CN103911000B - There is lustrous surface, reflexive, resisting etiolation and the modelling possibilities thermoplastic resin composition of excellence - Google Patents
There is lustrous surface, reflexive, resisting etiolation and the modelling possibilities thermoplastic resin composition of excellence Download PDFInfo
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- CN103911000B CN103911000B CN201310722752.4A CN201310722752A CN103911000B CN 103911000 B CN103911000 B CN 103911000B CN 201310722752 A CN201310722752 A CN 201310722752A CN 103911000 B CN103911000 B CN 103911000B
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Abstract
The invention discloses a kind of lustrous surface, reflexive, resisting etiolation and modelling possibilities thermoplastic resin composition with excellence, described thermoplastic resin composition comprises (A) thermoplastic resin；(B) inorganic filler；(C) Chinese white；(D) light stabilizer；(E) sodium ascorbyl phosphate, wherein, based on by weight 100% comprise thermoplastic resin (A), inorganic filler (B) and the base resin composition of Chinese white (C), thermoplastic resin composition comprises the inorganic filler (B) of by weight 0.1% to 4.7%, and wherein thermoplastic resin composition can have the lustrous surface of excellence, reflexive, resisting etiolation and modelling possibilities.
Description
Technical field
The present invention relates to a kind of thermoplastic resin composition.
Background technology
At present, high heat-resisting thermoplastic resin composition is used for the portion of light emitting diode (LED)
Part.Due to efficiency and the long-life of its excellence, LED instead of the most rapidly existing various light sources.
High heat-resisting thermoplastic resin composition is for the parts of LED, including reflecting mirror, reflector, scrambling
Device, housing etc..For example, it is possible to by resin based on modified polyamide heat-resisting for height, i.e. based on PPA
The resin of (polyphthalamide), as high heat-resisting thermoplastic resin, the highest heat-resisting based on
The resin of modified polyamide utilizes glass fiber-reinforced and includes the aromatic rings part as its main chain.
For the parts as LED, high heat-resisting thermoplastic resin should have such as in LED production
The toleration of high temperature, high initial white colour index and the reflexive performance of excellence that period produces.With
Time, the concordance of light source is irradiated and is caused yellow, and this yellow makes whiteness index reduce.Therefore,
High heat-resisting thermoplastic resin also should make the reduction of this whiteness index minimize.For in the led
For the heat-resisting thermoplastic resin of height used, may also need to non-conductive.
Reflecting mirror, parts of LED, can be manufactured by multiple material, such as, ceramic or resistance to
Thermoplastic materials.For pottery, problem is productivity, and for heat resistant plastice, problem be
In the case of injection-molded, sealant heat cure, or under actual environmental conditions due to color change
The reduction of the optical reflectance caused.Additionally, when injection-molded has complicated and small structure
During LED component, not enough modelling possibilities obstruction thin film molding.
Korean Patent Publication No. 2012-0066740 discloses one and declares by polyamide
Apply Chinese white, sodium ascorbyl phosphate and glass fibre and there is the poly-of excellent reflection and resistance to impact
Amide resin compositions.But, which depict substantial amounts of inorganic filler, and the inorganic filler of excess
Its lustrous surface and modelling possibilities reduction may be made.
Summary of the invention
The invention provides a kind of thermoplastic resin composition can with excellent surface gloss.
Present invention also offers a kind of thermoplastic resin composition can with excellent reflection.
Invention further provides and a kind of can have excellent modelling possibilities thermoplastic resin composition.
Invention further provides a kind of combinations of thermoplastic resins can with excellent resisting etiolation
Thing.
Invention further provides one can have while keeping mechanical performance such as impact strength
There are excellent surface gloss, reflexive, the modelling possibilities and thermoplastic resin composition of resisting etiolation.Cause
This, the thermoplastic resin composition of the present invention can substitute the existing pottery already functioning as LED component
Porcelain or heat resistant plastice.
The thermoplastic resin composition of the present invention comprise (A) thermoplastic resin, (B) inorganic filler,
(C) Chinese white, (D) light stabilizer and (E) sodium ascorbyl phosphate, wherein, based on by weight
Meter 100% comprise thermoplastic resin (A), inorganic filler (B) and the base of Chinese white (C)
Plinth resin combination, thermoplastic resin composition can comprise by weight 0.1% to 4.7% inorganic
Filler (B).
The thermoplastic resin composition of the present invention can comprise the thermoplastic of by weight 29.9% to 70%
Property resin (A), the inorganic filler (B) of by weight 0.1% to 4.7%, by weight 29.9% to
The Chinese white (C) of 70%, the light stabilizer (D) of 0.01 weight portion to 2 weight portions are (based on 100
Weight portion comprise (A), (B) and the base resin composition of (C)) and 0.01 weight portion
Sodium ascorbyl phosphate (E) to 2 weight portions (based on 100 weight portions comprises (A), (B) and (C)
Base resin composition).Thermoplastic resin (A) can be (a1) aromatic polyamide resin and
/ or (a2) high-heat-resistance polyester resin.
Aromatic polyamide resin (a1) can be by including the virtue of 10 moles of % to 100 mole of %
The dicarboxylic acid component of fragrant race dicarboxylic acids with include C4To C20Aliphatic diamine and/or alicyclic diamine
The polycondensation reaction of diamine components prepare；High heat-resistant polyester resin (a2) can pass through aromatic series dicarboxyl
Prepared by the polycondensation reaction of acid constituents and the diol component including alicyclic diol.
Aromatic polyamide resin (a1) can have the fusing point of 200 DEG C to 380 DEG C, and can
To include the repetitive represented by following chemical formula 3:
[chemical formula 3]
Wherein m is the integer of 4 to 12, and n is the integer of 50 to 500.
High heat-resistant polyester resin (a2) can have the fusing point of 200 DEG C to 380 DEG C, and permissible
Repetitive including being represented by following chemical formula 4:
[chemical formula 4]
Wherein l be n be the integer of 50 to 500.
Inorganic filler (B) can be carbon fiber, glass fibre, boron fibre, bead, glass thin
Sheet, white carbon black, clay, Kaolin, Talcum, Muscovitum, calcium carbonate, wollastonite, potassium titanate crystal whisker,
Aluminium borate whisker, ZnOw, calcium pyroborate or combinations thereof.Inorganic filler (B) is permissible
It is wollastonite, and wollastonite can have 0.1 μm average length to 100 μm.
Chinese white (C) can be titanium oxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, sulfur
Acid barium, calcium carbonate, aluminium oxide or combinations thereof.
Light stabilizer (D) can be compound based on benzophenone, chemical combination based on salicylate
Thing, compound based on benzotriazole, compound based on acrylonitrile, compound based on hindered amine,
Compound based on hindered phenol or combinations thereof.
Sodium ascorbyl phosphate (E) can be disodium-hydrogen, sodium dihydrogen phosphate, sodium phosphate, sodium pyrophosphate,
Acidic sodium pyrophosphate or combinations thereof.
Present invention also offers the mechanograph made by the thermoplastic resin composition according to the present invention.
The mechanograph made by the thermoplastic resin composition according to the present invention can have use colorimetric
90% or the higher initial reflectance that meter records under 440nm wavelength；85 DEG C and the phase of 85%
To the fall of the reflectance less than 4% recorded under 440nm wavelength before and after standing 300 hours under humidity
Low；And 85 DEG C and 85% relative humidity under stand record before and after 300 hours less than 4
Yellowing index change (Δ YI).
The present invention can provide a kind of can have excellence lustrous surface, reflexive, modelling possibilities and
/ or the thermoplastic resin composition of resisting etiolation.
Detailed description of the invention
In detailed description of the invention below, hereinafter will be more fully described the present invention, its
In describe the present invention some but and not all embodiments.It practice, the present invention can be with many
Different forms is implemented and should not be construed as limited to embodiments set forth herein；More true
Say with cutting, it is provided that these embodiments are so that present disclosure will meet the legal requiremnt being suitable for.
The present invention relates to a kind of can have excellence lustrous surface, reflexive, modelling possibilities and/or
The thermoplastic resin composition of resisting etiolation.
Thermoplastic resin composition
The thermoplastic resin composition of the present invention can comprise (A) thermoplastic resin, (B) is inorganic fills out
Material, (C) Chinese white, (D) light stabilizer and (E) sodium ascorbyl phosphate, wherein, based on by weight
Gauge 100% comprise thermoplastic resin (A), inorganic filler (B) and Chinese white (C)
Base resin composition, thermoplastic resin composition comprises by weight 0.1% to 4.7% inorganic fill out
Material (B).
The thermoplastic resin composition of the present invention can comprise the thermoplastic of by weight 29.9% to 70%
Property resin (A), the inorganic filler (B) of by weight 0.1% to 4.7%, by weight 29.9% to
The Chinese white (C) of 70%, the light stabilizer (D) of 0.01 weight portion to 2 weight portions are (based on 100
Weight portion comprise (A), (B) and the base resin composition of (C)) and 0.01 weight portion
Sodium ascorbyl phosphate (E) to 2 weight portions (based on 100 weight portions comprises (A), (B) and (C)
Base resin composition).
(A) thermoplastic resin
(a1) aromatic polyamide resin
The thermoplastic resin of the present invention can be aromatic polyamide resin (a1).
The aromatic polyamide resin (a1) of the present invention is included in the aromatic ring on its main chain, and permissible
By including the dicarboxylic acid component of the aromatic dicarboxylic acid of 10 moles of % to 100 mole of % and including C4
To C20Aliphatic diamine and/or the polycondensation reaction of diamine components of alicyclic diamine prepare.
Without limitation, the example of aromatic dicarboxylic acid monomer can include respectively by as follows
The p-phthalic acid comprising aromatic ring on its main chain that chemical formula 1 and chemical formula 2 represent and/or isophthalic two
Formic acid:
[chemical formula 1]
P-phthalic acid (TPA)
[chemical formula 2]
M-phthalic acid (IPA)
Typical aromatic polyamide resin (a1) can include the repetition represented by following chemical formula 3
Unit:
[chemical formula 3]
Wherein m is the integer of 4 to 12, and n is the integer of 50 to 500.
Without limitation, the typical case of the aromatic polyamide resin (a1) of chemical formula 3 is real
Example can include PA6T(m=6) and/or PA10T(m=10).PA6T(m=6) can pass through
Prepared by the polycondensation reaction of cyclohexanediamine and p-phthalic acid, PA10T(m=10) can be by 1,10-
Prepared by the polycondensation reaction of decamethylene diamine and p-phthalic acid.
The aromatic polyamide resin (a1) of the present invention can have 200 DEG C or higher fusing point, example
Such as 200 DEG C to 380 DEG C, and can be to include aromatic ring (as the part of main chain) on its main chain
Polymer or copolymer.Without limitation, its instantiation can include poly-(to benzene
Two formyl hexamethylene diamines) (PA6T), polycaprolactam/poly-(hexamethylene terephthalamide) copolymer (PA6/6T),
Poly-(hexamethylene adipamide)/poly-(hexamethylene terephthalamide) copolymer (PA66/6T), poly-(adipyl oneself
Diamidogen)/poly-(6I hexamethylene isoterephalamide) copolymer (PA66/6I), poly-(hexamethylene terephthalamide)/
Poly-(6I hexamethylene isoterephalamide) copolymer (PA6T/6I), poly-(hexamethylene terephthalamide)/poly-12
Amide copolymer (PA6T/12), poly-(hexamethylene adipamide)/poly-(hexamethylene terephthalamide)/poly-(
Hexamethylene terephthalamide) copolymer (PA66/6T/6I), poly-(hexamethylene terephthalamide)/poly-(to benzene two
Formyl 2 methyl pentamethylenediamine) copolymer (PA6T/M5T), poly-(paraphenylene terephthalamide's nonamethylene diamine) (PA9T),
Poly-(paraphenylene terephthalamide's decamethylene diamine) (PA10T) etc. and combinations thereof.
(a2) high heat-resistant polyester resin
Thermoplastic resin according to the present invention can be high heat-resistant polyester resin (a2).
The material for LED component using the thermoplastic resin composition of the present invention should have excellence
Thermostability with tolerance preparation process produce high temperature.Therefore, compositions can include having high-melting-point
Base resin to obtain excellent thermostability.But, too high fusing point may cause machinability
Reducing, it is useful for therefore having suitable fusing point.In the exemplary embodiment, the height of the present invention
Heat-resistant polyester resin (a2) can have 200 DEG C or a higher fusing point, such as 200 DEG C to 380 DEG C.
Because the polymer with ring typically exhibits high-melting-point, the therefore high heat-resistant polyester tree of the present invention
Fat (a2) is to include aromatic ring and the structure of alicyclic ring on its main chain (as the part of main chain),
And can be anti-with the polycondensation of the diol component including alicyclic diol by aromatic dicarboxylic acid component
Should prepare.Therefore, the dicarboxylic acid component being used for being formed high heat-resistant polyester resin (a2) can include virtue
Fragrant race's dicarboxylic acids and derivant thereof.Without limitation, the example of aromatic dicarboxylic acid is permissible
Including p-phthalic acid, M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid etc. and their group
Close.In the exemplary embodiment, it is possible to use p-phthalic acid.
Alicyclic diol, example can be included for forming the diol component of high heat-resistant polyester resin (a2)
Such as Isosorbide-5-Nitrae-cyclohexanedimethanol (CHDM), there is ring (as the part of main chain) on its main chain
Shape repetitive.
In the exemplary embodiment, high heat-resistant polyester resin (a2) can include based on poly-(to benzene
Dioctyl phthalate cyclohexanedimethylene terephthalate) resin of (PCT), it includes the repetitive knot represented by chemical formula 4
Structure, by the p-phthalic acid as dicarboxylic acid component and the Isosorbide-5-Nitrae-cyclohexanedimethanol as diol component
Polycondensation reaction produce.
[chemical formula 4]
Wherein l be n be the integer of 50 to 500.
In addition to Isosorbide-5-Nitrae-cyclohexanedimethanol, diol component may further include ethylene glycol (EG) and makees
For alicyclic diol.In the exemplary embodiment, when diol component includes ethylene glycol, glycol group
Divide and can include that the 1,4-cyclohexanedimethanol of 15 moles of % to 100 mole of % and 0 mole of % rub to 85
The ethylene glycol of you %, the Isosorbide-5-Nitrae-cyclohexanedimethanol of such as 30 moles of % to 100 mole of % and 0 mole of %
Ethylene glycol to 70 moles of %.When diol component includes ethylene glycol as diol component, high heat-resisting
Polyester resin (a2) can be poly-(p-phthalic acid cyclohexanedimethylene terephthalate) (PCTG) tree of glycol modification
Poly-(PETP) (PETG) resin of fat or glycol modification.
Diol component may further include one or more C6To C21Aromatic diol and/or C3
To C8Alicyclic diol is so that high heat-resistant polyester resin (a2) is modified, and it is based on 100 moles of %
The content of diol component can be 3 moles of % or lower.Without limitation, C6Extremely
C21Aromatic diol and/or C3To C8The example of aliphatic diol can include propane-1,3-glycol,
Butane-1,4-glycol, pentane-1,5-glycol, hexane-1,6-glycol, 3-methylpentane-2,4-glycol, 2-
Methylpentane-1,4-glycol, 2,2,4-trimethylpentane-1,3-glycol, 2-ethyl hexane-1,3-glycol, 2,2-
Diethyl propane-1,3-glycol, 1,4-ring fourth dimethanol, 2,2-bis-(3-hydroxyethoxyphenyl)-propane,
2,2-bis-(4-hydroxy propyloxy group phenyl)-propane etc. and combinations thereof.
Such as measure in the orthomonochlorphenol solution of 25 DEG C, high heat-resistant polyester resin (a2) can have
The intrinsic viscosity [η] of 0.4dl/g to 1.5dl/g, e.g., from about 0.5dl/g to 1.1dl/g.Work as intrinsic viscosity
When [η] is less than 0.4dl/g, the mechanical performance of thermoplastic resin composition may reduce；And when intrinsic
When viscosity [η] is higher than 1.5dl/g, the modelling possibilities of thermoplastic resin composition may reduce.
High heat-resistant polyester resin (a2) can be prepared by known conventional polycondensation reactions steps, and it can
The direct polycondensation reaction of the acid carried out to include using glycol or the ester exchange reaction of lower alkyl esters.
Based on by weight 100% comprise thermoplastic resin (A), inorganic filler (B) and white
The base resin composition of pigment (C), can comprise the basis of the amount of by weight 29.9% to 70%
The thermoplastic resin (A) of invention.
When the amount of thermoplastic resin (A) is less than by weight 29.9%, thermoplastic resin composition
Thermostability may reduce；And when the amount of thermoplastic resin (A) is higher than by weight 70%,
The reflexive of thermoplastic resin composition and mechanical performance may reduce.
(B) inorganic filler
The thermoplastic resin composition of the present invention can comprise inorganic filler (B), inorganic filler (B)
There is multiple grain shape to strengthen its mechanical performance, thermostability, dimensional stability etc..
The inorganic filler of any routine can be used in the present invention.Without limitation, its
Instantiation can include carbon fiber, glass fibre, boron fibre, bead, glass flake, white carbon black,
Clay, Kaolin, Talcum, Muscovitum, calcium carbonate etc. and combinations thereof.Silicon ash can be used
Stone, potassium titanate crystal whisker, aluminium borate whisker, ZnOw, calcium pyroborate and combinations thereof are made
For aciculiform inorganic filler.In order to improve the adhesive force to thermoplastic resin, can be by applicable organic material
The surface of inorganic filler (B) coated by material.
When using inorganic filler (B) in thermoplastic resin composition, mechanograph can be improved
Mechanical performance such as hot strength, bending stiffness and bending modulus, and thermostability such as heat distortion temperature.
Thermoplastic resin group is guaranteed in the thin film of micro-molding field such as thermoplastic resin composition moulds
The mobility of compound is important.Wollastonite can be used to improve thermoplastic resin as inorganic filler
The thin film of compositions is modelling possibilities.When wollastonite is used for the thin of micro-molding application such as 1mm or lower thickness
During the molding of film, excellent thermostability and the mechanical performance of thermoplastic resin composition can be kept, and
And can substantially ensure that it is modelling possibilities.The average length of wollastonite can be that 0.1 μm is to 100 μm, example
If 0.1 μm is to 20 μm.The body density (piling up (tapped)) of wollastonite can be at 0.1g/cm3Extremely
2g/cm3, such as 0.1g/cm3To 1g/cm3In the range of.The cross section of wollastonite do not limit and
Can select according to particular use.Wollastonite can have square-section, but the most permissible
Use the wollastonite of any shape.
Based on by weight 100% comprise thermoplastic resin (A), inorganic filler (B) and white
The base resin composition of pigment (C), comprise thermoplastic resin (A), inorganic filler (B) and
The base resin composition of Chinese white (C) can comprise by weight 0.1% to 4.7% inorganic
Filler (B).
When the amount of inorganic filler (B) is less than by weight 1%, the machine of thermoplastic resin composition
Tool performance such as impact strength may reduce；And because may be made by thermoplastic resin composition
The rate of cooling of mechanograph may be slack-off, and its discharging performance may reduce.When inorganic filler (B)
When amount is higher than by weight 4.7%, because inorganic filler may manufacture from by thermoplastic resin composition
The protrusion of surface of mechanograph, the outward appearance possible deviation of mechanograph；The flowing of thermoplastic resin composition
Property may cause moldability to reduce；And due to the low whiteness compared with Chinese white, mechanograph
Lustrous surface may be reduced.
(C) Chinese white
In the present invention, use Chinese white as obtaining the most reflexive necessary component.
Without limitation, the example of Chinese white (C) can include titanium oxide, oxidation
Zinc, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate, aluminium oxide etc..Chinese white is permissible
It is used alone or being applied in combination with two or more.
Silane coupler and/or titanium coupling agent can also be used to process Chinese white (C).Exemplary
In embodiment, its surface can use compound based on silane such as VTES,
APTES, 3-glycidoxypropyl triethoxysilane
(3-glycydoxypropyltriethoxysilane) etc. and combinations thereof processes.
The Chinese white (C) of the present invention can be titanium dioxide.Can make by using titanium dioxide
Optical property such as reflexive is improved with disguised for Chinese white (C).Titanium dioxide can be conventional
Titanium dioxide, and its preparation method or diameter are not limited.
Can use inorganic surface treatment agent and/or organic surface treatment that titanium dioxide is carried out surface
Process.Without limitation, the example of inorganic surface treatment agent can include aluminium oxide (vitriol
Soil, Al2O3), silicon dioxide (Silicon stone, SiO2), zirconium dioxide (zircon, ZrO2), sodium silicate,
Sodium aluminate, sodium aluminium silicate, zinc oxide, Muscovitum etc., and combinations thereof.Do not having conditional feelings
Under condition, the example of organic surface treatment can include poly-(dimethyl siloxane), trimethyl propane
(TMP), tetramethylolmethane etc. and combinations thereof.Titanium dioxide based on 100 weight portions,
Inorganic surface treatment agent and/or organic surface treatment can be used with the amount of 2 weight portions or lower.?
In illustrative embodiments, titanium dioxide based on 100 weight portions, can be using 2 weight portions as nothing
Alumina (the Al of machine surface conditioning agent2O3) coat the titanium dioxide of the present invention.
Can use further inorganic surface treatment agent (as silicon dioxide, zirconium dioxide, sodium silicate,
Sodium aluminate, sodium aluminium silicate and/or Muscovitum) and/or organic surface treatment (such as poly-(dimethyl silica
Alkane), trimethyl propane (TMP) and/or tetramethylolmethane) titanium dioxide that will process through alumina surfaces
Modified.
Based on by weight 100% comprise thermoplastic resin (A), inorganic filler (B) and white
The base resin composition of pigment (C), comprise thermoplastic resin (A), inorganic filler (B) and
The base resin composition of Chinese white (C) can comprise the amount of by weight 29.9% to 70%
Chinese white (C).
When the amount of Chinese white (C) is less than by weight 29.9%, thermoplastic resin composition's
Light resistance and reflectance may reduce；And when the amount of Chinese white (C) is higher than by weight 70%
Time, the mechanical performance of thermoplastic resin composition such as impact strength may reduce.
(D) light stabilizer
The thermoplastic resin composition of the present invention can comprise light stabilizer (D) to prevent variable color and to press down
The reduction of reflectance processed.
Light stabilizer (D) can be that the compound with ultraviolet-absorbing is as based on benzophenone
Compound, compound based on salicylate, compound based on benzotriazole, based on acrylonitrile
Compound and other resonant structure compound；There is the compound of capture free radical ability as based on being subject to
The compound of resistance amine and compound based on hindered phenol；And the combination of one or more in them.Make
Can show with the compound with capture free radical ability with the compound with ultraviolet-absorbing
Go out more preferable effect.
Based on 100 weight portions comprise thermoplastic resin (A), inorganic filler (B) and white face
The base resin composition of material (C), thermoplastic resin composition can comprise 0.01 weight portion to 2
The light stabilizer (D) of the amount of weight portion.
When light stabilizer (D) amount less than 0.01 time, the resisting etiolation of thermoplastic resin composition and
Reflectance may reduce；And when the amount of light stabilizer (D) is higher than 2 parts, thermoplastic resin group
The reflectance of compound and resisting etiolation may reduce.
(E) sodium ascorbyl phosphate
The sodium ascorbyl phosphate (E) of the present invention can be used to obtain the enough of thermoplastic resin composition
Reflexive, and guarantee thermo-color stability, hydrolytic stability and light stability simultaneously.
When using Chinese white (C) and sodium ascorbyl phosphate (E) in thermoplastic resin composition simultaneously
Time, except excellent thermo-color stability, it is also possible to obtain enough whiteness.Sodium ascorbyl phosphate itself has
Having high whiteness, therefore the mixture of sodium ascorbyl phosphate guarantees enough reflections of thermoplastic resin composition
Property.Furthermore, it is understood that because thermoplastic resin composition include having excellence thermo-color stability and
The sodium ascorbyl phosphate of hydrolytic stability, under high-temperature/damp condition after long-term standing, becomes hardly
Normal complexion reflectance reduction.
Additionally, sodium ascorbyl phosphate (E) can effectively remove may be based on thermoplastic resin composition
Moulding process in produce acid.Therefore the heat change of the thermoplastic resin composition of the present invention can be improved
Color stability and hydrolytic stability.
Without limitation, the instantiation of sodium ascorbyl phosphate (E) can include biphosphate
Sodium, disodium-hydrogen, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate etc. and combinations thereof.
Can properly select and use any sodium ascorbyl phosphate.
Manufacture method and diameter to sodium ascorbyl phosphate (E) do not limit, and can use through surface
The sodium ascorbyl phosphate processed is to improve and the comparability of thermoplastic resin (A) and thermoplastic resin-based
Dispersibility in matter.
Can use silane coupler such as silane, epoxy silane etc. and organic material such as titanium coupling agent,
Organic acid, polyhydric alcohol, silicon etc. and combinations thereof are as surface conditioning agent.
Based on 100 weight portions comprise thermoplastic resin (A), inorganic filler (B) and white face
The base resin composition of material (C), thermoplastic resin composition can comprise 0.01 weight portion to 2
The sodium ascorbyl phosphate (E) of the amount of weight portion.
When the amount of sodium ascorbyl phosphate (E) is less than 0.01 weight portion, the reflection of thermoplastic resin composition
Property may reduce；And when the amount of light stabilizer (D) is higher than 2 weight portion, thermoplastic resin group
The impact resistance of compound and resisting etiolation may reduce.
(F) additive
The thermoplastic resin of the present invention can comprise one or more additives (F) further.Do not having
In the case of conditional, the example of additive can include fluorescent whitening agent, lubricant, releasing agent,
Nucleator, antistatic additive, stabilizer, reinforcing agent, inorganic additive, pigment, dyestuff etc. and
Combinations thereof.
Based on 100 weight portions comprise thermoplastic resin (A), inorganic filler (B) and white face
The base resin composition of material (C), can comprise the adding of amount of 0.01 weight portion to 20 weight portions
Add agent (F).
Fluorescent whitening agent can improve the reflectance of thermoplastic resin composition.Do not having conditional situation
Under, the example of fluorescent whitening agent can include stibene-hexichol Zole derivatives such as 4-(benzo
Azoles-2-base)-4 '-(5-methyl benzothiazole-2-base) stibene, 4,4 '-two (benzothiazole-2-bases) are equal
Stilbene etc. and combinations thereof.
Without limitation, the example of releasing agent can include fluoropolymer, silicone oil, hard
The slaine of fat acid, the slaine of FUSIDICACID, the ester type waxes of FUSIDICACID, Tissuemat E etc. and they
Combination.
Without limitation, the example of nucleator can include Talcum, clay etc. and it
Combination.
The thermoplastic resin group of the present invention can be prepared by the preparation method of known resin combination
Compound.For example, it is possible to mix composition and other additive of the present invention, then in extruder simultaneously
Melt extrude to be configured to bead or small pieces.
Mechanograph
Present invention also offers the mechanograph made by thermoplastic resin composition.It is being not specifically limited
In the case of mechanograph be molding, and can use extrusion molded, injection-molded, hollow molding,
Compression molded or casting moulds to make mechanograph.Those skilled in the art can easily carry out this
A little method of moulding.
The mechanograph made by the thermoplastic resin composition of the present invention can have 200mm extremely
The Spiral flow length of 300mm, such as 200mm to 270mm, spiral flow length is at 130 DEG C
Recording under molding temperature and at a temperature of the injection-molded of 330 DEG C, wherein mould has 0.5mm × 5
Mm(thickness × width) helical cavity.
The mechanograph made by the thermoplastic resin composition of the present invention can have use tintometer and exist
Record under 440nm wavelength 90% or higher, the reflectance of such as 92% to 98%；At 85 DEG C and
The reflection less than 4% recorded under 440nm wavelength before and after standing 300 hours under 85% relative humidity
Rate reduces；And stand under 85 DEG C and 85% relative humidity record before and after 300 hours less than 4
Yellowing index change (Δ YI).
The mechanograph made by the thermoplastic resin composition of the present invention can have according to ASTM
D256 is 23 DEG C of the 2kgf cm/cm to 10kgf cm/cm recording the sample of 1/8 inch, examples
Cantilever beam impact strength such as 2kgf cm/cm to 7kgf cm/cm.By the thermoplastic resin of the present invention
The mechanograph that compositions makes can have the UGV-6P gloss meter pair that use is manufactured by SUGA Inc.
2.5mm thickness sample at 60 ° of angles record 90% to 99% lustrous surface, such as 92% to 97%.
The thermoplastic resin composition of the present invention can have the lustrous surface of excellence, reflexive, molding
Property and resisting etiolation, and therefore may be used for moulding multiple mechanograph.Specifically, due to same
Time comprise the inorganic filler of appropriate amount, Chinese white, light stabilizer and sodium ascorbyl phosphate, the present invention's
Thermoplastic resin composition can have the lustrous surface of excellence, reflexive and modelling possibilities.It is permissible
There is resisting etiolation and the hydrolytic stability of excellence further, as the most quiet under conditions of high temperature/high humidity
Postpone its reflexive of holding and yellowing index.Therefore, it can be used as being commonly exposed to high temperature/high humidity
The material of the LED reflection mirror of environment.
In addition to the reflecting mirror of LED, the thermoplastic resin composition of the present invention can be applicable to appoint
The purposes of what other light of reflection.For example, it is possible to be used as the most various TV of light-emitting device, intelligence
Phone, panel computer, electrical/electronic components, indoor lamp decoration, outdoor lamp decoration, vehicle lamp decoration, display
The reflecting mirror of device, headlamp etc..
The present invention be will be further illustrated in the examples below, and following example are merely to illustrate
Purpose, and be construed to never in any form limit by the model of the present invention defined in claims
Enclose.
Embodiment and comparative example
In examples and comparative examples of the present invention use thermoplastic resin (A), inorganic filler (B),
The details of Chinese white (C), light stabilizer (D) and sodium ascorbyl phosphate (E) is as follows:
(A) thermoplastic resin
(a11) aromatic polyamide resin (PA10T)
Use PA10T, a kind of prepared by the polycondensation reaction of p-phthalic acid Yu 1，10-diaminodecane
Aromatic polyamide resin, wherein PA10T has the fusing point of 315 DEG C and includes on its main chain
Aromatic ring.
(a12) aromatic polyamide resin (PA6T)
Use PA6T, a kind of fragrance prepared by the polycondensation reaction of p-phthalic acid Yu cyclohexanediamine
Polyamide resin, wherein PA6T has the fusing point of 325 DEG C and includes aromatic ring on its main chain.
(a2) high heat-resistant polyester resin (PCT)
Use poly-(p-phthalic acid cyclohexanedimethylene terephthalate) (PCT), a kind of by p-phthalic acid and Isosorbide-5-Nitrae-
High heat-resistant polyester resin prepared by the polycondensation reaction of cyclohexanedimethanol, wherein PCT has 290 DEG C
The intrinsic viscosity [η] of fusing point and 0.6dl/g.
(B) inorganic filler
Use average length and the 0.77g/cm with 2.2 μm3Body density (ProductName: NYAD
5000) wollastonite and by NYCO Corporation prepared is as inorganic filler.
(C) Chinese white
Use titanium dioxide (ProductName: the KRONOS prepared by KRONOS Corporation
2233) as Chinese white.
(D) light stabilizer
Use light stabilizer (ProductName: the CHIMASSORB prepared by BASF Corporation
944).
(E) sodium ascorbyl phosphate
Use the acidic sodium pyrophosphate prepared by INNOPHOS Corporation as sodium ascorbyl phosphate.
(F) heat stabilizer
Heat stabilizer (the product prepared by SUMITOMO Corporation is used in comparative example 5
Name: Sumilizer GA-80).
Embodiment 1 to 7 and comparative example 1 to 6
Amount according to table 1 below adds various compositions, is then being heated to 240 DEG C to 350 DEG C
Biaxial melt extruder melts/mediates to obtain the resin combination of bead state.The method will be passed through
The bead obtained is dried 5 hours or longer at 130 DEG C, uses the spiral shell being heated to 240 DEG C to 330 DEG C
Rod-type extrusion mechanism is ready for use on the sample of performance evaluation.
In the following table 1, based on by weight 100% (A), (B) and (C), (A),
(B) represent by % by weight with the mixed proportion of (C)；Based on 100 weight portions (A),
(B) and the base resin composition of (C), (D), (E) and (F) is represented by parts by weight.
[table 1]
Make to measure using the following method the performance of the sample of preparation, and its result is illustrated in table 2.
(1) thin film modelling possibilities (Spiral flow length): it is wide that use has 0.5mm thickness × 5mm
The mould of helical cavity under the molding temperature of 130 DEG C and the injection temperature of 330 DEG C by compositions injection mould
System, then measures the length filled in a mold.
(2) reflectance (reflectivity): use Konica Minota Corporation3600D CIE Lab.
Tintometer at 440nm wavelength, measure initial reflectance (SCI comprises specular light), so
After stand after 300 hours under 85 DEG C and 85% relative humidity and again measure reflectance to evaluate reflection
The reduction of rate.
(3) resisting etiolation (yellow colour index): use Konica Minolta Corporation3600D
The initial yellowing index of the colorimetric measurements (YI) of CIE Lab., then at 85 DEG C and 85% relative humidity
Lower standing measures yellowing index again to evaluate the change of yellowing index after 300 hours.
(4) resistance to impact (cantilever beam impact strength): according to ASTM D256 at 23 DEG C to 1/8
Cantilever beam impact strength measured by the sample of inch.
(5) lustrous surface: use the UGV-6P gloss meter pair manufactured by SUGA Corporation
Lustrous surface measured by sample thick for 2.5mm at 60 ° of angles.
(6) LED component is modelling possibilities: using 750 tons of syringes based on particular manufacturing craft by resin
Compositions, in the case of 300 DEG C of injection temperatures and 130 DEG C of molding temperature hemostasis moldings, determines
The non-molding of mechanograph cooling period and discharging performance, described syringe be equipped with have 8mm length,
48 chambeies of the cup-shaped LED reflection mirror structure of 1.5mm height and 40-100 μm wall thickness.
Modelling possibilities (o): because it cooled down within the scheduled time (15 seconds), the surface of mechanograph is excellent.
Modelling possibilities (x): because the surface of mechanograph does not has sufficiently cool, the surface difference of mechanograph.
Discharging performance (o): can discharge within the scheduled time (15 seconds).
Discharging performance is (x): can not discharge within the scheduled time (15 seconds).
[table 2]
As shown in Table 2, according to the thermoplastic resin composition of embodiments of the invention 1 to 7
The thin film also while preventing resistance to impact and lustrous surface from reducing with excellence is modelling possibilities, molding
Property, reflexive and resisting etiolation.
But, with the scope of the present invention outside amount use inorganic filler (B) comparative example 1,2 and
4 not have the thin film of excellence modelling possibilities, and when will have the LED component injection-molded of ad hoc structure
Time, due to not enough modelling possibilities, its mechanograph has poor surface.Do not comprise inorganic filler (B)
Comparative example 3 have when injection-molded and may insure that the modelling possibilities of LED component but be but difficult to really
The shortcoming protecting its discharging performance.Its performance such as resistance to impact also reduces.Using another kind of heat stabilizer
(F) replacing in the comparative example 5 of sodium ascorbyl phosphate (E), its reflectance and resisting etiolation reduce.Make
With in the comparative example 6 of excessive light stabilizer (D) exceeding the scope of the present invention, it is determined that its reflection
Rate and resisting etiolation reduce.
Benefit from the teaching gone out given in above description, those skilled in the art in the invention are come
Say, it is appreciated that the many of the present invention change and other embodiment.It is therefore to be understood that this
Invention is not limited to disclosed detailed description of the invention, and is intended to include change and other embodiment
Within the scope of the appended claims.Although there is used herein specific term, they are only with generality
And illustrative meaning use and be not limited to, the scope of the present invention is in the claims
Limit.
Claims (16)
1. a thermoplastic resin composition, comprises (A) thermoplastic resin；(B) inorganic filler；(C)
Chinese white；(D) light stabilizer；(E) sodium ascorbyl phosphate, wherein, based on by weight
Meter 100% comprise described thermoplastic resin (A), described inorganic filler (B) and described in vain
The base resin composition of color pigment (C), described thermoplastic resin composition comprises by weight
The described thermoplastic resin (A) of meter 29.9% to 70%, by weight 0.1% to 4.7%
Described inorganic filler (B) and the described Chinese white (C) of by weight 29.9% to 70%；
And wherein, based on 100 weight portions comprise (A), the described base of (B) and (C)
Plinth resin combination, described thermoplastic resin composition comprises 0.01 weight portion to 2 weight portions
Described light stabilizer (D) and the described sodium ascorbyl phosphate of 0.01 weight portion to 2 weight portions
(E)。
Thermoplastic resin composition the most according to claim 1, wherein said thermoplastic resin (A)
It is (a1) aromatic polyamide resin, (a2) high heat-resistant polyester resin or combinations thereof.
Thermoplastic resin composition the most according to claim 2, wherein said aromatic polyamide
Resin (a1) is by including the dicarboxyl of the aromatic dicarboxylic acid of 10 moles of % to 100 mole of %
Acid constituents with include C4To C20Prepared by the polycondensation reaction of the diamine components of aliphatic diamine.
Thermoplastic resin composition the most according to claim 2, wherein said high heat-resistant polyester tree
Fat (a2) is by the contracting of aromatic dicarboxylic acid component with the diol component including alicyclic diol
Poly-reaction preparation.
Thermoplastic resin composition the most according to claim 2, wherein said aromatic polyamide
Resin (a1) has the fusing point of 200 DEG C to 380 DEG C and is represented by following chemical formula 3
Repetitive:
Chemical formula 3
Wherein m is the integer of 4 to 12, and n is the integer of 50 to 500.
Thermoplastic resin composition the most according to claim 2, wherein said high heat-resistant polyester tree
Fat (a2) has the fusing point of 200 DEG C to 380 DEG C, and includes by following chemical formula 4 table
The repetitive shown:
Chemical formula 4
Wherein l is the integer of 50 to 500.
Thermoplastic resin composition the most according to claim 1, wherein said inorganic filler (B)
Including carbon fiber, glass fibre, boron fibre, bead, glass flake, white carbon black, clay,
Talcum, Muscovitum, calcium carbonate, wollastonite, potassium titanate crystal whisker, aluminium borate whisker, zinc oxide
Whisker, calcium pyroborate or combinations thereof.
Thermoplastic resin composition the most according to claim 1, wherein said inorganic filler (B)
It is wollastonite or Kaolin.
Thermoplastic resin composition the most according to claim 8, wherein said wollastonite has 0.1
μm is to the average length of 100 μm.
Thermoplastic resin composition the most according to claim 1, wherein said Chinese white (C)
Including titanium oxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate,
Aluminium oxide or combinations thereof.
11. thermoplastic resin compositions according to claim 1, wherein said light stabilizer (D)
Including compound based on benzophenone, compound based on salicylate, based on benzo three
The compound of azoles, compound based on acrylonitrile, compound based on hindered amine, based on being subject to
The compound of resistance phenol or combinations thereof.
12. thermoplastic resin compositions according to claim 1, wherein said sodium ascorbyl phosphate (E)
Including disodium-hydrogen, sodium dihydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate,
Or combinations thereof.
13. thermoplastic resin compositions according to claim 2, wherein said aromatic polyamide
Resin (a1) is by including the dicarboxyl of the aromatic dicarboxylic acid of 10 moles of % to 100 mole of %
Acid constituents with include C4To C20Prepared by the polycondensation reaction of the diamine components of alicyclic diamine.
14. 1 kinds of mechanographs, including the thermoplastic resin composition described in claim 1.
15. mechanographs according to claim 14, wherein said mechanograph has use tintometer and exists
90% or the higher reflectance recorded at 440nm wavelength；Relative with 85% wet at 85 DEG C
Degree is lower stand 300 hours before and after anti-less than 4% that record under 440nm wavelength
Rate of penetrating reduces；And stand before and after 300 hours under 85 DEG C and 85% relative humidity
The change of the yellowing index less than 4 recorded.
16. mechanographs according to claim 14, wherein said mechanograph is LED reflection mirror.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0158196 | 2012-12-31 | ||
| KR1020120158196A KR101566063B1 (en) | 2012-12-31 | 2012-12-31 | Thermoplastic Resin Composition Having Excellent Surface Gloss, Reflectance, Anti-yellowing property and Moldability |
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| Publication Number | Publication Date |
|---|---|
| CN103911000A CN103911000A (en) | 2014-07-09 |
| CN103911000B true CN103911000B (en) | 2016-11-30 |
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| CN101787183A (en) * | 2009-10-15 | 2010-07-28 | 上海锦湖日丽塑料有限公司 | Low warping high surface gloss glass fiber reinforced polyester composite material and preparation method thereof |
| WO2012081801A1 (en) * | 2010-12-15 | 2012-06-21 | 제일모직주식회사 | Polyamide resin composition having excellent reflectivity, heat resistance, and water resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101421357A (en) * | 2006-04-13 | 2009-04-29 | 三菱工程塑料株式会社 | Thermoplastic resin composition and resin molded article |
| CN101616989A (en) * | 2006-11-22 | 2009-12-30 | 沙伯基础创新塑料知识产权有限公司 | Thermoplastic compounds, its preparation method and be derived from its goods |
| CN101787183A (en) * | 2009-10-15 | 2010-07-28 | 上海锦湖日丽塑料有限公司 | Low warping high surface gloss glass fiber reinforced polyester composite material and preparation method thereof |
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