CN106133058A - Polycarbonate resin composition and molded article - Google Patents

Polycarbonate resin composition and molded article Download PDF

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Publication number
CN106133058A
CN106133058A CN201580016762.3A CN201580016762A CN106133058A CN 106133058 A CN106133058 A CN 106133058A CN 201580016762 A CN201580016762 A CN 201580016762A CN 106133058 A CN106133058 A CN 106133058A
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mass
polycarbonate resin
resin composition
phenol
poly carbonate
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Inventor
泷本正己
菅浩
菅浩一
堀尾庆彦
山崎康宣
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0065—Manufacturing aspects; Material aspects
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material

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

Abstract

The invention provides a polycarbonate resin composition which is improved in fluidity and color tone and excellent in molding stability at high temperatures, and a molded article thereof. The present invention provides (1) a polycarbonate resin composition comprising 0.005 to 0.5 parts by mass of a phosphorus antioxidant (B) per 100 parts by mass of a polycarbonate resin (A) comprising 10 to 100% by mass of a polycarbonate resin (A-1) and 90 to 0% by mass of a polycarbonate resin (A-2) other than the polycarbonate resin (A-1), wherein the polycarbonate resin (A-1) is produced by using an end-capping agent comprising 1% by mass or less of a resorcinol derivative and/or 2.5% by mass or less of a phenol derivative, the total content of the resorcinol derivative and the phenol derivative being 2.5% by mass or less, and further comprising 3-pentadecylphenol having a purity of 97.5% by mass or more as a raw material, and wherein a 380nm light transmittance in a molded article having a thickness of 3mm and molded at 350 ℃ is 85.0% or more, and (2) a molded article, is obtained by molding the polycarbonate resin composition.

Description

Poly carbonate resin composition and formed body
Technical field
The present invention relates to poly carbonate resin composition and formed body, more specifically, relate to following polycarbonate resin Oil/fat composition, is mobility and tone is improved, the poly carbonate resin composition of hot forming excellent in stability, as light Learn formed products, especially as useful for light guide plate, further relate to employ the formed body of this poly carbonate resin composition.
Background technology
The excellences such as the transparency of aromatic polycarbonate resin, engineering properties, thermal property, electrical property and weatherability, utilize Its characteristic is in the optical forming pieces such as light guide plate, lens, optical fiber.Material for optical forming piece, it is desirable to high light conductivity Can, therefore carry out the exploitation of copolymerized panlite, by the improved properties of various additives.In recent years, smart mobile phone, Big picture and the slim display of commodity compared with existing product such as flat board PC start to popularize, and therefore enter one for its material Step requires the raising of mobility.
In order to improve the mobility of aromatic polycarbonate resin, such as, proposed to reduce aromatic polycarbonate resin The method of molecular weight or as disclosed in patent documentation 1 and 2 with copolymerization the height of the PTMEGs such as poly-BDO The method that the copolymerized panlite of flowing combines and makes poly carbonate resin composition.But, if utilizing such side Method improves mobility, then have the problem that the moisture resistance properties of formed body reduces.If additionally, in order to tackle hot forming and to virtue Adding phosphite ester (phosphite) in fragrant adoption carbonate resin is antioxidant, then the antioxidant of phosphite ester system holds Facile hydrolysis, even if after being processed as light guide plate, in the hot resistance test that also can carry out under temperature more than certain, damp condition Hydrolysis, there are the problem that the guide-lighting performance of light guide plate reduces.It addition, use the poly-carbonic acid of the low-molecular-weight that improve mobility The light guide plate of ester resin, after hot resistance test, easily cracks inside light guide plate, also has and easily forms internal flaw Problem.
It addition, in patent documentation 3, record to employ there is a Merlon of pentadecyl phenoxy group terminal groups Optical record medium, but tone can not make us fully being satisfied with.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-298994 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-40843 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-41011 publication
Summary of the invention
Invent problem to be solved
It is an object of the invention to, it is provided that it is poly-that mobility and tone are improved, shape stability under high temperature is excellent Polycarbonate resin composition and formed body thereof.
For the method solving problem
The present invention relates to following 1～15.
1. a poly carbonate resin composition, its relative to comprise polycarbonate resin (A-1) 10～100 mass %, And polycarbonate resin (A) 100 mass parts of polycarbonate resin (A-2) 90～0 mass % beyond described (A-1), contain Having phosphorous antioxidant (B) 0.005～0.5 mass parts, described polycarbonate resin (A-1) uses containing with following as raw material The phenol derivatives 2.5 represented below resorcinol derivatives 1 mass % that logical formula (I) represents and/or with following formula (II) Below quality %, this resorcinol derivatives is below 2.5 mass % with the total content of this phenol derivatives and also contains Purity is the end-capping reagent of the 3-pentadecyl phenol of more than 97.5 mass %, in 350 DEG C of formed bodies thick for the 3mm shaped 380nm light transmittance is more than 85.0%.
[changing 1]
R in formula1、R2For hydrogen atom or the aliphatic alkyl of carbon number 1～20.R3For hydrogen atom or saturated or insatiable hunger The aliphatic alkyl of the carbon number 1～20 of sum.R1、R2、R3Both can be the same or different.But, in above-mentioned logical formula (II) In, remove with R1=H, R3=C15H31The 3-pentadecyl phenol represented.
2. according to the poly carbonate resin composition described in described 1, wherein, relative to described (A) composition 100 mass Part, possibly together with aliphatic cyclic epoxide (C) 0.001～0.5 mass parts.
3. according to the poly carbonate resin composition described in described 1 or 2, wherein, described 3-pentadecyl phenol is pure Degree is more than 99.0 mass %.
4. according to the poly carbonate resin composition recorded any one of described 1～3, wherein, described 3-pentadecyl benzene Phenol be by after distillation, carry out crystallize and obtain.
5. according to the poly carbonate resin composition recorded any one of described 1～4, wherein, the 3-in described (A) composition The content of pentadecyl phenoxy group is 0.1～10 mass %.
6., according to the poly carbonate resin composition recorded any one of described 1～5, wherein, described (B) composition has season Penta tetrol structure.
7., according to the poly carbonate resin composition recorded any one of described 1～6, wherein, described (B) composition is following State that formula represents, double (2,4-dicumylphenyl) pentaerythritol diphosphites.
[changing 2]
8., according to the poly carbonate resin composition recorded any one of described 2～7, wherein, described (C) composition is to be selected from 3,4-epoxy hexane ylmethyls-3 ', 4 '-epoxy hexane formic acid esters, 2, the 1 of double (the hydroxymethyl)-n-butyl alcohol of 2-, 2-ring At least one in oxygen-4-(2-epoxy ethyl) hexamethylene addition product and their mixture.
9. according to the poly carbonate resin composition recorded any one of described 1～8, wherein, relative to described (A) composition 100 mass parts, possibly together with polysiloxane (D) 0.02～0.15 mass parts with functional group.
10. according to the poly carbonate resin composition described in described 9, wherein, described functional group is selected from alkoxyl, virtue At least one in epoxide, polyoxyalkylenes, carboxyl, silanol base, amino, sulfydryl, epoxy radicals and vinyl.
11. according to the poly carbonate resin composition described in described 9 or 10, wherein, described in there is the poly-of functional group have The refractive index of organic siloxane (D) is less than 0.13 with the difference of the refractive index of described polycarbonate resin (A).
12. according to the poly carbonate resin composition recorded any one of described 1～11, wherein, described polycarbonate resin The viscosity-average molecular weight of fat (A) is 8,000～19,000.
13. 1 kinds of formed bodies, are to shape the poly carbonate resin composition recorded any one of described 1～12 to form.
14. according to the formed body described in described 13, and wherein, formed body is light conducting member.
15. according to the formed body described in described 14, and wherein, light conducting member is light guide plate.
Invention effect
According to the present invention it is possible to provide mobility and tone is improved, the poly-carbon of shape stability excellence under high temperature Acid ester resin compositions and formed body.
Detailed description of the invention
[poly carbonate resin composition]
The poly carbonate resin composition of the present invention relative to comprise polycarbonate resin (A-1) 10～100 mass %, with And polycarbonate resin (A) 100 mass parts of polycarbonate resin (A-2) 90～0 mass % beyond described (A-1), contain Phosphorous antioxidant (B) 0.005～0.5 mass parts.Hereinafter, the poly carbonate resin composition of the present invention is illustrated.
(polycarbonate resin (A-1))
Polycarbonate resin (A-1) is with below containing resorcinol derivatives 1 mass % represented with following formula (I) And/or below phenol derivatives 2.5 mass % represented with following formula (II), this resorcinol derivatives and this phenol derivative The content that adds up to of thing is below 2.5 mass % and also by containing the 3-pentadecyl phenol that purity is more than 97.5 mass % End-capping reagent as raw material use obtained by resin.
The 3-pentadecyl benzene that purity is more than 97.5 mass % used as the end-capping reagent of polycarbonate resin (A-1) Phenol is preferably obtained by natural goods.
And, in this specification, sometimes the 3-pentadecyl phenol that purity is more than 97.5 mass % is referred to as " high-purity 3-pentadecyl phenol ".
<high-purity 3-pentadecyl phenol>
The purity of the high-purity 3-pentadecyl phenol used in the present invention needs to be more than 97.5 mass %.If its purity Less than 97.5 mass %, then when the raw material as macromolecular materials such as polycarbonate resins uses, yellow chromaticity is high, it is possible to make The transparency, deteriorated appearance.From the viewpoint of above, the purity of high-purity 3-pentadecyl phenol be preferably 99.0 mass % with On.
In order to obtain such high-purity 3-pentadecyl phenol, use the extraction of the natural goods of the shell liquid coming from Fructus anacardii Thing.Particularly effective way is to use comprising the Cardanol about 10 mass % in the shell liquid of Fructus anacardii as manufacturing raw material. 3-pentadecyl phenol that Cardanol contained in cashew nut shell liquid mainly represents with following formula (III), 3-pentadecyl benzene Phenol monoene, 3-pentadecyl phenol diene and the mixture of 3-pentadecyl phenol triolefin.
[changing 3]
In above-mentioned formula (III), at R4For-(CH2)14CH3In the case of, for 3-pentadecyl phenol, at R4For-(CH2)7CH =CH (CH2)5CH3In the case of, for 3-pentadecyl phenol monoene, at R4For-(CH2)7CH=CHCH2CH=CH (CH2)CH3 In the case of, for 3-pentadecyl phenol diene, at R4For-(CH2)7CH=CHCH2CH=CHCH2CH=CH2In the case of, for 3-pentadecyl phenol triolefin.
As it has been described above, the main component of Cardanol contained in cashew nut shell liquid is included in 3 (metas) and has the benzene of alkyl Amphyl, described alkyl has saturated bond and the unsaturated double-bond of 1～3, and carbon number is 15.
In order to effectively obtain the high-purity 3-pentadecyl benzene that purity is more than 97.5 mass % used in the present invention Phenol, is preferably used in cashew nut shell liquid contained Cardanol it is best to use carry out this Cardanol obtained by hydrogenation process The method that thick pentadecyl phenol (low-purity pentadecyl phenol) carries out high purity.Alternatively, it is also possible to use following side Method, i.e. use by cashew nut shell liquid is directly carried out hydrogenation treatment and the hydrogenation treatment liquid to gained carry out distillable slightly Pentadecyl phenol carries out high purity.And, commercially available pentadecyl phenol is to enter Cardanol contained in cashew nut shell liquid Row hydrogenation treatment and obtain, be usually less than 97.5 mass % yet with its purity, therefore using commercially available pentadecyl phenol In the case of, need to carry out high purity.
<hydrogenation treatment method>
In order to obtain 3-pentadecyl phenol, the unsaturated bond of the straight-chain hydrocarbon part to Cardanol preferably described above (double bond) hydrogenates, and is converted to saturated bond.In order to improve 3-when straight-chain hydrocarbon part contains a lot of unsaturated bond Pentadecyl phenol purity, must be repeated distillation or crystallize sometimes, and productivity ratio reduces.Therefore, obtain not by hydrogenation The conversion ratio (hydrogenation ratio) of saturated bond is preferably 90 moles of more than %, more preferably 95 moles more than %.Cardanol after hydrogenation In unsaturated bond survival rate (number of the unsaturated bond in every 1 molecule of Cardanol) be preferably 0.2/molecule with Under, below more preferably 0.1/molecule.
As the method for hydrogenation, it is not particularly limited, it is possible to use usual way.As catalyst, can enumerate palladium, The noble metals such as ruthenium, rhodium, platinum or nickel, maybe the metal selected from them is supported on the carriers such as activated carbon, activated alumina, kieselguhr Material.As reactive mode, the catalyst of the stirring powder that suspends can be used to carry out the interval reacted Mode or use are filled with the continuation mode of the reaction tower of the catalyst shaped.Mode according to hydrogenation can not also use Solvent during hydrogenation, in the case of using solvent, generally can enumerate alcohols, ethers, esters, saturated hydrocarbons.During hydrogenation Reaction temperature is not particularly limited, but generally can be set as 20～250 DEG C, is preferably set to 50～200 DEG C.If reaction temperature Spend low, then hydrogenation rate is slack-off, if the most too high, then catabolite has the trend becoming many.Hydrogen pressure during hydrogenation generally may be used To be set as normal pressure～80kgf/cm2(normal pressure～78.4 × 105Pa), 3～50kgf/cm it are preferably set to2(2.9×105~ 49.0×105Pa)。
<high purity method>
Utilize the purity of the thick pentadecyl phenol (low-purity pentadecyl phenol) that above-mentioned hydrogenation treatment method obtains Usually 90～93 mass %, the phenol contained beyond various resorcinol derivatives or 3-pentadecyl phenol as impurity spreads out Biological.
And, in this specification, so-called resorcinol derivatives, is to have the meta at phenyl ring to have 2 OR base (R tables Show hydrogen atom or the aliphatic alkyl of carbon number 1～20.) the compound of structure, so-called phenol derivatives, is to have Phenyl ring has the compound of the structure of 1 this OR base.
As the side obtaining the high-purity 3-pentadecyl phenol that purity is more than 97.5 mass % used in the present invention Method, can enumerate and utilize distillation to carry out high purity the thick pentadecyl phenol utilizing aforesaid hydrogenation treatment method to obtain Method, crystallize is utilized to carry out the method for high purity, utilize crystallize to carry out the method etc. of high purity after distillation.These methods In the middle of, the method carrying out crystallize after preferably being distilled by thick pentadecyl phenol.Further, it is possible to use purity high purity is arrived 3-pentadecyl phenol more than 97.5 mass %, then distillation, crystallize are repeated, it is hereby achieved that the 3-ten of higher purity Five alkylphenols.
As the method utilizing distillation to carry out high purity, such as, air-distillation or decompression distillation can be utilized to carry out high-purity Degreeization, wherein carries out high purity preferably by decompression distillation.When utilizing decompression distillation to carry out high purity, preferably master is evaporated It is divided into temperature and the pressure of 1～10mmHg of 200～260 DEG C, uses filler to process, now in vacuum distillation tower Preferably reflux ratio (capacity of returns/quantity of distillate) is set to 0.5～10.As filler used in vacuum distillation tower, it is possible to use McMahon packing, Dixon filler, Raschig ring, Pall ring, ring packing, the filler such as inter-pack packing in the last of the twelve Earthly Branches, but preferably Use McMahon packing.
As utilizing the crystallize method by 3-pentadecyl phenol high purity, can make in crystallization solvent in crystallize groove In be dissolved with thick pentadecyl phenol the temperature of solution reduce, utilize 3-pentadecyl phenol for the purpose of high purity molten The hypersaturated state of liquid and the difference of the saturated concentration of this compound, make 3-pentadecyl phenol separate out and generate 3-pentadecyl benzene The crystal of phenol, then by 3-pentadecyl phenol solid-liquid separation from solution of crystal state, it is hereby achieved that highly purified 3-pentadecyl phenol.Crystallize operation can be entered in the large-scale temperature province of the boiling point of crystallization solvent used to fusing point OK.As long as it addition, crystallization solvent can dissolve the solvent of 3-pentadecyl phenol, be just not particularly limited, it is possible to use third Ketone, ethyl acetate, hydrocarbon system solvent, acetonitrile, methanol, ethanol etc..In the middle of them, preferred hydrocarbons series solvent, more preferably hexane, heptane. The usage amount of crystallization solvent can suitably set, but uses 2～20 matter preferably with respect to 3-pentadecyl phenol 1 mass parts Amount part, more preferably uses the crystallization solvent of 4～10 mass parts, thus effectively can give birth to while guaranteeing desired purity Produce.Although it addition, crystallize can also be carried out without crystal seed, but by putting into crystal seed, can effectively carry out crystallize.
During it addition, make the temperature being dissolved with the solution of thick pentadecyl phenol in crystallization solvent reduce in crystallize groove, Known have control cooling method, straight line cooling method, natural cooling etc., but cooling method is not particularly limited, additionally rate of cooling Can suitably set.Wherein, control cooling method and reduce variations in temperature (slow down rate of cooling) at the initial stage that crystallization content is few, at knot Brilliant quantitative change increases variations in temperature (quickening rate of cooling) at many latter stage, thus the degree of supersaturation of saturated solution is protected the most lower Holding certain, therefore the generation of secondary core is inhibited, and can only obtain monodisperse particle, thus preferably.Exist as rate of cooling Initial stage is preferably set to 0 DEG C (temperature is certain)～-10 DEG C/h, is more preferably set as 0 DEG C (temperature is certain)～-5 DEG C/h, Latter stage is preferably to carry out-5 DEG C/h～-30 DEG C/h of high purity, more preferably to be allowed to lower the temperature with-10 DEG C～-20 DEG C/h.
Utilize the high purity method of above-mentioned record, can by thick pentadecyl phenol obtain purity be 97.5 mass % with On 3-pentadecyl phenol.
In the high-purity 3-pentadecyl phenol used in the present invention, it is desirable between representing with following formula (I) Below phenol derivatives 2.5 mass % represented below hydroquinone derivatives 1 mass % and/or with following formula (II), and This resorcinol derivatives is below 2.5 mass % with the total amount of this phenol derivatives.If this resorcinol derivatives and should In the content of phenol derivatives is above-mentioned scope, then can improve the transparency of polycarbonate resin (A-1), outward appearance.It addition, In the case of the purity of high-purity 3-pentadecyl phenol is more than 99.0 mass %, the preferably content of this resorcinol derivatives Be the content of below 0.8 mass % and/or this phenol derivatives be below 0.8 mass %, and this resorcinol derivatives with The total amount of this phenol derivatives is below 0.8 mass %.
[changing 4]
In above-mentioned logical formula (I) and logical formula (II), R1、R2For hydrogen atom or the aliphatic alkyl of carbon number 1～20.R3For Hydrogen atom is saturated or the aliphatic alkyl of undersaturated carbon number 1～20.R1、R2、R3Both can be the same or different. But, in above-mentioned logical formula (II), remove with R1=H, R3=C15H31The 3-pentadecyl phenol represented.
For R1、R2For the aliphatic alkyl of carbon number 1～20, can exemplify methyl, ethyl, propyl group, butyl, penta Base, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, myristyl, pentadecyl, cetyl, heptadecyl, 18 The alkyl such as alkyl.For R3For the aliphatic alkyl of saturated or undersaturated carbon number 1～20, except above-mentioned R1、R2Middle illustration Alkyl beyond, it is also possible to exemplify the monoene as the unsaturated double-bond in described alkyl with one or more carbon-to-carbons, Diene, the unsaturated fatty hydrocarbons base of triolefin.
For compound contained in above-mentioned logical formula (I), as R1、R2It is all the compound of hydrogen atom, 5-can be exemplified Pentadecyl resorcinol, oreinol diphenol, 5-ethyl resorcinol, 5-propyl diphenol, 5-butyl resorcinol, Between 5-hexyl resorcin, 5-octyl resorcinol, 5-decyl resorcinol, 5-dodecyl resorcinol, 5-myristyl The R such as Benzodiazepines, 5-octadecyl resorcinol, 5-nonadecyl resorcinol3Chemical combination for the alkyl of carbon number 1～20 Thing, additionally in described alkyl, it is also possible to is the monoene of the unsaturated double-bond with one or more carbon-to-carbons, diene, triolefin etc. Unsaturated fatty hydrocarbons base.
It addition, in above-mentioned logical formula (I), as R1Aliphatic alkyl, R for carbon number 1～202For hydrogen atom, R3For The compound of the saturated or undersaturated aliphatic alkyl of carbon number 1～20, such as, can exemplify 3-methoxyl group-5-15 Alkylphenol, 3-ethyoxyl-5-pentadecyl phenol, 3-propoxyl group-5-pentadecyl phenol, 3-butoxy-5-pentadecyl Phenol, 3-methoxyl group-5-hexylphenol, 3-methoxyl group-5-octyl phenol, 3-methoxyl group-5-decyl phenol, 3-methoxyl group-5- Dodecyl phenol, 3-methoxyl group-5-myristyl phenol, 3-methoxyl group-5-heptadecyl phenol, 3-methoxyl group-5-18 Alkylphenol, 3-methoxyl group-5-nonadecyl phenol, 3-ethyoxyl-5-hexylphenol, 3-ethyoxyl-5-octyl phenol, 3-second Epoxide-5-decyl phenol, 3-ethyoxyl-5-dodecyl phenol, 3-ethyoxyl-5-myristyl phenol, 3-ethyoxyl-5-ten The compounds such as seven alkylphenols, 3-ethyoxyl-5-octadecylphenol, 3-ethyoxyl-5-nonadecyl phenol, additionally described In the alkyl of 5, it is also possible to be that there is the unsaturated lipids such as the monoene of unsaturated double-bond of one or more carbon one carbon, diene, triolefin Fat race alkyl.
For compound contained in above-mentioned logical formula (II), as R1For hydrogen atom, R3For saturated or undersaturated carbon atom The compound of the aliphatic alkyl of several 1～20, it is also possible to be 3-hexylphenol, 3-octyl phenol, 3-decyl phenol, 3-dodecane Base phenol, 3-tridecyl phenol, 3-myristyl phenol, 3-cetyl phenol, 3-octadecylphenol, 3-nonadecyl Phenol etc. are at 3 compounds with alkyl or the list of the unsaturated double-bond in described alkyl with one or more carbon-to-carbons The unsaturated fatty hydrocarbons bases such as alkene, diene, triolefin.
It addition, as R1For the compound of the aliphatic alkyl of carbon number 1～20, such as, it is the situation of hexyl at 3 Under, 1-methoxyl group-3-hexyl benzene, 1-ethyoxyl-3-hexyl benzene, 1-propoxyl group-3-hexyl benzene, 1-butoxy-3-can be enumerated Hexyl benzene, 1-amoxy-3-hexyl benzene, 1-hexyloxy-3-hexyl benzene, 1-octyloxy-3-hexyl benzene, 1-decyloxy-3-hexyl The compounds such as benzene, 1-dodecyloxy-3-hexyl benzene, 1-tetradecyloxyaniline-3-hexyl benzene.It is the situation of pentadecyl at 3 Under, can enumerate 1-methoxyl group-3-pentadecyl benzene, 1-ethyoxyl-3-pentadecyl benzene, 1-propoxyl group-3-pentadecyl benzene, 1-butoxy-3-pentadecyl benzene, 1-amoxy-3-pentadecyl benzene, 1-hexyloxy-3-pentadecyl benzene, 1-octyloxy-3- Pentadecyl benzene, 1-decyloxy-3-pentadecyl benzene, 1-dodecyloxy-3-pentadecyl benzene, 1-tetradecyloxyaniline-3-ten The compounds such as five alkylbenzenes.
And, in described logical formula (I) and logical formula (II), illustrated alkyl both can be straight-chain alkyl, it is also possible to It it is branched-chain alkyl.
<polycarbonate resin (A-1)>
Polycarbonate resin (A-1) is preferably aromatic polycarbonate resin, and main chain comprises and represents with following formula (IV) Repetitive.
Polycarbonate resin (A-1) both can be used alone or two or more kinds may be used.
[changing 5]
In formula, R5And R6Represent halogen atom, the alkyl of carbon number 1～6 or the alkane of carbon number 1～6 independently of one another Epoxide.X represents the ring Asia of singly-bound, the alkylidene of carbon number 1～8, the alkylidene radical of carbon number 2～8, carbon number 5～15 Alkyl, the ring alkylidene radical of carbon number 5～15, fluorenes diyl, the aryl alkylene of carbon number 7～15, carbon number 7～15 Arylalkylidenyl ,-S-,-SO-,-SO2-,-O-or-CO-.A and b represents the integer of 0～4 independently of one another.
As R5And R6The halogen atom represented independently of one another, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine former Son.
As R5And R6The alkyl represented independently of one another, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, various fourth Base (so-called " various ", including straight-chain and the group of all branched, the most identical.), various amyl group, various hexyl.As R5And R6The alkoxyl represented independently of one another, can enumerate the situation that alkyl portion is described alkyl.
As R5And R6, the preferably alkyl of carbon number 1～4 or the alkoxyl of carbon number 1～4.
As the alkylene base represented by X, such as can enumerate methylene base, ethylene group, 1,3-trimethylene base, Isosorbide-5-Nitrae-fourth support group, 1,6-hexamethylene base etc., the preferably alkylene base of carbon number 1～5.As the alkylidene radical represented by X, ethidine, isopropyl can be enumerated Fork base etc..As the cycloalkylene represented by X, Pentamethylene. diyl or hexamethylene diyl, cyclooctane diyl etc. can be enumerated, preferably The ring alkylidene of carbon number 5～10.As the ring alkylidene radical represented by X, such as, can enumerate cyclohexylidene base, 3,5,5-front threes Base cyclohexylidene base, 2-adamantylidene base etc., the preferably ring alkylidene radical of carbon number 5～10, the more preferably ring of carbon number 5～8 Alkylidene radical.
As the aryl portion of the Arylalkylidenyl represented by the aryl portion of the aryl-n-hold base represented by X and X, The aryl of the ring carbons numbers 6～14 such as phenyl, naphthyl, xenyl, anthryl can be enumerated.
A and b represents the integer of 0～4, preferably 0～2, more preferably 0 or 1 independently of one another.
<manufacture method of polycarbonate resin (A-1)>
Below, the manufacture method of polycarbonate resin (A-1) is illustrated.In order to manufacture polycarbonate resin (A-1), Need to use the described high-purity 3-pentadecyl phenol becoming terminal groups as end-capping reagent.
As end-capping reagent, it is also possible to by the end-capping reagent (other end-capping reagents) beyond high-purity 3-pentadecyl phenol with high-purity Degree 3-pentadecyl phenol is also used.As other end-capping reagents, it is possible to use used in the past for manufacturing polycarbonate resin End-capping reagent, such as can enumerate phenol, paracresol, p-t-butyl phenol, p-cumylphenol, tribromphenol, nonyl phenol, to uncle Octyl phenol etc..In the middle of them, preferably p-t-butyl phenol and p-cumylphenol.By high-purity 3-pentadecyl phenol and its His end-capping reagent and with in the case of, for its usage rate, preferably (3-pentadecyl phenol): the mol ratio of (other end-capping reagents) It is 99: 1～20: 80, more preferably 90: 10～30: 70.
In order to manufacture polycarbonate resin (A-1), need the dihydric phenol used for constituting main chain.As dihydric phenol, can To use various known dihydric phenol, but the dihydric phenol that with following formula (1) represent is preferably used.
[changing 6]
Herein, in above-mentioned formula (1), R5、R6, X, a and b same as previously described.
As the dihydric phenol represented with above-mentioned formula (1), it is not particularly limited, but is suitably for 2, double (the 4-hydroxy benzenes of 2- Base) propane (common name: bisphenol-A).
As the dihydric phenol beyond bisphenol-A, such as can enumerate double (4-hydroxy phenyl) methane, 1, double (the 4-hydroxy benzenes of 1- Base) ethane, 2, double (4-hydroxy phenyl) butane of 2-, 2, double (4-hydroxy phenyl) octane of 2-, double (4-hydroxy phenyl) phenylmethane, Double (4-hydroxy phenyl) diphenyl methane, 2,2-double (4-hydroxy-3-methyl phenyl) propane, double (4-hydroxy phenyl) naphthyl first Alkane, 1, double (4-hydroxy-tert-butyl phenyl) propane of 1-, 2, double (4-hydroxyl-3-bromophenyl) propane of 2-, 2,2-double (4-hydroxyl-3, 5-3,5-dimethylphenyl) propane, 2, double (4-hydroxyl-3-chlorphenyl) propane of 2-, 2, double (4-hydroxyl-3, the 5-Dichlorobenzene base) third of 2- Alkane, 2, double (hydroxyaryl) alkanes such as double (4-hydroxyl-3,5-dibromo phenyl) propane of 2-, 1, double (4-hydroxy phenyl) ring penta of 1- Alkane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1, double (the 4-hydroxy phenyl)-3 of 1-, 5,5-trimethyl-cyclohexanes, 2, double (the 4-hydroxyl of 2- Base phenyl) norbornane, 1, double (hydroxyaryl) cycloalkane, 4, the 4 '-dihydroxy such as double (4-hydroxy phenyl) cyclododecanes of 1- Diphenyl ether, 4,4 '-dihydroxy-3, the dihydroxy aryl ethers such as 3 '-3,5-dimethylphenyl ether, 4,4 '-dihydroxydiphenyl thioether, 4,4 '-dihydroxy-3, the dihydroxy diaryl thioether class such as 3 '-dimethyl diphenyl sulfide, 4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxy-3, the dihydroxy diaryl sulfoxide type such as 3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, 4, 4 '-dihydroxy-3, the dihydroxybiphenyls such as dihydroxy diaryl sulfone class, 4,4 '-dihydroxybiphenyl such as 3 '-dimethyl diphenyl sulfone Class, 9, double (4-hydroxy phenyl) fluorenes of 9-, 9, the dihydroxy diaryl fluorenes class such as double (4-hydroxy-3-methyl phenyl) fluorenes of 9-, 1,3-is double (4-hydroxy phenyl) diamantane (obsolete), 2, double (4-hydroxy phenyl) diamantane (obsolete) of 2-, 1, double (the 4-hydroxy phenyl)-5 of 3-, 7-dimethyl Buddha's warrior attendant The dihydroxy diaryl adamantanes such as alkane, 4,4 '-[1,3-phenylene double (1-methyl ethidine)] bis-phenols, 10, double (the 4-hydroxyl of 10- Base phenyl)-9-anthrone, 1, double (the 4-hydroxy benzenes sulfenyl)-2 of 5-, 3-dioxa pentane etc..
These dihydric phenols can be used alone, it is also possible to is used in mixed way two or more.
Additionally, as the dihydric phenol being not included in the dihydric phenol that represents with above-mentioned formula (1), can be containing with following The dihydric phenol of the Component units that formula (2) represents and the dihydric phenol represented with above-mentioned formula (1) are also used.Had so by formation The copolymer of Component units, it is possible to improve anti-flammability and the impact resistance of the polycarbonate resin (A-1) of gained.Comprise with The dihydric phenol of the Component units that following formula (2) represents can represent in order to the polysiloxane that following formula (2-1) represents.
[changing 7]
In above-mentioned formula (2) or formula (2-1), R7、R8、R9And R10Represent hydrogen atom, halogen atom, carbon independently of one another The alkyl of atomic number 1～6, the alkoxyl of carbon number 1～6 or the aryl of carbon number 6～12.Z represents by having pi-allyl Oxybenzene compound phenol residues derivative, that there is trimethylene.N represents 70～1000.
The polysiloxane represented with above-mentioned formula (2-1) is by the end use-case of the end polysiloxane as hydrogen As 2-chavicol and acetaminol etc. have material obtained by the oxybenzene compound modification of pi-allyl at end.By at end There is polysiloxane obtained by the oxybenzene compound modification of pi-allyl can utilize in No. 2662310 publications of Japanese Patent No. The method recorded synthesizes.
As above-mentioned polysiloxane, it is suitably for polydimethylsiloxane.
In addition it is also possible to above-mentioned dihydric phenol is used branching agent, make that the main chain of this polycarbonate resin has side chain Structure.The addition of this branching agent is preferably 0.01～3 mole of % relative to above-mentioned dihydric phenol, and more preferably 0.1～1.0 rub You are %.
As branching agent, such as, can enumerate 1,1,1-tri-(4-hydroxy phenyl) ethane, 4,4 '-[1-[4-[1-(4-hydroxyl Phenyl)-1-Methylethyl] phenyl] ethidine] bis-phenol, α, α ', α "-three (4-hydroxy phenyls)-1,3,5-triisopropylbenzenes, 1- [Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α ', α '-bis-(4 "-hydroxy phenyl) ethyl] benzene, phloroglucinol, inclined benzene three Acid, isatin di-cresol etc. have the compound of the functional group of more than 3.
Polycarbonate resin (A-1) can manufacture by making carbonate source react with dihydric phenol.So-called carbonic ester is former Material, is available with the polymer reaction of formation such as condensation reaction or exchange reaction and generates carbonic acid ester bond in polycarbonate backbone Compound.As such compound, in the case of utilizing interface polycondensation to manufacture Merlon, headed by phosgene, can To enumerate three phosgenes, bromine phosgene, double (2,4,6-trichlorophenyl) carbonic ester, double (2,4-Dichlorobenzene base) carbonic ester, double (2- Cyano-phenyl) phosgene derivatives such as carbonic ester, trichloromethyl chloroformate.
It addition, in the manufacture of Merlon based on ester exchange reaction method (fusion method), use as carbonate source Carbonic diester, as carbonic diester, can enumerate diaryl carbonate compounds, dialkyl carbonate compounds, alkyl carbonate Aryl ester compound etc..
Herein, as the concrete example of diaryl carbonate compounds, can enumerate diphenyl carbonate, carboxylol ester, Double (chlorphenyl) carbonic ester, a cresyl carbonate, dinaphthyl carbonate, double (diphenyl) carbonic ester, bisphenol-A diphenyl carbonic acid Ester etc..As the concrete example of dialkyl carbonate compounds, can enumerate diethyl carbonate, dimethyl carbonate, dibutyl carbonate, Dicyclohexyl carbonate, bisphenol-A dimethyl carbonate etc..As the concrete example of carbonate alkyl aryl ester compound, carbon can be enumerated Acid methyl phenylester, carbonic acid ethyl phenyl ester, carbonic acid butyl phenyl ester, carbonic acid cyclohexyl phenyl ester, bisphenol-A methyl phenyl carbonate Ester etc..
Polycarbonate resin (A-1) can use customary way in the manufacture of common polycarbonate resin, such as make Manufacture with phosgene or the interface polycondensation of phosgene derivatives and ester-interchange method (fusion method) etc., and in the middle of them preferably Interface polycondensation.
As using phosgene or the interface polycondensation of phosgene derivatives, such as, can enumerate in advance by described dihydric phenol The polycarbonate oligomer of described dihydric phenol organic molten to the inertia of this oligomer is synthesized with phosgene or phosgene derivatives In agent solution add containing described dihydric phenol aqueous alkali and comprise described high-purity 3-pentadecyl phenol end-capping reagent and The method being allowed to reaction；Or to the aqueous alkali of described dihydric phenol and comprise the end-blocking of described high-purity 3-pentadecyl phenol The mixed liquor of agent and inert organic solvents adds phosgene or phosgene derivatives and is allowed to the method etc. of reaction, and they are worked as In be suitably for the former oligomer method.
Below, the method utilizing oligomer legal system to make polycarbonate resin (A-1) is illustrated, first, make described two Unit's phenol is dissolved in the aqueous solution of alkali metal hydroxide, prepares the aqueous alkali (aqueous solutions of sodium hydroxide etc.) of dihydric phenol. Then, in the mixed liquor of this aqueous alkali and inert organic solvents organic solvents such as () dichloromethane, phosgene or phosphinylidyne are imported Chlorine derivative, synthesizes the polycarbonate oligomer of described dihydric phenol.Now, the alkali concn of this aqueous alkali preferably 1～15 matter The scope of amount %, additionally organic facies is usually 5: 1～1: 7 with the volumetric ratio of aqueous phase, is preferably in the scope of 2: 1～1: 4.For Reaction temperature, carries out water-bath cooling, and generally 0～50 DEG C, preferably selection in the scope of 5～40 DEG C, the response time is usually 15 minutes～4 hours, preferably 30 minutes～about 2 hours.The degree of polymerization of so obtained polycarbonate oligomer is usually Less than 20, preferably 2～about 10.
Herein, in the so obtained organic facies containing polycarbonate oligomer, the aqueous alkali adding described dihydric phenol is molten Liquid, the end-capping reagent comprising described high-purity 3-pentadecyl phenol, it is stirred according to the inert organic solvents of required addition Deng, be thus brought into contact with, generally at 0～50 DEG C, preferably at a temperature of the scope of 5～40 DEG C, be generally allowed to interfacial polycondensation 10 Minute～about 6 hours.Now, the alkali concn of this aqueous alkali is preferably 1～15 mass %, additionally organic facies and the appearance of aqueous phase Long-pending than usually 7: 1～1: 2, it is preferably in the scope of 4: 1～1: 1.Additionally, for described dihydric phenol and polycarbonate oligomer Ratio so that the mol ratio of (dihydric phenol)/(the chloro-carbonic acid ester group of polycarbonate oligomer) is usually 0.4～0.55, preferably Be 0.45～0.5 mode select.It addition, for the ratio of alkali metal hydroxide Yu polycarbonate oligomer, so that (alkali gold Belonging to hydroxide)/the mol ratio of (the chloro-carbonic acid ester group of polycarbonate oligomer) is usually 1.0～2.0, is preferably 1.2～1.7 Mode select.It addition, for the usage amount of end-capping reagent, so that (end-capping reagent)/(the chloro-carbonic acid ester group of polycarbonate oligomer) Mol ratio be usually 0.02～0.20, be preferably the mode of 0.04～0.17 and select.Additionally, in the reaction, can basis Required use catalyst.For the usage amount of catalyst, so that (catalyst)/(the chloro-carbonic acid ester group of polycarbonate oligomer) Mol ratio is usually 1.0 × 10-3～10.0 × 10-3, be preferably 1.0 × 10-3～5.0 × 10-3Mode select.
As alkali-metal hydroxide used in the manufacture of polycarbonate resin (A-1), such as, can enumerate hydrogen Sodium oxide, potassium hydroxide, Lithium hydrate and Cesium hydrate. etc..In the middle of them, preferably sodium hydroxide and potassium hydroxide.It addition, As inert organic solvents, there is various solvents.Such as can enumerate dichloromethane (dichloromethane)；Chloroform；1,1- Dichloroethanes；1,2-dichloroethanes；1，1，1-trichloroethane；Vinyl trichloride；Unsym.-tetraehloroethane；1,1,2,2- Sym-tetrachloroethane；Pentalin., chlorinated hydrocabon or the 1-Phenylethanone. etc. such as chlorobenzene.These organic solvents both can individually use, it is possible to Two or more to be applied in combination.In the middle of them, preferably chloroform, dichloromethane, particularly preferred dichloromethane.
As described catalyst, it is possible to use various catalyst.Specifically, quaternary ammonium salt, quaternary salt or uncle can be enumerated Amine etc..As quaternary ammonium salt, such as, can enumerate trimethyl benzyl ammonia chloride, triethyl benzyl ammonia chloride, tributyl Benzylmagnesium chloride Ammonium, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, tetrabutyl ammonium bromide etc..It addition, as quaternary salt, such as can enumerate Tetrabutyl chlorination, tetrabutyl phosphonium bromide etc., additionally, as tertiary amine, such as can enumerate triethylamine, tri-n-butylamine, N, N-diformazan Basic ring hexylamine, pyridine, dimethylaniline etc..
In the catalyst, preferred tertiary amine, particularly preferred triethylamine.By from so obtained containing polycarbonate resin In the organic solvent solution of fat, carry out reclaimer operation according to usual way, polycarbonate resin (A-1) can be obtained.
In the manufacture of polycarbonate resin based on ester exchange reaction method (fusion method), use dihydric phenol, carbonic diester, And the end-capping reagent that comprises described high-purity 3-pentadecyl phenol and the branching agent etc. used as required, in molten condition Under be allowed to carry out ester exchange reaction, phenol pair generated removes outside system reduced pressure etc. is lower, it is hereby achieved that poly- Carbonate resin (A-1).In ester exchange reaction method, it is possible to use for promoting the ester exchange catalyst of reaction.Hand over as ester Salt or ammonium salt, the salt such as catalyst changeout, preferably sodium, calcium and caesium.
Polycarbonate resin (A-1) is to use, using high-purity 3-pentadecyl phenol, the material obtained as end-capping reagent, tool There is the terminal groups coming from 3-pentadecyl phenol.
Polycarbonate resin (A-1) at the 380nm light transmittance of formed body thick for 3mm obtained by 350 DEG C of shapings is More than 85.0%.If described 380nm light transmittance is more than 85.0%, then go for the liquid crystal of the requirement transparency with leading In the liquid crystal light conducting member of light component and thin-walled and big picture.From the viewpoint of above, described 380nm light is saturating The rate of penetrating is preferably more than 86%, and more preferably more than 87%.
The viscosity-average molecular weight of polycarbonate resin (A-1) is not particularly limited, but from guaranteeing to become the formed products of thin-walled From the viewpoint of mobility during shape and intensity, it is preferably set to 8,000～19,000, more preferably it is set to 9,000～17,000, enters One step is preferably set to 10,000～15,000.
The yellow colour index (YI) of polycarbonate resin (A-1) is preferably less than 1.5.If the YI of polycarbonate resin (A-1) It is less than 1.5, then goes for excellent hue, require in transparent liquid crystal component.From the viewpoint of above, poly-carbon The YI of acid ester resin (A-1) is more preferably less than 1.3, and more preferably less than 1.1.
(polycarbonate resin (A-2))
The poly carbonate resin composition of the present invention can also contain the polycarbonate resin beyond polycarbonate resin (A-1) Fat (A-2).
As described polycarbonate resin (A-2), various known polycarbonate resin can be used without particular limitation Fat, but optimization aromatic polycarbonate resin.
For the viscosity-average molecular weight of the polycarbonate-based resin of this (A-2) composition, in terms of physical property from the viewpoint of, preferably It is 10,000～40,000, more preferably 11,000～17,000.
Above-mentioned aromatic polycarbonate resin preferably main chain comprises the tree of the repetitive represented with following formula (V) Fat.
[changing 8]
In formula, R9And R10Represent halogen atom, the alkyl of carbon number 1～6 or carbon number 1～6 independently of one another Alkoxyl.X ' represents singly-bound, the alkylidene of carbon number 1～8, the alkylidene radical of carbon number 2～8, the ring of carbon number 5～15 Alkylidene, the ring alkylidene radical of carbon number 5～15 ,-S-,-SO-,-SO2-,-O-or-CO-.D and e represent independently of one another 0～ The integer of 4.
As R9And R10Concrete example, can enumerate and described R5And R6Identical example.As R9And R10, preferably carbon The alkyl of atomic number 1～6 or the alkoxyl of carbon number 1～6.As the concrete example of X ', the example identical with described X can be enumerated Son, preferred example is the most identical.D and e is each independent, preferably 0～2, more preferably 0 or 1.
Specifically, above-mentioned aromatic polycarbonate resin can use utilization such as inferior conventional aromatic copolycarbonate The resin that obtains of autofrettage, i.e. in the presence of inert organic solvent, aqueous alkali for reaction, with aromatic series After dihydric phenol based compound and phosgene reaction, add the polymerization catalyst such as tertiary amine or quaternary ammonium salt and be allowed to the interfacial polymerization of polymerization Method；Aromatic dicarboxylic phenol system compound is dissolved in pyridine or pyridine with in the mixed solution of atent solvent, import phosgene and The pyridine method directly manufactured.
When above-mentioned reaction, as required, it is possible to use molecular weight regulator (end-capping reagent), branching agent etc..
And, as above-mentioned aromatic dicarboxylic phenol system compound, the compound represented with following formula (3) can be enumerated.
[changing 9]
In formula, R9、R10, X ', d and e as defined above shown in, preferred example is the most identical.
As the concrete example of this aromatic dicarboxylic phenol system compound, the binary can enumerated with represent with above-mentioned formula (1) The example that phenol is identical, preferred example is the most identical.It addition, as being not included in the dihydric phenol that represents with above-mentioned formula (3) Dihydric phenol, can using as the dihydric phenol comprising the Component units represented with above-mentioned formula (2), with above-mentioned formula (2-1) table The polysiloxane shown and the dihydric phenol represented with formula (3) are also used.
Above-mentioned dihydric phenol both can be used alone or two or more kinds may be used.
As branching agent, can similarly enumerate the material of foregoing illustrative.
As end-capping reagent, it is possible to use the end-capping reagent for manufacturing polycarbonate resin used in the past, such as, can lift Go out phenol, paracresol, p-t-butyl phenol, p-cumylphenol, tribromphenol, nonyl phenol, to tert-octyl phenol etc..They are worked as In, preferably p-t-butyl phenol and p-cumylphenol.
(polycarbonate resin (A))
Polycarbonate resin (A) comprises described polycarbonate resin (A-1) 10～100 mass % and described poly-carbonic acid Ester resin (A-2) 90～0 mass %.
The content of described polycarbonate resin (A-1) is 10～100 mass % in (A) composition, preferably 30～100 matter Amount %, more preferably 50～100 mass %, more preferably 70～100 mass %.
Containing the polycarbonate-based resin beyond above-mentioned (A-1) composition in the poly carbonate resin composition of the present invention (A-2), in the case of, its content is below 90 mass % in (A) composition, below preferably 70 mass %, and more preferably 50 matter Amount below %, more preferably below 30 mass %.
The content of the 3-pentadecyl phenoxy group in described (A) composition is preferably 0.1～10 mass %, and more preferably 0.5 ～8 mass %, more preferably 0.8～7 mass %.If the content of the 3-pentadecyl phenoxy group (A) in composition is described Scope, then mobility improve, tone improve, and durability improve.
The viscosity-average molecular weight of polycarbonate resin (A) is not particularly limited, but from guaranteeing the formed products shaping of thin-walled Time mobility and intensity from the viewpoint of, be preferably set to 8,000～19,000, be more preferably set to 9,000～17,000, enter one Step is preferably set to 10,000～15,000.
(phosphorous antioxidant (B))
The poly carbonate resin composition of the present invention contains phosphorous antioxidant (B).By containing phosphorous antioxidant (B), the rising of the YI value of poly carbonate resin composition can be suppressed, even if at high temperature making resin during this external forming Compositions is detained, it is also possible to keep good tone, can give excellent processing stability to poly carbonate resin composition.
As phosphorous antioxidant, it is possible to use phosphorous acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc..Wherein, Preferably there is the antioxidant of tetramethylolmethane structure, more preferably there is the Asia of the tetramethylolmethane structure represented with following formula (4) Phosphate ester.
[changing 10]
In formula (4), R7And R8Each represent hydrogen, alkyl, cycloalkyl or aryl.And, cycloalkyl and aryl can also be by Alkyl replaces.
At R7And R8In the case of aryl, R7And R8It is preferably the aryl represented with following formula (a), (b) or (c).
[changing 11]
In formula (a), R9Represent the alkyl of carbon number 1～10.
[changing 12]
In formula (b), R10Represent the alkyl of carbon number 1～10.
[changing 13]
As having the phosphite ester of the tetramethylolmethane structure represented with described formula (4), specifically, except can be with example Double (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites of following formula (5), following formula (6) are shown Beyond double (2,4-dicumylphenyl) pentaerythritol diphosphites, it is also possible to exemplify following formula (7)～the chemical combination of (10) Thing.
[changing 14]
In the middle of them, as phosphorous antioxidant (B), double (2,6-di-t-butyl-4-methyl of the most described formula (5) Phenyl) pentaerythritol diphosphites [such as Adekastab PEP-36:(strain) ADEKA (strain) system], described formula (6) double (2,4-dicumylphenyl) pentaerythritol diphosphites [such as Doverphos S-9228PC:Dover Chemical Corporation system], double (2,4-dicumylphenyl) pentaerythritol diphosphites of the most described formula (6).
The content of the phosphorous antioxidant (B) in the poly carbonate resin composition of the present invention is relative to (A) composition 100 matter Amount part is 0.005～0.5 mass parts, preferably 0.01～0.2 mass parts, more preferably 0.02～0.1 mass parts.If being less than 0.005 mass parts, then cannot suppress the rising of YI value, and if at high temperature make resin combination be detained when forming, Then cannot keep good tone.On the other hand, if more than 0.5 mass parts, then the Merlon caused by analyte can be promoted Hydrolysis, it is impossible to embody desired performance.
(aliphatic cyclic epoxide (C))
The poly carbonate resin composition of the present invention can contain aliphatic cyclic epoxide (C) as required.
As aliphatic cyclic epoxy resin (C), the compound that a part for structure has been at least partially epoxidized can be enumerated.Pass through Containing aliphatic cyclic epoxide (C) in the poly carbonate resin composition of the present invention, the resistance to of formed body can be improved Property for a long time.
In such aliphatic cyclic epoxide (C), it is preferably selected from 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters (trade name " CELLOXIDE 2021P " etc. of Daicel chemical industrial company), 2,2-is double The 1 of (hydroxymethyl)-n-butyl alcohol, 2-epoxy-4-(2-epoxy ethyl) hexamethylene addition product be (Daicel chemical industrial company Trade name " EHPE3150 " etc.), in this mixture of 2 kinds (trade name EHPE3150CE of Daicel chemical industrial company) At least one.
The content of the aliphatic cyclic epoxide (C) in the poly carbonate resin composition of the present invention is relative to (A) Composition 100 mass parts is preferably 0.001～0.5 mass parts.If described content is more than 0.001 mass parts, then durability is abundant Ground improves, if below 0.5 mass parts, then can suppress nebulousurine, and tone becomes good.From the viewpoint of above, aliphatic The content of cyclic epoxy compound (C) is more preferably 0.005～0.3 mass parts, more preferably 0.01～0.1 mass parts.
(there is the polysiloxane (D) of functional group)
The poly carbonate resin composition of the present invention as required can be containing the polysiloxane with functional group (D)。
The above-mentioned polysiloxane with functional group preferably has selected from alkoxyl, aryloxy group, polyoxyalkylenes, carboxylic At least one functional group in base, silanol base, amino, sulfydryl, epoxy radicals and vinyl.
For the viscosity of the above-mentioned polysiloxane (D) with functional group, from the viewpoint of lubricity effect, 25 DEG C time, preferably 10mm2More than/the second, from the viewpoint of the dispersibility polycarbonate resin (A), more preferably 200mm2Below/the second.Considering from above-mentioned viewpoint, the range of viscosities of the above-mentioned polysiloxane (D) with functional group is further It is preferably 20～150mm2/ the second, particularly preferably 40～120mm2/ the second.
For the refractive index of the above-mentioned polysiloxane (D) with functional group, in order to not make the Merlon of the present invention The transparency reduction of resin combination, the smaller the better with the difference of the refractive index of polycarbonate resin (A).Examine from above viewpoint Considering, the refractive index of the above-mentioned polysiloxane (D) with functional group is excellent with the difference of the refractive index of described polycarbonate resin (A) Elect less than 0.13 as, more preferably less than 0.08, more preferably less than 0.05.Further, since the folding of polycarbonate resin The rate of penetrating is about 1.58, and the refractive index of the most above-mentioned polysiloxane (D) with functional group is preferably more than 1.45, more preferably It is more than 1.50, more preferably more than 1.51.
The content of the polysiloxane (D) with functional group in the poly carbonate resin composition of the present invention relative to Polycarbonate resin (A) 100 mass parts is preferably 0.02～0.15 mass parts, more preferably 0.03～0.12 mass parts.If will (D) content of composition coordinates in above-mentioned scope, then can improve release property together with other composition.This is external significantly Under the conditions of hot forming more than 300 DEG C, particularly under the conditions of progressive forming, it is also possible to silver color (silver) is greatly reduced Generation and mould attachment.
[poly carbonate resin composition/formed body]
In the poly carbonate resin composition of the present invention, except above-mentioned (A) composition and (B) composition and according to Need beyond above-mentioned (C) composition and (D) composition of interpolation, it is also possible in not damaging the scope of effect of the present invention, root According to needs, coordinate and added the known various additives in poly carbonate resin composition in the past to.
As these additives, the antioxidant beyond phosphorous antioxidant, UV absorbent, fire-retardant can be enumerated Agent, releasing agent, inorganic filling material (glass fibre, Talcum, titanium oxide, Muscovitum etc.), coloring agent, light diffusing agent etc..
The formed body being made up of the polycarbonate-based resin composition of the present invention can by by with above-mentioned each composition And material forming obtains obtained by mixing.
As compounding process, be not particularly limited, such as can enumerate use ribbon stirrer, Henschel mixer, Banbury blender, drum agitator, single shaft screw extruder, biaxial screw extruder, compound motion kneader, multiaxis screw rod The method of extruder etc..It addition, mixing time heating-up temperature generally at 240～330 DEG C, preferably in the scope of 250～320 DEG C Select.
As manufacturing process, it is possible to use existing known various manufacturing process, such as, can enumerate injection molding method, note Penetrate compression forming method, extrusion molding method, blow-moulding process, punching formation, vacuum forming process and foaming and molding method etc..
And, beyond polycarbonate resin containing composition can also in advance with polycarbonate resin or other thermoplasticity Resin melting is mixing, i.e. adds as masterbatch.
Additionally, it is preferred that be allowed to granulate and injection moulding, it is possible to use general injection molding method or ejection compress moulding The special forming processes such as method and gas assist formation method, can manufacture various formed products.
Formed body obtained by being shaped by the poly carbonate resin composition of the present invention can be as light conducting member, light diffusing sheet Resin use suitably.As light conducting member, can enumerate portable phone, LCD TV, PC, electronic dictionary, The liquid crystal machine light conducting members such as the light guide plate of liquid crystal indicator used in e-book, smart mobile phone or flat board PC etc., attached Be located in head lamp day portable lighter or LED illumination etc. in light conducting member used.The stream of the poly carbonate resin composition of the present invention Dynamic property is excellent, therefore in the case of manufacturing the formed body that thickness is extremely thin, shapes preferably by injection moulding, can conduct The light guide plate of liquid crystal indicator or the resin of light diffusing sheet use suitably.
Embodiment
Hereinafter will enumerate embodiment, the present invention will be described in more detail.And, the present invention is not limited by these examples Fixed.And, the evaluation of measuring in embodiment and comparative example utilizes method shown below to carry out.
<purity of 3-pentadecyl phenol and the assay method of impurity level>
The Agilent Technologies system of utilization " AGILENT1200 ", as chromatographic column use " L-column ODS " (4.6mmID × 150mm, particle diameter 3 μm), use acetonitrile/formic acid buffer=95/5 (vol/vol) to measure 3-pentadecyl benzene mutually as flowing Phenol and resorcinol derivatives.
Utilize Jeol Ltd.'s system " JMS-Q1000GC ", use long 30m × internal diameter 250 μ m thickness 0.25 μm Chromatographic column " VF-1 " measure phenol derivatives.
<mensuration of viscosity number (VN)>
The viscosity number (VN) of polycarbonate resin (A) is measured according to ISO1628-4 (1999).
<mensuration of viscosity-average molecular weight (Mv)>
The viscosity-average molecular weight (Mv) of polycarbonate resin (A) is to use Ubbelohde viscometer, and the dichloromethane measuring 20 DEG C is molten The viscosity of liquid, is obtained intrinsic viscosity [η] by this viscosity, utilizes following formula to calculate.
[η]=1.23 × 10-5Mv0.83
<mensuration of light transmittance>
In polycarbonate resin (A-1) 100 mass parts of gained, add Adekastab PEP36 (Co., Ltd. ADEKA system, double (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) 500 mass ppm interpolations, with logical The single shaft extruder of the 40mm φ in air port carries out melting mixing extrusion with resin temperature 280 DEG C, screw speed 100rpm, obtains Grain, uses the granule of gained, carries out injection moulding barrel zone temperature 350 DEG C, the 380nm light to formed body thick for the 3mm of gained Line absorbance utilizes the U-4100 spectrophotometer of high-tech company of Hitachi to be measured.Qualified benchmark is the absorbance of 380nm It is more than 85%.
<mensuration of terminal groups composition amounts>
Use Jeol Ltd.'s system " JNM-LA500 ", measure1H-NMR, calculates the terminal groups of polycarbonate resin Composition amounts.It addition, calculated the content (quality %) of 3-pentadecyl phenoxy group in polycarbonate resin by terminal groups composition amounts.
Preparation example 1
To internal diameter 30mm, capacity 500mL post in fill McMahon packing (Mc.MAHON Packing, specification: 6mm) make rectifying column, be installed in the 2L flask with interior temperature determinator, (return filling tower top mounting and adjusting reflux ratio Flow/quantity of distillate) utensil and measure tower top temperature device, be additionally mounted with degree of decompression adjusting apparatus.Supply to flask 3-pentadecyl phenol (capital chemical conversion Industrial Co., Ltd system, purity 92.10 mass %, resorcinol derivatives: 2.15 matter Amount %, phenol derivatives 5.11 mass %) 1006.96g, after carrying out nitrogen displacement, begin to warm up decompression.It is set as degree of decompression 2mmHg, capacity of returns/quantity of distillate=1, separate and collect tower top temperature 205～the fraction of 210 DEG C.Now, flask temperature be 230～ 245℃.The amount of separating and collecting is 825.71g (82 mass % fed intake), and the purity of 3-pentadecyl phenol is 93.61 mass %.
Then, after the thick 3-pentadecyl phenol of gained being melted in the water-bath of 60 DEG C and weighing 70g in standard jar, Add the normal hexane of 420g and be allowed to dissolve.12 hours are stood, after the solid filtration under diminished pressure that will separate out, at reduced pressure at room temperature in room temperature It is dried 8 hours, thus obtains the 3-pentadecyl phenol 48g of correspondence.3-pentadecyl in the 3-pentadecyl phenol of gained Phenol containing ratio is 97.75 mass %.Make the 3-pentadecyl phenol 70g of purity 97.75 mass % of gained at the water of 60 DEG C Bath melts, after weighing 70g in standard jar, adds the normal hexane of 420g and be allowed to dissolve.12 hours are stood in room temperature, will analysis After the solid filtration under diminished pressure gone out, reduced pressure at room temperature 8 hours, thus obtain the 3-pentadecyl benzene of purity 99.33 mass % Phenol 54g.Resorcinol derivatives containing ratio in the 3-pentadecyl phenol of gained is 0.23 mass %, and phenol derivatives is 0.02 mass %.
Manufacture example 1
(manufacture of polycarbonate resin (A-1))
(1) manufacture of polycarbonate oligomer
In concentration 5.6 mass % sodium hydrate aqueous solution, adding relative to the bisphenol-A (BPA) dissolved thereafter is 0.2 matter The sodium dithionite of amount %, dissolves BPA in the way of making BPA concentration be 13.5 mass % wherein, prepares the hydrogen-oxygen of BPA Change sodium water solution.Internal diameter 6mm, pipe range 30m tube-type reactor in, be passed through above-mentioned BPA's continuously with the flow of 40L/hr Sodium hydrate aqueous solution, is passed through dichloromethane continuously with the flow of 15L/hr in addition, and the flow with 4.0kg/hr is continuous Be passed through phosgene.Tube-type reactor has jacket portion, is passed through cooling water and the temperature of reactant liquor is remained in chuck Less than 40 DEG C.
The reactant liquor sent from tube-type reactor is imported continuously possess swept-back blade internal volume 40L with The tank reactor of baffle plate, the flow with 2.8L/hr supplies the sodium hydrate aqueous solution of BPA the most again, with 0.07L/hr's Flow supplies 25 mass % sodium hydrate aqueous solutions, supplies feedwater with the flow of 17L/hr, supplies 1 matter with the flow of 0.64L/hr Amount % triethylamine aqueous solution, the dichloromethane supplying 20 mass % p-t-butyl phenols (PTBP) with the flow of 149.2kg/hr is molten Liquid, reacts at 29～32 DEG C.Extraction liquid continuously from tank reactor, stands, thus by aqueous phase separation Remove, acquire dichloromethane phase.The oligomer concentrations of so obtained polycarbonate oligomer solution is 321g/L, chloro-carbonic acid Ester group concentration is 0.75mol/L.
(2) manufacture of polycarbonate resin
Above-mentioned oligomer solution is added in the tank reactor of internal volume 50L possessing baffle plate, paddle type stirring vane 19L, dichloromethane 11L, dissolve the 3-pentadecyl phenol (m-PDP) of purity 99.33 mass % obtained in preparation example 1 After 361g and PTBP64g, add triethylamine 5.6mL, be under agitation added to 6.4 mass % sodium hydrate aqueous solutions 1814g, carries out reaction in 10 minutes.The sodium hydrate aqueous solution adding BPA (dissolves NaOH701g and Lian Erya in water 10.8L Sodium sulfate 2.9g, dissolves solution obtained by BPA1462g in the aqueous solution of gained), carry out 50 minutes polyreactions.
Adding for the dichloromethane 4L of dilution and after stirring 10 minutes, be separated into the organic facies containing Merlon and Containing superfluous bisphenol-A and the aqueous phase of NaOH, isolate organic facies.The dichloromethane solution of the polycarbonate resin of gained is depended on Secondary with relative to the 0.03mol/L sodium hydrate aqueous solution that this solution is 15 capacity % and the cleaning of 0.2mol/L hydrochloric acid, then use The electrical conductivity that pure water cleans in the aqueous phase to cleaning repeatedly is below 0.5mS/m.The polycarbonate resin obtained is cleaned by utilizing The dichloromethane solution of fat concentrates, pulverizes, by the thin slice of gained under reduced pressure, 100 DEG C be dried, obtain polycarbonate resin.Profit With1The ratio of components of the m-PDP that H-NMR obtains be the ratio of components of 4.07mol%, PTBP be 4.24mol%.Polycarbonate resin 380nm light transmittance is 87.95%.
Manufacture example 2
(manufacture of polycarbonate resin (A-1))
Except, in manufacturing the manufacture of (2) polycarbonate resin of example 1, not using beyond PTBP64g, utilize and manufacture The method that example 1 is identical, obtains polycarbonate resin.Utilize1The ratio of components of the m-PDP that H-NMR obtains is 4.08mol%, PTBP Ratio of components be 2.89mol%.The 380nm light transmittance of polycarbonate resin is 87.90%.
Manufacture example 3
(manufacture of polycarbonate resin (A-1))
Except, in manufacturing the manufacture of (2) polycarbonate resin of example 1, the usage amount of m-PDP being changed to from 361g 72g, and the usage amount of PTBP is changed to beyond 171g from 64g, utilize the method identical with manufacturing example 1, obtain poly-carbonic acid Ester resin.Utilize1The ratio of components of the m-PDP that H-NMR obtains be the ratio of components of 0.80mol%, PTBP be 6.74mol%.Poly-carbon The 380nm light transmittance of acid ester resin is 86.92%.
Manufacture example 4
(manufacture of polycarbonate resin (A-1))
Except, in manufacturing the manufacture of (2) polycarbonate resin of example 1, the usage amount of m-PDP being changed to from 361g 217g, and the usage amount of PTBP is changed to beyond 100g from 64g, utilize the method identical with manufacturing example 1, obtain poly-carbonic acid Ester resin.Utilize1The ratio of components of the m-PDP that H-NMR obtains be the ratio of components of 2.41mol%, PTBP be 5.14mol%.Poly-carbon The 380nm light transmittance of acid ester resin is 87.60%.
Manufacture example 5
(manufacture of polycarbonate resin (A-1))
Except manufacture example 1 (2) polycarbonate resin manufacture in, by the usage amount of PTBP from 64g be changed to 29g with Outward, utilize the method identical with manufacturing example 1, obtain polycarbonate resin.Utilize1The ratio of components of the m-PDP that H-NMR obtains is The ratio of components of 4.06mol%, PTBP is 3.27mol%.The 380nm light transmittance of polycarbonate resin is 87.86%.
Embodiment 1～14, comparative example 1～4
(manufacture of poly carbonate resin composition)
In polycarbonate resin (A) 100 mass parts described in table 1, coordinate the phosphorous antioxidant described in table 1 (B) 0.05 mass parts, then coordinate the aliphatic cyclic epoxide (C) described in table 1 with the ratio described in table 1 and have The polysiloxane (D) of functional group, uses the single shaft extruder of the 40mm φ with vent with resin temperature 280 DEG C, spiral shell Bar rotating speed 1000ppm carries out melting mixing extrusion, and pelletize, obtains the granule of poly carbonate resin composition.
The method of evaluating performance of moulding material used and formed body is expressed as follows.The results are shown in Table 1.
(A-1) composition
" PDP1100-5 " manufactures the polycarbonate resin obtained in example 1
" PDP1300-5 " manufactures the polycarbonate resin obtained in example 2
" PDP1200-1 " manufactures the polycarbonate resin obtained in example 3
" PDP1200-3 " manufactures the polycarbonate resin obtained in example 4
" PDP1200-5 " manufactures the polycarbonate resin obtained in example 5
(A-2) composition
" Tarflon FN1200 " (go out light emerging product (strain) system, bisphenol A polycarbonate resin, viscosity-average molecular weight (Mv)= 11500)
" Tarflon FN1500 " (go out light emerging product (strain) system, bisphenol A polycarbonate resin, viscosity-average molecular weight (Mv)= 14500)
(B) composition
" Adekastab PEP-36 " ((strain) ADEKA system, double (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane two Phosphite ester)
" Doverphos S-9228PC " (Dover Chemical company system, double (2,4-dicumylphenyl) tetramethylolmethane Diphosphites)
(C) composition
" Celloxide 2021P " (Daicel chemical industry (strain) system, 3,4-epoxy hexane ylmethyl-3 ', 4 '-ring Oxygen cyclohexenecarboxylic acid ester)
(D) composition
" KR511 " (SHIN-ETSU HANTOTAI Silicone (strain) makes, has the organopolysiloxane of methoxyl group, phenyl and vinyl, refraction Rate=1.518)
[performance evaluation]
(1)MVR
To the granule obtained in said method, use peace Tian Jingji Co., Ltd. system, machine name MFR meter E machine, with 300 DEG C, load 1.2kg determine melt fluidity MVR (cm3/ 10 minutes).
(2) YI value
Use above-mentioned in the granule that obtains, under the barrel temperatures set of 320 DEG C, with mold temperature 80 DEG C, circulation time Within 50 seconds, shape the tabular formed body of 50mm × 90mm × thickness 5mm.Formed body to gained, uses spectrophotometer, at C light YI value is determined under conditions of source, 2 degree of visuals field.
(3) YI value (350 DEG C, 3 minutes) and YI value (350 DEG C, 10 minutes)
To the granule obtained in said method, utilize injection moulding to carry out as shown below being detained heat stabilization test, survey Make the YI value of the formed products of 3 minutes holdup times and 10 minutes.
<injection moulding>
Injection machine: toshiba machine (strain) EC40N processed (trade name)
Formed products shape: 80mm × 40mm × 3.2mm
Forming machine barrel zone temperature: 350 DEG C
Holdup time in machine barrel: 3 minutes or 10 minutes
Mold temperature: 80 DEG C
(4) bending strength
Under the barrel temperatures set of 350 DEG C, within 50 seconds, shape 50mm × 90mm with mold temperature 110 DEG C, circulation time The tabular formed body of × thick 0.5mm.Formed body to gained, is being set as placing on fixture wide for the 50mm of 30mm between fulcrum Above-mentioned sample, implements test with test speed 0.5mm/m, determines the bending strength of formed body.
[table 1]
According to the contrast of above-described embodiment 1～14 with comparative example 1～4, belong to using as end-capping reagent of the present invention The resin combination containing polycarbonate resin that high-purity 3-pentadecyl phenol manufactures with conventional containing polycarbonate resin The resin combination of fat is compared, and mobility is excellent, and YI value is low, and tone and the transparency are excellent, and the shape stability under high temperature is excellent.
Industrial applicability
It is excellent, high that the poly carbonate resin composition of the present invention can obtain mobility excellence, light transmittance and brightness The formed body that shape stability under Wen is excellent, photopermeability is excellent, even if formed body is under hot and humid environment for a long time, Variable color, deterioration also will not occur.Therefore, the poly carbonate resin composition of the present invention can serve as optical forming piece especially, especially It may be used for light guide plate, additionally can serve as the light guide plate of the liquid crystal indicator of the big picture of thin-walled.

Claims (15)

1. a poly carbonate resin composition, its relative to comprise polycarbonate resin (A-1) 10～100 mass % and Polycarbonate resin (A) 100 mass parts of polycarbonate resin (A-2) 90～0 mass % beyond described (A-1), containing phosphorus Being antioxidant (B) 0.005～0.5 mass parts, described polycarbonate resin (A-1) uses containing with following formula as raw material (I) amphyl 2.5 mass % represented below resorcinol derivatives 1 mass % represented and/or with following formula (II) Below, this resorcinol derivatives and this amphyl total content be below 2.5 mass % and also containing purity be The end-capping reagent of 3-pentadecyl phenol more than 97.5 mass %, described polycarbonate resin (A-1) becomes in the temperature with 350 DEG C Shape be 380nm light transmittance during formed body thick for 3mm be more than 85.0%；
R in formula1、R2For hydrogen atom or the aliphatic alkyl of carbon number 1～20；R3Saturated or undersaturated for hydrogen atom The aliphatic alkyl of carbon number 1～20；R1、R2、R3Both can be the same or different；But, in above-mentioned logical formula (II), Get rid of with R1=H, R3=C15H31The 3-pentadecyl phenol represented.
Poly carbonate resin composition the most according to claim 1, wherein,
Relative to described (A) composition 100 mass parts, possibly together with aliphatic cyclic epoxide (C) 0.001～0.5 mass parts.
Poly carbonate resin composition the most according to claim 1 and 2, wherein,
The purity of described 3-pentadecyl phenol is more than 99.0 mass %.
4. according to the poly carbonate resin composition according to any one of claims 1 to 3, wherein,
Described 3-pentadecyl phenol be by after distillation, carry out crystallize and obtain.
5. according to the poly carbonate resin composition according to any one of Claims 1 to 4, wherein,
The content of the 3-pentadecyl phenoxy group in described (A) composition is 0.1～10 mass %.
6. according to the poly carbonate resin composition according to any one of Claims 1 to 5, wherein,
Described (B) composition has tetramethylolmethane structure.
7. according to the poly carbonate resin composition according to any one of claim 1～6, wherein,
Described (B) composition is double (2, the 4-dicumylphenyl) pentaerythritol diphosphites represented with following formula,
8. according to the poly carbonate resin composition according to any one of claim 2～7, wherein,
Described (C) composition is selected from 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters, 2, the double (hydroxyl of 2- Methyl)-n-butyl alcohol 1, at least 1 in 2-epoxy-4-(2-epoxy ethyl) hexamethylene addition product and their mixture Kind.
9. according to the poly carbonate resin composition according to any one of claim 1～8,
It is relative to described (A) composition 100 mass parts, possibly together with the polysiloxane (D) 0.02～0.15 with functional group Mass parts.
Poly carbonate resin composition the most according to claim 9, wherein,
Described functional group is selected from alkoxyl, aryloxy group, polyoxy alkylidene, carboxyl, silanol base, amino, sulfydryl, epoxy radicals and second At least one in thiazolinyl.
11. according to the poly carbonate resin composition described in claim 9 or 10, wherein,
The refractive index of the described polysiloxane (D) with functional group and the difference of the refractive index of described polycarbonate resin (A) It is less than 0.13.
12. according to the poly carbonate resin composition according to any one of claim 1～11, wherein,
The viscosity-average molecular weight of described polycarbonate resin (A) is 8,000～19,000.
13. 1 kinds of formed bodies, it is for by the poly carbonate resin composition shaping according to any one of claim 1～12 Become.
14. formed bodies according to claim 13, wherein,
Formed body is light conducting member.
15. formed bodies according to claim 14, wherein,
Light conducting member is light guide plate.
CN201580016762.3A 2014-03-31 2015-03-27 Polycarbonate resin composition and molded article Pending CN106133058A (en)

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EP3546521B1 (en) * 2016-11-28 2024-04-03 Mitsubishi Engineering-Plastics Corporation Polycarbonate resin composition
JP6960799B2 (en) * 2016-11-28 2021-11-05 三菱エンジニアリングプラスチックス株式会社 Polycarbonate resin composition
US20240016940A1 (en) * 2020-11-24 2024-01-18 The Brigham And Women`S Hospital, Inc. Long-acting and long-circulating delivery vehicles

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363850A (en) * 1970-10-26 1974-08-21 Imp Chemocal Ind Ltd Purification ltd
JP2002332400A (en) * 2001-05-10 2002-11-22 Teijin Chem Ltd Polycarbonate molding material for optics having high precision transferability, and optical disk base board formed therefrom
CN1449429A (en) * 2000-08-18 2003-10-15 出光石油化学株式会社 Aromatic polycarbonate resin composition and moldings
US20030212241A1 (en) * 2002-05-09 2003-11-13 General Electric Company Method of enhancing pit replication in optical disks
JP2004331688A (en) * 2003-04-30 2004-11-25 Teijin Chem Ltd Optical member formed from polycarbonate copolymer
CN101610906A (en) * 2007-01-29 2009-12-23 拜尔材料科学股份公司 Multilayer composite with polycarbonate layer
WO2013088796A1 (en) * 2011-12-13 2013-06-20 出光興産株式会社 Aromatic polycarbonate resin composition and optical molded article
WO2013130752A1 (en) * 2012-02-28 2013-09-06 Sabic Innovative Plastics Ip B.V. Processes for preparing polycarbonates with enhanced optical properties

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3454080B2 (en) * 1997-05-23 2003-10-06 三菱化学株式会社 Aromatic polycarbonate resin composition and optical product member comprising the same
JP2014224245A (en) * 2013-04-19 2014-12-04 出光興産株式会社 Method of producing polycarbonate resin
JPWO2014171509A1 (en) * 2013-04-19 2017-02-23 出光興産株式会社 Polycarbonate resin for liquid crystal member, polycarbonate resin composition for liquid crystal member containing the same, and liquid crystal member

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363850A (en) * 1970-10-26 1974-08-21 Imp Chemocal Ind Ltd Purification ltd
CN1449429A (en) * 2000-08-18 2003-10-15 出光石油化学株式会社 Aromatic polycarbonate resin composition and moldings
JP2002332400A (en) * 2001-05-10 2002-11-22 Teijin Chem Ltd Polycarbonate molding material for optics having high precision transferability, and optical disk base board formed therefrom
US20030212241A1 (en) * 2002-05-09 2003-11-13 General Electric Company Method of enhancing pit replication in optical disks
JP2004331688A (en) * 2003-04-30 2004-11-25 Teijin Chem Ltd Optical member formed from polycarbonate copolymer
CN101610906A (en) * 2007-01-29 2009-12-23 拜尔材料科学股份公司 Multilayer composite with polycarbonate layer
WO2013088796A1 (en) * 2011-12-13 2013-06-20 出光興産株式会社 Aromatic polycarbonate resin composition and optical molded article
WO2013130752A1 (en) * 2012-02-28 2013-09-06 Sabic Innovative Plastics Ip B.V. Processes for preparing polycarbonates with enhanced optical properties

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
毛治博，等: "腰果酚催化加氢工艺及产品的纯化和表征", 《林产化学与工业》 *

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