymer of modified rubber amount this in the range of, the resin combination
Object can show excellent compatibility between polycarbonate resin and the vinyl graft copolymer of modified rubber.
(C) aromatic vinyl-vinyl cyan copolymer
Aromatic vinyl-vinyl cyan copolymer (C) can have 70,000g/mol to 400,000g/mol, such as 80,
The weight average molecular weight of 000g/mol to 200,000g/mol.
In the exemplary embodiment, aromatic vinyl-vinyl cyan copolymer (C) can include styrene-acrylonitrile
Copolymer.
Can by 60wt% to 80wt%, such as 70wt% to 80wt% aromatic vinyl compound and 20wt% extremely
The combined polymerization of the vinyl cyanide compound of 40wt%, such as 20wt% to 30wt% forms aromatic vinyl-vinyl cyanide copolymerization
Object.
In some embodiments, aromatic vinyl-vinyl cyan copolymer can with 60,61,62,63,64,65,66,
67th, the amount of 68,69,70,71,72,73,74,75,76,77,78,79 or 80wt% includes aromatic vinyl compound.In addition,
According to certain embodiments of the present invention, aromatic vinyl compound can with from any one in above-mentioned amount into above-mentioned amount
Another amount exists.
In some embodiments, aromatic vinyl-vinyl cyan copolymer can with 20,21,22,23,24,25,26,
27th, the amount of 28,29,30,31,32,33,34,35,36,37,38,39 or 40wt% includes vinyl cyanide compound.In addition, root
According to some embodiments of the present invention, vinyl cyanide compound can be with another in from any one in above-mentioned amount to above-mentioned amount
A amount exists.
When each monomer of the amount comprising above range, which can show improved anti-impact
Hitting property, and can have quite big improved appearance by the product of injection-molded manufacture using the resin combination.
Based on polycarbonate resin, the vinyl graft copolymer of modified rubber, aromatic vinyl-vinyl cyanide copolymerization
The total weight (100wt%) of object and (methyl) acrylic copolymer, thermoplastic resin composition can with 2wt%, 3wt%,
4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%,
15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt% or
The amount of 25wt% includes aromatic vinyl-vinyl cyan copolymer.In addition, aromatic vinyl-vinyl cyan copolymer can be with
Another the amount in any one and Yi Shang numerical value in more than numerical value exists.For example, changed based on polycarbonate resin, rubber
The gross weight of the vinyl graft copolymer of property, aromatic vinyl-vinyl cyan copolymer and (methyl) acrylic copolymer
Amount, aromatic vinyl-vinyl cyan copolymer can exist with the amount of 2wt% to 25wt%, such as 2wt% to 20wt%.
In the range of this of the amount of aromatic vinyl-vinyl cyan copolymer, which changes in polycarbonate resin and rubber
Property vinyl graft copolymer between compatibility and paintability in terms of can show excellent specific property.
(D) (methyl) acrylic copolymer
(methyl) acrylic copolymer can include (methyl) acrylic compounds being total to as copolymerization monomer
Polymers and the glossiness for improving the product manufactured using thermoplastic resin composition according to the present invention.For example, (first
Base) acrylic copolymer (D) can include methylmethacrylate copolymer.
For example, (methyl) acrylic copolymer can include Methyl Methacrylate-Styrene-acrylonitrile compolymer
Object (MSAN).
In thermoplastic resin composition according to the present invention, aromatic vinyl-vinyl cyan copolymer and metering system
The weight ratio of sour methyl esters-styrene-acrylonitrile copolymer can be 1:0.25、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、
1:0.8、1:0.9、1:1.0、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、1:1.9、1:
2.0、1:2.1、1:2.2、1:2.3、1:2.4、1:2.5、1:2.6、1:2.7、1:2.8、1:2.9、1:3.0、1:3.1、1:3.2、
1:3.3、1:3.4、1:3.5、1:3.6、1:3.7、1:3.8、1:3.9 or 1:4.0.In addition, in thermoplastic resin composition,
The weight ratio of aromatic vinyl-vinyl cyan copolymer and Methyl Methacrylate-Styrene-acrylonitrile copolymer can with
In the scope of one in one to more than numerical value in upper numerical value.For example, in thermoplastic resin composition, aromatic ethylene
The weight ratio of base-vinyl cyan copolymer and Methyl Methacrylate-Styrene-acrylonitrile copolymer can be 1:0.25 to 1:
In the range of 4.
In addition, (methyl) acrylic copolymer can include methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)
Graft copolymer (g-MABS).
Based on polycarbonate resin, the vinyl graft copolymer of modified rubber, aromatic vinyl-vinyl cyanide copolymerization
The total weight (100wt%) of object and (methyl) acrylic copolymer, thermoplastic resin composition can with 5wt%,
6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%,
17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%,
The amount of 28wt%, 29wt% or 30wt% include (methyl) acrylic copolymer.In addition, (methyl) acrylic copolymer
Can exist with any one in more than numerical value and another the amount in Yi Shang numerical value.For example, (methyl) acrylic compounds are common
Polymers can be copolymerized with the vinyl graft copolymer based on polycarbonate resin, modified rubber, aromatic vinyl-vinyl cyanide
Object is with the 5wt% to 30wt% of the total weight (100wt%) of (methyl) acrylic copolymer and as another example
The amount of 7wt% to 25wt% exists.
As needed, thermoplastic resin composition can be further comprising one or more additives.The reality of additive
Example can include but is not limited to fire retardant, lubricant, plasticizer, heat stabilizer, antioxidant, light stabilizer, colorant etc..It takes
Certainly in the desired characteristic of final mechanograph, these additives can be used individually or with mixture.
Fire retardant can include phosphate/salt compound, phosphite ester/salt chemical combination for reducing inflammability and fire retardant
Object, phosphonate ester/salt compound, polysiloxanes, phosphazene compound, phosphinate/salt compound, and/or melamine compound
At least one of, but not limited to this.
Lubricant contacts the metal of poly carbonate resin composition for lubrication during processing, molding and/or extrusion
Surface can include any any typical lubrication known in the art to promote the flowing of resin combination and/or movement
Agent.
Plasticizer is used to improve the flexibility, machinability, and/or person's dilatancy of poly carbonate resin composition, and can
To include any typical plasticizer known in the art.
Heat stabilizer is used in kneading and/or molding inhibit at high temperature the pyrolysis of poly carbonate resin composition, and
It can include any typical heat stabilizer known in the art.
Antioxidant is for inhibiting and/or blocking the chemical reaction between poly carbonate resin composition and oxygen, so as to anti-
Only due to resin combination decomposition resin combination inherent characteristic loss, and can include phenol, phosphite ester/salt
At least one of class, thioether class and/or amine antioxidants, but not limited to this.
Light stabilizer is used for the poly carbonate resin composition for inhibiting and/or blocking the decomposition caused by UV light
Discoloration and/or mechanical property loss and can include Hinered phenols light stabilizer, benzophenone light stabilizer and/
Or at least one of benzotriazole light stabilizer, but not limited to this.
Colorant can include any typical pigment and/or dyestuff.
Additive can be with the amount of 0.1 parts by weight of the thermoplastic resin composition based on 100 parts by weight to 15 parts by weight
In the presence of.
Thermoplasticity according to the present invention can be prepared by being used to prepare any typical known method of resin combination
Resin combination.For example, by more than component and optionally one or more other additives can mix, then squeezing out
Melting extrusion in machine, so as to prepare resin combination in granular form.
According to other illustrative embodiments, thermoplastic resin composition as set forth above can be used to manufacture molding
Product.The thermoplastic resin composition can show excellent thermal stability and glossiness.Therefore, coating processing is used no
In the case of, the deposition on the product that thermoplastic resin composition is used to pass through injection-molded manufacture can be effectively realized.
The mechanograph can have excellent glossiness., mechanograph can be with according to reflections of the ASTM D523 at 20 °
The glossiness of the 95GU measured under angle to 110GU, such as 98GU to 110GU, and can have and be measured under 60 ° of angle of reflection
90GU to 105GU, such as 95GU to 105GU glossiness.
In addition, the mechanograph can have excellent colourability.The mechanograph can have through international lighting committee member
Meeting (CIE) Lab colorimeter systems to measured on the sample comprising black colorant be less than 29, be, for example, less than 28 brightness (L).
Using spectrophotometer (CM-3600D, Konica Minolta Co., Ltd.s) including specular components
(SCI) brightness (L) is measured under pattern.Here, higher brightness value represents brighter colour gamut, it means that relative black is relatively low
Colourability.
In addition, the mechanograph can have excellent thermal stability, so as to reduce escaping gas at high temperature
It generates.As used in this article, can thermal stability be measured by atomization measure.
Specifically, in atomization measure, the particle of the 5g prepared by thermoplastic resin composition is placed on Pi Shi cultures
In ware, then covered and at 250 DEG C with inserts of glass when heating 3 is small on hot plate, then measure the weight of inserts of glass,
So as to find the yield of escaping gas at high temperature.
Mechanograph according to the present invention can have by atomization measure measure 900ppm or less, such as 450ppm or
Less escaping gas yield.
In addition, as described above, carry out atomization measure after, by measurement leave 3 it is small when after inserts of glass it is turbid
Angle value, it can be estimated that the haze characteristics of mechanograph.The turbidity value expression of reduction is deposited on the escaping gas on inserts of glass
Reduction amount so as to haze characteristics more preferably.
Mechanograph according to the present invention can be with the turbid of 3% to 18% inserts of glass before and after atomization measure
Angle value is poor.This refers to that mechanograph has excellent haze characteristics.
Mechanograph according to the present invention can have excellent characteristic in terms of glossiness, colourability and thermal stability,
So as to unlimitedly with the mechanograph for being required excellent glossiness, colourability and thermal stability.For example, mechanograph
It can be useful as the visor for automotive lamp or lens, be to require deposition processes after injection-molded
Mechanograph.
Embodiment
Hereinafter, it will describe to prove the test result of the advantageous effects of thermoplastic resin composition according to the present invention.
For the component of following embodiment and comparative example, Details as Follows：
(A) polycarbonate resin
Use the polycarbonate resin (Samsung SDI) of the weight average molecular weight with 20,000g/mol.
(B) vinyl graft copolymer of modified rubber
(B-1) using by the polybutadiene rubber polymer core of 45wt% and shell (Samsung SDI) group of 55wt%
Into acrylonitrile-butadiene-phenylethene grafted copolymer.Here, the shell is styrene by 71wt% and the propylene of 29wt%
The styrene-acrylonitrile copolymer of nitrile composition, and the polybutadiene rubber polymer has the average grain diameter of 300nm.
(B-2) using the acrylic nitrile-butadiene being made of the polybutadiene rubber polymer core of 45wt% and the shell of 55wt%
Styrene graft copolymer (Samsung SDI).Here, the shell is styrene by 71wt% and the propylene of 29wt%
The styrene-acrylonitrile copolymer of nitrile composition, and the polybutadiene rubber polymer has the average grain diameter of 130nm.
(C) aromatic vinyl-vinyl cyan copolymer
Use the styrene of the acrylonitrile comprising 24wt% and 76wt% and dividing equally again with 150,000g/mol
Aromatic vinyl-vinyl cyan copolymer (Samsung SDI) of son amount.
(D) (methyl) acrylic copolymer
(D-1) using the acrylonitrile comprising 5wt%, the styrene of 20wt% and the methyl methacrylate of 75wt%
And Methyl Methacrylate-Styrene-acrylonitrile copolymer (Samsung of the weight average molecular weight with 100,000g/mol
SDI)。
(D-2) using the methacrylic acid being made of the polybutadiene rubber polymer core of 55wt% and the shell of 45wt%
Methacrylate-acrylonitrile-butadiene-styrene graft copolymer (Samsung SDI).Here, the shell be by 20wt% styrene,
Methyl Methacrylate-Styrene-acrylonitrile of the acrylonitrile of 10wt% and the methyl methacrylate composition of 70wt% is common
Polymers, and polybutadiene rubber polymer has the average grain diameter of 240nm.
According to the amount ratiometric such as listed in table 1 for the thermoplastic resin composition of embodiment and comparing embodiment.Often
The amount of kind component is expressed as the weight % (wt%) of the total weight based on thermoplastic resin composition.
Table 1
Carbon black (the Hi-black 50L, Orion of the component that 100 parts by weight are listed in table 1 and 1 parts by weight
Engineered Carbons Co., Ltd.s) it dry mixed and is introduced continuously into consistent amount to double-screw type extruder
(L/D=29, φ=45mm), subsequent melting/kneading, so as to prepare particle.Here, it is 250 DEG C to set barrel zone temperature.Hereafter,
When drying 2 is small at 80 DEG C by the poly carbonate resin composition of granulation, cylinder temperature of the 6oz. injectors at 260 DEG C is then used
It is injection-molded under degree and 60 DEG C of molding temperature, so as to prepare the sample for characteristic evaluation.
Assess the impact resistance of thermoplastic resin composition prepared in embodiment and comparing embodiment, thermal stability,
Glossiness, haze characteristic and colourability.It is for the appraisal procedure of various evaluation items as follows, and is shown in table 2
As a result.
1) impact resistance：Cantilever-type impact strength
It is measured at 23 DEG C according to ASTM D256 and is prepared by the poly carbonate resin composition of embodiment and comparing embodiment
The 1/4 " cantilever-type impact strength of the Notch Izod sample of thickness.
2) thermal stability：Atomization measure
The particle of the 5g prepared by the poly carbonate resin composition of embodiment and comparing embodiment is placed on Pi Shi trainings
It supports in ware, is then covered and at 250 DEG C with inserts of glass when heating 3 is small on hot plate, then measure glass after 3 hours
The weight of glass panel, so as to find the yield of escaping gas.
3) glossiness
According to ASTM D523 under 20 ° and 60 ° of angle of reflection to the polycarbonate resin by embodiment and comparing embodiment
Each sample measurement glossiness prepared by composition and that there is 9cm × 5cm × 0.2cm sizes.
4) haze characteristics：Turbidity
The particle of the 5g prepared by the poly carbonate resin composition of embodiment and comparing embodiment is placed on Pi Shi trainings
It supports in ware, is then covered and at 250 DEG C with inserts of glass when heating 3 is small on hot plate, then measure glass after 3 hours
The turbidity value of glass panel, so as to compare the degree generated as the turbidity caused by depositing escaping gas on a glass.Make
Turbidity is measured with nephelometer (NDH5000, Nippon Denshoku Industries).
5) colourability：Brightness (L)
Using spectrophotometer (CM-3600D, Konica Minolta Co., Ltd.s) to include specular components
(SCI) sample measurement brightness (L) of the pattern to the size with 9cm × 5cm × 0.2cm.
Table 2
As can be seen that the thermoplastic resin composition of embodiment is in impact resistance, thermal stability, gloss from table 1 and 2
There is excellent specific property in terms of degree, turbidity and colourability.
Thus, it will be seen that the species of each component of thermoplastic resin composition and amount and being included in modified rubber
Vinyl graft copolymer in the scope of average grain diameter of rubber polymer be to significantly affect thermoplasticity according to the present invention
The impact resistance of resin combination, thermal stability, glossiness, the factor of turbidity and colourability.
Although some embodiments are being described above it should be appreciated that these embodiments be only for
Illustrate to provide and the limitation present invention cannot be construed in any way, and before do not depart from the spirit and scope of the present invention
It puts those skilled in the art various modifications may be made, change, replacing and equivalent embodiment.Therefore, model of the invention
Enclosing should be limited by appended claims and its equivalent.
Claims (10)
1. a kind of thermoplastic resin composition, comprising：
(A) polycarbonate resin；
(B) vinyl graft copolymer of modified rubber includes the rubber of the average grain diameter with 230nm to 380nm including (B-1)
The vinyl graft copolymer and (B-2) of first modified rubber of xanthan polymer include the average grain with 60nm to 200nm
The vinyl graft copolymer of second modified rubber of the rubber polymer in footpath；
(C) aromatic vinyl-vinyl cyan copolymer；And
(D) (methyl) acrylic copolymer, wherein, (methyl) acrylic copolymer (D) includes methyl methacrylate
Ester-styrene-acrylonitrile copolymer.
2. thermoplastic resin composition according to claim 1 is changed based on the polycarbonate resin (A), the rubber
Vinyl graft copolymer (B), the aromatic vinyl-vinyl cyan copolymer (C) and (methyl) acrylic compounds of property
The total weight of copolymer (D), comprising：
The polycarbonate resin (A) of 65wt% to 85wt%；
The vinyl graft copolymer (B) of the modified rubber of 2wt% to 15wt%；
Aromatic vinyl-the vinyl cyan copolymer (C) of 2wt% to 25wt%；And
(methyl) acrylic copolymer (D) described in 5wt% to 30wt%,
Wherein, the sum of weight percent of each component in the thermoplastic resin composition is equal to 100wt%.
3. thermoplastic resin composition according to claim 1, wherein, the vinyl graft copolymer of the modified rubber
(B) it is 1 comprising weight ratio:0.25 to 1:The vinyl graft copolymer (B-1) and described second of 4 first modified rubber
The vinyl graft copolymer (B-2) of modified rubber.
4. thermoplastic resin composition according to claim 1, wherein, the vinyl graft copolymer of the modified rubber
(B) acrylonitrile-butadiene-phenylethene grafted copolymer is included.
5. thermoplastic resin composition according to claim 1, wherein, the aromatic vinyl-vinyl cyan copolymer
(C) styrene-acrylonitrile copolymer is included.
6. thermoplastic resin composition according to claim 1, wherein, the aromatic vinyl-vinyl cyan copolymer
(C) with the weight ratio of the Methyl Methacrylate-Styrene-acrylonitrile copolymer 1:0.25 to 1:In the range of 4.
7. a kind of be used for motor vehicle using what thermoplastic resin composition according to any one of claim 1 to 6 manufactured
The mechanograph of component.
8. the mechanograph according to claim 7 for automotive component, wherein, the mechanograph has by with lower section
The 900ppm or less escaping gas yield of method measurement：It in the method, will be by the thermoplastic resin composition
The particle of the 5g of preparation is placed in petri diss and covers the culture dish with inserts of glass, and in heat at 250 DEG C
When heating 3 is small on plate, then measuring the weight of the inserts of glass increases.
9. the mechanograph according to claim 7 for automotive component, wherein, the mechanograph has according to ASTM
The glossiness of the 95GU that D523 is measured under 20 ° of angle of reflection to 110GU and the 90GU that is measured under 60 ° of angle of reflection are extremely
The glossiness of 105GU.
10. the mechanograph according to claim 7 for automotive component, wherein, when the mechanograph comprising black
During toner, the mechanograph has the brightness for being less than 29 measured by International Commission on Illumination's Lab colorimeter systems.
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| KR1020160051488A KR101950069B1 (en) | 2015-04-30 | 2016-04-27 | Thermoplastic resin composition and molded parts using the same |
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| KR102013018B1 (en) * | 2016-12-09 | 2019-08-21 | 롯데첨단소재(주) | Thermoplastic resin composition for plating |
| KR101991584B1 (en) | 2016-12-23 | 2019-06-20 | 롯데첨단소재(주) | Expandable resin composition, method for preparing the same and foam using the same |
| KR101961994B1 (en) * | 2016-12-27 | 2019-03-25 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| EP3562885B1 (en) * | 2016-12-28 | 2020-08-19 | Covestro Deutschland AG | Polycarbonate compositions with good mechanical properties |
| EP3564314A4 (en) * | 2016-12-30 | 2020-07-29 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article using same |
| CN108264748B (en) | 2016-12-30 | 2020-07-24 | 乐天尖端材料株式会社 | Thermoplastic resin composition and molded article using same |
| KR101945603B1 (en) * | 2016-12-30 | 2019-02-07 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| KR102001484B1 (en) * | 2016-12-30 | 2019-07-17 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR102018715B1 (en) * | 2016-12-30 | 2019-09-05 | 롯데첨단소재(주) | Resin compositions and articles using the same |
| TWI630232B (en) * | 2017-03-31 | 2018-07-21 | 奇美實業股份有限公司 | Thermoplastic resin composition and molding product thereof |
| KR102257967B1 (en) | 2017-12-11 | 2021-05-28 | 주식회사 엘지화학 | Heat-resistant resin composition and automobile spoiler using the same |
| KR101958884B1 (en) | 2017-12-29 | 2019-03-15 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR102553255B1 (en) * | 2017-12-29 | 2023-07-07 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR102117741B1 (en) | 2017-12-31 | 2020-06-01 | 롯데첨단소재(주) | Thermoplastic resin composition for plating |
| US11214645B2 (en) | 2018-02-07 | 2022-01-04 | Lg Chem, Ltd. | Method for preparing graft copolymer and thermoplastic resin molded article |
| KR102226065B1 (en) * | 2018-03-20 | 2021-03-11 | 주식회사 엘지화학 | Thermoplastic resin composition |
| CN111954687B (en) * | 2018-03-28 | 2022-12-27 | 科思创知识产权两合公司 | Composition for producing molded articles having increased gloss and thermoplastic molding compounds |
| KR102106695B1 (en) * | 2018-05-25 | 2020-05-04 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| KR102188340B1 (en) | 2018-11-29 | 2020-12-08 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| JP7386983B2 (en) * | 2020-10-29 | 2023-11-27 | エルジー・ケム・リミテッド | Thermoplastic resin composition, method for producing the same, and molded articles produced therefrom |
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