CN102224182B - Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article - Google Patents

Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article Download PDF

Info

Publication number
CN102224182B
CN102224182B CN2009801466415A CN200980146641A CN102224182B CN 102224182 B CN102224182 B CN 102224182B CN 2009801466415 A CN2009801466415 A CN 2009801466415A CN 200980146641 A CN200980146641 A CN 200980146641A CN 102224182 B CN102224182 B CN 102224182B
Authority
CN
China
Prior art keywords
polycarbonate resin
weight part
resin
compound
poly carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009801466415A
Other languages
Chinese (zh)
Other versions
CN102224182A (en
Inventor
安藤正人
田中智彦
佐佐木一雄
横木正志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Priority to CN201310285560.1A priority Critical patent/CN103351463B/en
Publication of CN102224182A publication Critical patent/CN102224182A/en
Application granted granted Critical
Publication of CN102224182B publication Critical patent/CN102224182B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws

Abstract

Disclosed is a polycarbonate resin which contains a constituent unit derived from a specific dihydroxy compound, and has excellent heat resistance and transparency. Also disclosed is a composition containing the polycarbonate resin. The polycarbonate resin contains at least a constituent unit derived from a dihydroxy compound having a bond structure represented by structural formula (1). The polycarbonate resin is characterized in that the ratio of (A) the number of end groups represented by structural formula (2) relative to (B) the total number of end groups, namely (A)/(B), is not less than 20%. (In this connection, a hydrogen atom is not bonded to the oxygen atom in structural formula (1).)

Description

Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings
Technical field
The present invention relates to polycarbonate resin etc., more particularly, the present invention relates to have polycarbonate resin from the structural unit of specific dihydroxy compound etc.
Background technology
In recent years, about using the polycarbonate resin of the raw material that is obtained by Biological resources, there is document to put down in writing use plant origin monomer---Isosorbide, obtains the technology (referring to patent documentation 1) of polycarbonate by the transesterify with diphenyl carbonate.Patent documentation 2 has been put down in writing the polycarbonate resin that Isosorbide and dihydroxyphenyl propane copolymerization are obtained.Patent documentation 3 has been put down in writing by improving the outspoken nature of polycarbonate resin with Isosorbide and aliphatic diol copolymerization.
The look-ahead technique document
Patent documentation
Patent documentation 1: English Patent the 1st, 079, No. 686 specification sheetss
Patent documentation 2: the spy of Japan opens clear 56-055425 communique
Patent documentation 3: international disclosing No. 2004/111106
Summary of the invention
On the other hand, compare with existing aromatic copolycarbonate from petroleum, use polycarbonate resin that the Isosorbide as the plant origin monomer obtains in thermotolerance, unsatisfactory aspect transparent.And, xanthochromia takes place when also having melt molding, be difficult to the problem as transparent component, optics.
The object of the present invention is to provide a kind of thermotolerance from the structural unit of specific dihydroxy compound, the polycarbonate resin of transparency excellence and composition that contains this polycarbonate resin of containing.
Can provide following polycarbonate resin, poly carbonate resin composition, blooming, polycarbonate resin moldings by the present invention.
＜1〉a kind of polycarbonate resin, described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), it is characterized in that, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 1]
Figure BDA0000063054310000021
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 2]
Figure BDA0000063054310000022
＜2〉as＜1〉described polycarbonate resin, it is characterized in that described polycarbonate resin contains the dihydroxy compound of the bond structure that has following structural formula (1) below the 60ppm.
[changing 3]
Figure BDA0000063054310000023
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜3〉as＜1〉or＜2〉described polycarbonate resin, it is characterized in that described polycarbonate resin contains the carbonic diester shown in the following following general formula (3) of 60ppm.
[changing 4]
Figure BDA0000063054310000024
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜4〉as＜1 〉～＜3〉polycarbonate resin as described in each, it is characterized in that this polycarbonate resin contains the following aromatic monohydroxy compound of 700ppm, it is alkyl below 5 that this aromatic monohydroxy compound has or do not have carbonatoms.
＜5〉a kind of polycarbonate resin, it contains the structural unit from dihydroxy compound at least, and this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin is characterised in that,
Contain the following aromatic monohydroxy compound of 700ppm, it is alkyl below 5 that this aromatic monohydroxy compound has or do not have carbonatoms.
[changing 5]
Figure BDA0000063054310000031
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜6〉a kind of polycarbonate resin, it contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin is characterised in that the content of the carbonic diester shown in the following general formula (3) is 0.1ppm～60ppm.
[changing 6]
Figure BDA0000063054310000032
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 7]
Figure BDA0000063054310000033
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜7〉as＜6〉described polycarbonate resin, it is characterized in that the remaining content of dihydroxy compound with bond structure of described structural formula (1) is below the 60ppm.
＜8〉a kind of polycarbonate resin, it contains the structural unit from dihydroxy compound at least, and this dihydroxy compound has the bond structure of following structural formula (1), it is characterized in that,
The content of dihydroxy compound with bond structure of described structural formula (1) is below the 60ppm.
[changing 8]
Figure BDA0000063054310000041
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜9〉as＜1 〉～＜8〉each described polycarbonate resin, it is characterized in that the dihydroxy compound with bond structure of described structural formula (1) has heterocyclic radical.
＜10〉as＜1 〉～＜9〉each described polycarbonate resin, it is characterized in that the dihydroxy compound with bond structure of described structural formula (1) is the compound with the heterocyclic radical shown in the following general formula (4).
[changing 9]
Figure BDA0000063054310000042
＜11〉as＜5 〉～＜8〉each described polycarbonate resin, it is characterized in that, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 10]
Figure BDA0000063054310000043
＜12〉as＜1 〉～＜11〉each described polycarbonate resin, it is characterized in that second-order transition temperature is more than 90 ℃.
＜13〉as＜1 〉～＜12〉each described polycarbonate resin, it is characterized in that described polycarbonate resin also contains from being selected from by aliphatics dihydroxy compound, ester ring type dihydroxy compound, oxyalkylene group glycol, bis-phenol, having a structural unit of at least a compound in the group that the glycol of cyclic acetal structure forms.
＜14〉a kind of poly carbonate resin composition is characterized in that, described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin and the lipid acid of 0.0001 weight part～2 weight parts.
＜15〉as＜14〉described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin and the natural system wax of 0.0001 weight part～2 weight parts.
＜16〉as＜14〉or＜15〉described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin and 0.0001 weight part～2 weight parts be selected from least a compound in olefines wax, the silicone oil.
＜17〉as＜14 〉～＜16〉each described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin and 0.00001 weight part～0.1 weight part acidic cpd.
＜18〉as＜14 〉～＜17〉each described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin and 0.001 weight part～1 weight part phosphorus series compound.
＜19〉as＜14 〉～＜18〉each described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin, 0.00001 weight part～at least a acidic cpd of 0.1 weight part and 0.001 weight part～at least a phosphorus series compound of 1 weight part.
＜20〉as＜14 〉～＜19〉each described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described polycarbonate resin, 0.001 weight part～1 weight part aromatic monohydroxy compound that to have 1 above carbonatoms be the alkyl substituent more than 5.
＜21〉as＜14 〉～＜20〉each described poly carbonate resin composition, it is characterized in that described composition contains 100 weight parts＜1 〉～＜13〉each described poly carbonate resin composition and 0.000001 weight part～1 weight part bluing agent.
＜22〉a kind of blooming is characterized in that, it contains＜and 1 〉～＜13〉each described polycarbonate resin.
＜23〉a kind of polycarbonate resin moldings is characterized in that, it is by will＜1 〉～＜13〉each described polycarbonate resin or＜14～＜21〉each described poly carbonate resin composition carry out moulding and obtain.
＜24〉as＜23〉described polycarbonate resin moldings, it is characterized in that described polycarbonate resin moldings obtains by the injection moulding moulding.
＜25〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part～100 weight part mineral fillers,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 11]
Figure BDA0000063054310000061
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 12]
Figure BDA0000063054310000062
＜26〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part～100 weight part mineral fillers,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains and has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl below 5 below the 700ppm.
[changing 13]
Figure BDA0000063054310000063
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜27〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part～100 weight part mineral fillers,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of the carbonic diester shown in the following general formula (3) is 0.1ppm～60ppm.
[changing 14]
Figure BDA0000063054310000071
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 15]
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜28〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part～100 weight part mineral fillers,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of dihydroxy compound with bond structure of following structural formula (1) is below the 60ppm.
[changing 16]
Figure BDA0000063054310000073
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜29〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 0.01 weight part～30 parts by weight of flame retardant,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 17]
Figure BDA0000063054310000081
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 18]
Figure BDA0000063054310000082
＜30〉as＜29〉described poly carbonate resin composition, it is characterized in that fire retardant is to be selected from least a in the group of being made up of P contained compound flame retardant, halogen contained compound flame retardant.
＜31〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.01 weight part～30 parts by weight of flame retardant,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains and has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl below 5 below the 700ppm.
[changing 19]
Figure BDA0000063054310000083
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜32〉as＜31〉described poly carbonate resin composition, it is characterized in that fire retardant is to be selected from least a in the group of being made up of P contained compound flame retardant, halogen contained compound flame retardant.
＜33〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.01 weight part～30 parts by weight of flame retardant,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of the carbonic diester shown in the following general formula (3) is 0.1ppm～60ppm.
[changing 20]
Figure BDA0000063054310000091
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 21]
Figure BDA0000063054310000092
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜34〉as＜33〉described poly carbonate resin composition, it is characterized in that fire retardant is to be selected from least a in the group of being made up of P contained compound flame retardant, halogen contained compound flame retardant.
＜35〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.01 weight part～30 parts by weight of flame retardant,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of dihydroxy compound with bond structure of following structural formula (1) is below the 60ppm.
[changing 22]
Figure BDA0000063054310000093
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜36〉as＜35〉described poly carbonate resin composition, it is characterized in that fire retardant is to be selected from least a in the group of being made up of P contained compound flame retardant, halogen contained compound flame retardant.
＜37〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part～5 weight part UV light absorber,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 23]
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 24]
Figure BDA0000063054310000102
＜38〉as＜37〉described poly carbonate resin composition, it is characterized in that, described UV light absorber at the ratio of the molar absorptivity at wavelength 210nm place and the maximum value of molar absorptivity from wavelength 250nm to wavelength 350nm less than 1.75.
＜39〉as＜37〉or＜38〉described poly carbonate resin composition, it is characterized in that described UV light absorber is to be selected from least a in the group of being made up of triazine based compound, oxanilide based compound, malonic ester based compound.
＜40〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part～5 weight part UV light absorber,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains and has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl below 5 below the 700ppm.
[changing 25]
Figure BDA0000063054310000103
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜41〉as＜40〉described poly carbonate resin composition, it is characterized in that, described UV light absorber at the ratio of the molar absorptivity at wavelength 210nm place and the maximum value of molar absorptivity from wavelength 250nm to wavelength 350nm less than 1.75.
＜42〉as＜40〉or＜41〉described poly carbonate resin composition, it is characterized in that described UV light absorber is to be selected from least a in the group of being made up of triazine based compound, oxanilide based compound, malonic ester based compound.
＜43〉a kind of poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 0.005 weight part～5 weight part UV light absorber,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of the carbonic diester shown in the following general formula (3) is 0.1ppm～60ppm.
[changing 26]
Figure BDA0000063054310000111
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 27]
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜44〉as＜43〉described poly carbonate resin composition, it is characterized in that, described UV light absorber at the ratio of the molar absorptivity at wavelength 210nm place and the maximum value of molar absorptivity from wavelength 250nm to wavelength 350nm less than 1.75.
＜45〉as＜43〉or＜44〉described poly carbonate resin composition, it is characterized in that described UV light absorber is to be selected from least a in the group of being made up of triazine based compound, oxanilide based compound, malonic ester based compound.
＜46〉a kind of poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part～5 weight part UV light absorber,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of dihydroxy compound with bond structure of following structural formula (1) is below the 60ppm.
[changing 28]
Figure BDA0000063054310000121
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜47〉as＜46〉described poly carbonate resin composition, it is characterized in that, described UV light absorber at the ratio of the molar absorptivity at wavelength 210nm place and the maximum value of molar absorptivity from wavelength 250nm to wavelength 350nm less than 1.75.
＜48〉as＜46〉or＜47〉described poly carbonate resin composition, it is characterized in that described UV light absorber is to be selected from least a in the group of being made up of triazine based compound, oxanilide based compound, malonic ester based compound.
＜49〉a kind of poly carbonate resin composition is characterized in that, it contains 10 weight parts～90 weight part polycarbonate resins (a) and 90 weight parts～10 weight part thermoplastic resins (b),
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%.
[changing 29]
Figure BDA0000063054310000122
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 30]
＜50〉as＜49〉described poly carbonate resin composition, it is characterized in that thermoplastic resin (b) is that to be selected from phenylethylene resin series, saturated polyester resin, bis-phenol be at least a in polycarbonate resin, polyolefin-based resins and the acrylic resin.
＜51〉a kind of poly carbonate resin composition is characterized in that, it contains 10 weight parts～90 weight part polycarbonate resins (a) and 90 weight parts～10 weight part thermoplastic resins (b),
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains and has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl below 5 below the 700ppm.
[changing 31]
Figure BDA0000063054310000131
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜52〉as＜51〉described poly carbonate resin composition, it is characterized in that thermoplastic resin (b) is that to be selected from phenylethylene resin series, saturated polyester resin, bis-phenol be at least a in polycarbonate resin, polyolefin-based resins and the acrylic resin.
＜53〉a kind of poly carbonate resin composition is characterized in that, it contains 10 weight parts～90 weight part polycarbonate resins (a) and 90 weight parts～10 weight part thermoplastic resins (b),
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of the carbonic diester shown in the following general formula (3) is 0.1ppm～60ppm.
[changing 32]
Figure BDA0000063054310000132
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
[changing 33]
Figure BDA0000063054310000133
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
＜54〉as＜53〉described poly carbonate resin composition, it is characterized in that thermoplastic resin (b) is that to be selected from phenylethylene resin series, saturated polyester resin, bis-phenol be at least a in polycarbonate resin, polyolefin-based resins and the acrylic resin.
＜55〉a kind of poly carbonate resin composition is characterized in that, it contains 10 weight parts～90 weight part polycarbonate resins (a) and 90 weight parts～10 weight part thermoplastic resins (b),
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and in described polycarbonate resin, the content of dihydroxy compound with bond structure of following structural formula (1) is below the 60ppm.
[changing 34]
Figure BDA0000063054310000141
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
＜56〉as＜55〉described poly carbonate resin composition, it is characterized in that thermoplastic resin (b) is that to be selected from phenylethylene resin series, saturated polyester resin, bis-phenol be at least a in polycarbonate resin, polyolefin-based resins and the acrylic resin.
＜57〉a kind of polycarbonate resin moldings is characterized in that, it is with＜25 〉～＜56〉each described poly carbonate resin composition carry out moulding and obtain.
＜58〉as＜57〉described polycarbonate resin moldings, it is characterized in that polycarbonate resin moldings carries out moulding by injection moulding and obtains.
Can obtain the excellent polycarbonate resin of thermotolerance, the transparency according to the present invention and contain the poly carbonate resin composition of this polycarbonate resin.
Description of drawings
[Fig. 1] shows is the polycarbonate resin A-1 that contains heterocycle 1The H-NMR collection of illustrative plates.
Embodiment
Below the working of an invention mode is specifically described.Need to prove that the present invention is not limited to following embodiment, can carry out various variations in the scope of its main points during enforcement.In addition, employed accompanying drawing does not represent its actual size for the explanation present embodiment.In addition, among the present invention, if no special instructions, ppm represents the part by weight with respect to the standard substance of object.
[1] polycarbonate resin
The polycarbonate resin that the present invention uses has the structure that contains at least from the structural unit of dihydroxy compound, and this dihydroxy compound has the bond structure of following structural formula (1).
[changing 35]
Figure BDA0000063054310000151
(wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).)
(dihydroxy compound)
Dihydroxy compound as the bond structure with said structure formula (1), for example can enumerate 9,9-two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-isopropyl phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-isobutyl phenenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-cyclohexyl phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3-phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl)-3, the 5-3,5-dimethylphenyl) fluorenes, 9,9-two (4-(2-the hydroxyl-oxethyl)-3-tertiary butyl-6-aminomethyl phenyl) fluorenes, 9,9-two (4-(3-hydroxyl-2,2-dimethyl propoxy-) phenyl) fluorenes etc. are illustrated to have the aromatic series base and has the compound of the ether that is bonded in the aromatic series base at main chain at side chain; Illustrated oxyalkylene group glycolss such as Diethylene Glycol, triethylene glycol, Tetraglycol 99; Two [4-(2-hydroxyl-oxethyl) phenyl] methane, two [4-(2-hydroxyl-oxethyl) phenyl] ditane, 1, two [4-(2-hydroxyl-oxethyl) phenyl] ethane of 1-, 1, two [4-(2-hydroxyl-oxethyl) the phenyl]-1-diphenylphosphino ethanes of 1-, 2, two [4-(2-hydroxyl-oxethyl) phenyl] propane of 2-, 2, two [4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl] propane of 2-, 2,2-two [3,5-dimethyl-4-(2-hydroxyl-oxethyl) phenyl] propane, 1, two [4-(2-hydroxyl-oxethyl) phenyl]-3 of 1-, 3, the 5-trimethyl-cyclohexane, 1, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthenes of 1-, 1, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthenes of 4-, 1, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthenes of 3-, 2, two [4-(2-the hydroxyl-oxethyl)-3-phenyl] propane of 2-, 2, two [(2-the hydroxyl-oxethyl)-3-isopropyl phenyl] propane of 2-, 2, two [the 3-tertiary butyl-4-(2-hydroxyl-oxethyl) phenyl] propane of 2-, 2, two [4-(2-hydroxyl-oxethyl) phenyl] butane of 2-, 2, two [4-(2-hydroxyl-oxethyl) the phenyl]-4-methylpentanes of 2-, 2, two [4-(2-hydroxyl-oxethyl) phenyl] octanes of 2-, 1, two [4-(2-hydroxyl-oxethyl) phenyl] decane of 1-, 2, two [3-bromo-4-(2-hydroxyl-oxethyl) phenyl] propane of 2-, illustrated two (hydroxy alkoxy Ji Fangji) paraffinics such as two [3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-; Two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthenes, 1 of 1,1-, two [3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl] hexanaphthenes, 1 of 1-, illustrated two (hydroxy alkoxy Ji Fangji) loop chain alkanes such as two [4-(2-hydroxyl-oxethyl) phenyl] pentamethylene of 1-; 4,4 '-two (2-hydroxyl-oxethyl) diphenyl ether, 4,4 '-two (2-hydroxyl-oxethyls)-3, illustrated dihydroxyl alkoxyl group diaryl ethers such as 3 '-dimethyl diphenyl ether; 4,4 '-two (2-hydroxyl-oxethyl phenyl) sulfide, 4, illustrated pair of hydroxy alkoxy base aromatic yl sulfide classes such as 4 '-two [4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfide; 4,4 '-two (2-hydroxyl-oxethyl phenyl) sulfoxide, 4, illustrated pair of hydroxy alkoxy Ji Fangji sulfoxide classes such as 4 '-two [4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfoxide; 4,4 '-two (2-hydroxyl-oxethyl phenyl) sulfone, 4, illustrated pair of hydroxy alkoxy base aryl sulfones such as 4 '-two [4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfone; With 1, the two hydroxyl-oxethyl benzene, 1 of 4-, the two hydroxyl-oxethyl benzene, 1 of 3-, the two hydroxyl-oxethyl benzene, 1 of 2-, two [2-[4-(2-hydroxyl-oxethyl) phenyl] propyl group of 3-] benzene, 1, two [2-[4-(2-hydroxyl-oxethyl) phenyl] propyl group of 4-] benzene, 4,4 '-two (2-hydroxyl-oxethyl) biphenyl, 1, two [4-(2-hydroxyl-oxethyl) phenyl]-5 of 3-, the dihydroxy compound shown in 7-dimethyladamantane, the following general formula (4) is the dihydroxy compound with heterocyclic radical of representative; And 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-alcohol, 3,9-two (2-hydroxyl-1,1-dimethyl ethyl)-2,4,8,10-, four oxaspiros [5,5] the spiroglycol class such as undecane, these can use separately, also can be used in combination more than 2 kinds.
Wherein, the dihydroxy compound shown in the preferred following general formula (4).
[changing 36]
Figure BDA0000063054310000161
As the dihydroxy compound shown in the above-mentioned general formula (4), for example can enumerate, be in Isosorbide, isomannite, the different idose of the relation of steric isomer.These can use a kind separately, also can be used in combination more than 2 kinds.Among these dihydroxy compound, from the aspect of the easiness that obtains and make, optical characteristics, formability, the Isosorbide that is obtained through dehydrating condensation by the Sorbitol Powder of aboundresources, the various starch manufacturings that obtain easily most preferably.
It should be noted that Isosorbide is easily by oxygen oxidation at leisure.Therefore, preserving, when the processing when making, for the decomposition that prevents from being caused by oxygen, importantly do not sneaking into moisture and use reductor or under nitrogen atmosphere, carry out.After Isosorbide was oxidized, can produce with formic acid was the resolvent of representative.For example, when using the Isosorbide contain these resolvents to make polycarbonate resin, cause resulting polycarbonate resin to take place painted or cause the obvious variation of physicals.In addition, it is also influential to polyreaction sometimes, can not obtain high molecular weight polymers, so be not preferred.In addition, add under the such situation of the stablizer of the generation prevent formic acid, the polycarbonate resin that some stabilizer type can cause obtaining takes place painted or causes the obvious variation of physicals.As stablizer, can use reductive agent, antacid.Wherein, as reductive agent, sodium borohydride, lithium borohydride etc. can be enumerated, as antacid, an alkali metal salts such as sodium hydroxide can be enumerated.Because basic metal or polymerizing catalyst, so when adding such an alkali metal salt, if excessive interpolation then can not be controlled polyreaction, so be not preferred.Need to prove, in this specification sheets, employed term " basic metal " and " alkaline-earth metal " respectively with long period type periodictable (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) in " the 1st family's metal " identical with the implication of " group II metal ".
In order to obtain the Isosorbide of oxygen-free resolvent, can distill Isosorbide as required.In addition, for the oxidation that prevents Isosorbide, decomposition and added under the situation of stablizer, also can distill Isosorbide as required.In this case, the distillation of Isosorbide can be simple distillation, can be continuous still battery also, and this is not particularly limited.About distillation, under inert gas atmospheres such as argon, nitrogen, implement underpressure distillation.Be the following high purity Isosorbide of following, the special 5ppm of 20ppm by carrying out such distillation to Isosorbide, can obtaining formic acid content.
In addition, about formic acid content measuring method in the Isosorbide, use ion chromatograph to measure by following order.
Accurately take by weighing about 0.5g Isosorbide, put in the volumetric flask of 50ml, carry out constant volume with pure water.Use aqueous sodium formate solution as standard test specimen, the peak consistent with retention time with standard test specimen is formic acid, according to peak area, utilizes the absolute standard curve method, carries out quantitatively.
Ion chromatograph uses the DX-500 type of Dionex society system, and detector uses electrical conductivity degree detector.About measuring column, Dionex society makes guard column and uses AG-15, and separator column uses AS-15.To measure the sample loop that sample injects 100 μ l, use 10mM-NaOH as elutriant, continue for 35 ℃ to measure in flow velocity 1.2ml/min, thermostatic bath temperature.Suppressor uses membrane suppressor, and regenerated liquid uses 12.5mM-H 2SO 4The aqueous solution.
(ester ring type dihydroxy compound)
The polycarbonate resin that the present invention uses preferably also contains the structural unit from the ester ring type dihydroxy compound except the above-mentioned structural unit that comes the dihydroxy compound shown in the self-drifting (4).
The ester ring type dihydroxy compound is had no particular limits, can enumerate the compound that contains 5 ring structures or 6 ring structures usually.When the ester ring type dihydroxy compound is 5 yuan of rings, 6 ring structures, can improve the thermotolerance of resulting polycarbonate resin.6 ring structures can be fixed as chair form or boat formula by covalent linkage.
The carbonatoms that the ester ring type dihydroxy compound contains is generally below 70, is preferably below 50, more preferably below 30.When carbonatoms was too much, thermotolerance increased, but the synthetic difficulty that becomes, perhaps purifying becomes difficult, has the trend of cost up.Carbonatoms is more little, more easy purification, and obtain easily.
As the ester ring type dihydroxy compound that contains 5 ring structures or 6 ring structures, specifically can enumerate following general formula (II) or (III) shown in the ester ring type dihydroxy compound.
HOCH 2-R 1-CH 2OH(II)
HO-R 2-OH(III)
(wherein, in formula (II), the formula (III), R 1, R 2The expression carbonatoms is 4～20 ring alkylidene group)
As the cyclohexanedimethanol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (II), it comprises R in the general formula (II) 1For following general formula (IIa) (in the formula, R 3The expression carbonatoms is 1～12 alkyl) shown in various isomer under the structure situation.As such compound, specifically can enumerate 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol etc.
[changing 37]
As the tristane dimethanol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (II), pentacyclopentadecandimethanol dimethanol, it comprises R in the general formula (II) 1Be the various isomer shown in the following general formula (IIb) (in the formula, n represents 0 or 1).
[changing 38]
Figure BDA0000063054310000182
As the naphthalane dimethanol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (II) or three ring tetradecane dimethanols, it comprises R in the general formula (II) 1Be the various isomer shown in the following general formula (IIc) (m represents 0 or 1 in the formula).As such compound, specifically can enumerate 2,6-naphthalane dimethanol, 1,5-naphthalane dimethanol, 2,3-naphthalane dimethanol etc.
[changing 39]
Figure BDA0000063054310000191
In addition, as the norcamphane dimethanol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (II), it comprises R in the general formula (II) 1Be the various isomer shown in the following general formula (IId).As such compound, specifically can enumerate 2,3-norcamphane dimethanol, 2,5-norcamphane dimethanol etc.
[changing 40]
Figure BDA0000063054310000192
As the diamantane dimethanol that belongs to the ester ring type dihydroxy compound shown in the general formula (II), it comprises R in the general formula (II) 1Be the various isomer shown in the following general formula (IIe).As such compound, specifically can enumerate 1,3-diamantane dimethanol etc.
[changing 41]
Figure BDA0000063054310000193
In addition, as the cyclohexanediol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (III), it comprises R in the general formula (III) 2Be following general formula (IIIa) (R in the formula 3The expression carbonatoms is 1～12 alkyl) shown in various isomer.As such compound, specifically can enumerate 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl isophthalic acid, 4-cyclohexanediol etc.
[changing 42]
Figure BDA0000063054310000194
As the three ring decanediols, five rings five decanediols that belong to the ester ring type dihydroxy compound shown in the above-mentioned general formula (III), it comprises R in the general formula (III) 2Be the various isomer shown in the following general formula (IIIb) (n represents 0 or 1 in the formula).
[changing 43]
Figure BDA0000063054310000201
As the naphthalane glycol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (III) or three rings, four decanediols, it comprises R in the general formula (III) 2Be the various isomer shown in the following general formula (IIIc) (m represents 0 or 1 in the formula).As such compound, specifically can use 2,6-naphthalane glycol, 1,5-naphthalane glycol, 2,3-naphthalane glycol etc.
[changing 44]
Figure BDA0000063054310000202
As the norcamphane glycol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (III), it comprises R in the general formula (III) 2Be the various isomer shown in the following general formula (IIId).As such compound, specifically can use 2,3-norcamphane glycol, 2,5-norcamphane glycol etc.
[changing 45]
Figure BDA0000063054310000203
As the diamantane glycol that belongs to the ester ring type dihydroxy compound shown in the above-mentioned general formula (III), it comprises R in the general formula (III) 2Be the various isomer shown in the following general formula (IIIe).As such compound, specifically can use 1,3-diamantane glycol etc.
[changing 46]
Figure BDA0000063054310000204
Among the concrete example of above-mentioned ester ring type dihydroxy compound, preferred especially cyclohexanedimethanol class, tristane diformazan alcohols, diamantane glycols, pentacyclopentadecandimethanol diformazan alcohols, consider from easy acquisition, processing aspect easily, preferred 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tristane dimethanol.
Need to prove that above-mentioned exemplary compounds is an example that can be used in ester ring type dihydroxy compound of the present invention, is not limited to these.These ester ring type diol compounds can use a kind separately, can use mixing more than 2 kinds.
In the polycarbonate resin that the present invention uses, for from the structural unit of the dihydroxy compound shown in the above-mentioned general formula (4) with from proportional being not particularly limited that contain of the structural unit of ester ring type dihydroxy compound, can select with ratio arbitrarily.
This contains proportional being generally (coming the structural unit of the dihydroxy compound shown in the self-drifting (4)): (from the structural unit of ester ring type dihydroxy compound)=(1: 99)～(99: 1) (mole %) is preferably (structural unit that comes the dihydroxy compound shown in the self-drifting (4)) especially: (from the structural unit of ester ring type dihydroxy compound)=(10: 90)～(90: 10) (mole %).
Compare with above-mentioned scope, the structural unit that comes the dihydroxy compound shown in the self-drifting (4) too much and when very few from the structural unit of ester ring type dihydroxy compound, polycarbonate resin has color easily.On the contrary, the structural unit that comes the dihydroxy compound shown in the self-drifting (4) is very few and when too much from the structural unit of ester ring type dihydroxy compound, the molecular weight of polycarbonate resin is difficult for increasing.
(other dihydroxy compound)
In addition, the polycarbonate resin that uses of the present invention can also contain the structural unit of other dihydroxy compound except coming the dihydroxy compound shown in the self-drifting (4) and above-mentioned ester ring type dihydroxy compound.
As other such dihydroxy compound, for example can enumerate aliphatics dihydroxy compound, oxyalkylene group glycol, bis-phenol, have the glycol of cyclic acetal structure etc.
As the aliphatics dihydroxy compound, for example can enumerate ethylene glycol, 1, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,2-butyleneglycol, 1,5-heptanediol, 1,6-hexylene glycol etc.
As bis-phenol, for example can enumerate 2,2-two (4-hydroxy phenyl) propane [=dihydroxyphenyl propane], 2,2-two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, 2,2-two (4-hydroxyl-3,5-diethyl phenyl) propane, 2,2-two (4-hydroxyl-(3, the 5-phenylbenzene) propane phenyl), 2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane, 2,2-two (4-hydroxy phenyl) pentane, 2,4 '-dihydroxyl-ditane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 3,3-two (4-hydroxy phenyl) pentane, 1,1-two (4-hydroxy phenyl) hexanaphthene etc.
In addition, as bis-phenol, can also enumerate for example two (4-hydroxy phenyl) sulfone, 2,4 '-dihydroxy-diphenyl sulfone, two (4-hydroxy phenyl) sulfide, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-dichloro diphenyl ether, 4,4 '-dihydroxyl-2,5-diethoxy diphenyl ether, 9,9-two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes, 9,9-two (4-(2-hydroxyl-oxethyl-2-methyl) phenyl) fluorenes, 9,9-two (4-hydroxy phenyl) fluorenes, 9,9-two (4-hydroxy-2-methyl phenyl) fluorenes.
In addition, as the glycol with cyclic acetal structure, for example can enumerate the spiroglycol, dioxane glycol etc.
These other dihydroxy compound can use more than a kind or 2 kinds.
By using other dihydroxy compound, the flexibility that can improve, improve thermotolerance, improve effects such as formability.Especially, proportional when too much from containing of the structural unit of other dihydroxy compound, the performance of optical characteristics is originally reduced.
Therefore, in the polycarbonate resin that the present invention uses, the total amount of the dihydroxy compound shown in the preferred formula (4) and ester ring type dihydroxy compound is 90 moles more than the % with respect to the ratio of the whole dihydroxy compound that constitute polycarbonate resin.
Dihydroxy compound in the polycarbonate resin that preferred especially the present invention uses only is made of the dihydroxy compound shown in the general formula (4) and ester ring type dihydroxy compound.
The polymerization degree of the polycarbonate resin that uses about the present invention, reduced viscosity (being designated hereinafter simply as " polycarbonate resin reduced viscosity ") in following mensuration, more than 0.40dl/g, be preferably the such polymerization degree of 0.40dl/g～2.0dl/g especially, further the preferred polymerization degree such in the scope of 0.45dl/g～1.5dl/g.The mensuration of described reduced viscosity is following carries out: the weight ratio of using phenol and sym.-tetrachloroethane be 1: 1 mixing solutions as solvent, be 1.00g/dl with polycarbonate resin lipid concentration fine setting, measure for 20.0 ℃ ± 0.1 ℃ in temperature.
The reduced viscosity of polycarbonate resin is crossed when low, and the physical strength when being shaped to lens etc. reduces easily.In addition, when the reduced viscosity of polycarbonate resin was excessive, the flowability when carrying out moulding reduced, and cycle characteristics is reduced, and it is big that the degree of birefringence of moulding product becomes easily.
The Abbe number of the polycarbonate resin that the present invention uses is preferably more than 50, is preferably more than 55 especially.This value is more big, and then the wavelength dispersion of specific refractory power is more little, for example diminishes as the aberration under the situation of simple lens use, obtains distincter image easily.Abbe number is more little, and then the wavelength dispersion of specific refractory power is more big, and under the situation as the simple lens use, it is big that aberration becomes, and it is big that the fog-level of image becomes.
5% thermal weight loss temperature of the polycarbonate resin that the present invention uses is preferably more than 340 ℃, is preferably especially more than 345 ℃.5% thermal weight loss temperature is more big, and then thermostability is more high, can stand to use under higher temperature; 5% thermal weight loss temperature is more little, and then thermostability is more low, is difficult at high temperature use.In addition, the control during manufacturing allows that amplitude narrows down, and is difficult to make.Moreover, make temperature and also can increase, span of control can be wideer during manufacturing, so make easily.
The photoelastic coefficient of the polycarbonate resin that the present invention uses is preferably 40 * 10 -12Pa -1Below, more preferably 20 * 10 -12Pa -1Below.If the value of photoelastic coefficient is higher, then utilize melt extrude, the value of the phase differential of film that film processed such as solution casting method obtains increases, under the situation with its stretching, the small vibrations of tension force will cause the fluctuation of the interior phase differential of face further to increase.In addition, paste under the situation of such phase retardation film, not only can cause desired phase differential to be offset by the tension force when pasting, also cause the phase difference value variation because of the contraction of the polaroid after pasting etc. easily.Photoelastic coefficient is more little, and then the fluctuation of phase differential is more little.
The preferred cantilever beam impact strength of the polycarbonate resin that the present invention uses is 30J/m 2More than.Cantilever beam impact strength is more big, and then the intensity of formed body is more high, more is not easy to damage.
The polycarbonate resin that the present invention uses is 5ng/cm gas generated (below, abbreviate " gas generated " sometimes as) of 110 ℃ of following per unit areas except phenol preferably 2Below, in addition, more preferably come the gas generated 0.5ng/cm of being of the dihydroxy compound in addition of the dihydroxy compound shown in the self-drifting (4) 2Below.This is gas generated more few, more can be applied to avoid produce the purposes of the influence of gas, for example preserves the housing of the purposes of electronic units such as semi-conductor, the interior dress material purposes of buildings, tame electrical article etc. etc.
In addition, the measuring method of the Abbe number of the polycarbonate resin of the present invention's use, 5% thermal weight loss temperature, photoelastic coefficient, cantilever beam impact strength, generation gas volume is specifically as described later shown in embodiment one joint.
Polycarbonate resin for the present invention uses when measuring, can observe single second-order transition temperature by differential scanning calorimeter (DSC).By adjusting the dihydroxy compound shown in the general formula (4) and kind, the proportioning of ester ring type dihydroxy compound, can according to purposes with about 45 ℃～polymer form that has any second-order transition temperature in 155 ℃ of left and right sides scopes obtains the polycarbonate resin that the present invention uses.
For example, for the film purposes that needs flexibility, preferably the second-order transition temperature with polycarbonate resin is adjusted into more than 45 ℃, for example 45～100 ℃.
Particularly for requiring formed body purposes such as stable on heating bottle, bag, the second-order transition temperature of polycarbonate resin preferably is adjusted into more than 90 ℃, for example 90～130 ℃.
In addition, second-order transition temperature is more than 120 ℃ the time, can be suitable as the lens purposes of optics.That is, have the polycarbonate resin of such second-order transition temperature by use, even under the such hot and humid degree of 85 ℃ of temperature, relative humidity 85%, also be difficult for deforming, can access the little lens of fluctuation of surface accuracy.
(manufacture method of polycarbonate resin)
The polycarbonate resin that the present invention uses can be made by existing known polymerization process.As polymerization process, can use phosgene solution polymerization process, make any means in the melt phase polycondensation of carbonic diester and oxy-compound reaction.
Wherein, preferably in the presence of polymerizing catalyst, make the melt phase polycondensation of the dihydroxy compound of the bond structure with said structure formula (1), other dihydroxy compound that use as required and carbonic diester reaction.
(carbonic diester)
As the carbonic diester that melt phase polycondensation uses, can enumerate the carbonic diester shown in the following general formula (3) usually.These carbonic diesters can use a kind separately, can use mixing more than 2 kinds.
[changing 47]
Figure BDA0000063054310000241
(in the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.)
As the carbonic diester shown in the above-mentioned general formula (3), for example can enumerate diphenyl carbonate, xylyl carbonate etc. and replace diphenyl carbonate; Methylcarbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc.
Among these, preferred especially diphenyl carbonate, replacement diphenyl carbonate, diphenyl carbonate.
In the above-mentioned melt phase polycondensation, with respect to being used for containing of reaction have structural formula whole dihydroxy compound of dihydroxy compound of bond structure of (1), the molar ratio of the carbonic diester shown in the employed general formula (3) is 0.90～1.10, more preferably 0.96～1.04.
When the mol ratio of the carbonic diester that uses in the melt phase polycondensation was too small, the terminal OH base of the polycarbonate resin of manufacturing increased, the thermostability variation of polymkeric substance, and may can not get desired high molecular weight material.On the other hand, when the mol ratio of employed carbonic diester was excessive, under identical polymerizing condition, the speed of transesterification reaction reduced, and may be difficult to make the polycarbonate resin of desired molecular weight.In addition, carbonic diester amount remaining in the polycarbonate resin of manufacturing may increase, when remaining carbonic diester may cause moulding or the peculiar smell of moulding product.
Consider from such aspect, the remaining content of dihydroxy compound of bond structure that in the polycarbonate resin that the present invention uses, preferably has a structural formula (1) as 60ppm below, more preferably below the 50ppm, be preferably below the 30ppm especially.
When the remaining content of the dihydroxy compound of the bond structure with structural formula (1) in the polycarbonate resin is too much, the thermostability variation of polymkeric substance, the dirt settling that is attached on the metal pattern when injection molding simultaneously increases, when carrying out the extrusion moulding of sheet, film, the amount of roller dirt settling increases, and exists to cause the impaired possibility of appearance.
In addition, the remaining content of the carbonic diester shown in the preferred formula in the polycarbonate resin that the present invention uses (3) as 60ppm below, 0.1ppm～60ppm more preferably, further preferred 0.1ppm～50ppm, preferred especially 0.1ppm～30ppm.
When the content of the carbonic diester shown in the general formula in the polycarbonate resin (3) is too much, the dirt settling that is attached on the metal pattern when injection molding increases, when carrying out the extrusion moulding of sheet, film, the amount of roller dirt settling increases, and exists to cause the impaired possibility of appearance.
(the terminal group structure of polycarbonate resin)
As described above, in the manufacture method of the polycarbonate resin that the present invention uses, preferably use diphenyl carbonate as carbonic diester.In this case, the terminal group shown in the following structural formula of the polycarbonate resin of manufacturing (2) (following note do " phenyl end ") sometimes exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) preferably in the scope more than 20%.
In addition, the phenyl end of polycarbonate resin exists number (A) further preferred in the scope more than 25%, particularly preferably in the scope more than 30% with respect to the ratio (A/B) of whole terminal numbers (B).
The phenyl end exist number (A) very few with respect to the ratio (A/B) of whole terminal numbers (B) time, be under the condition of high temperature at polymeric reaction temperature, injecting forming temperature etc., have the possibility of painted increase.
[changing 48]
Figure BDA0000063054310000251
Have no particular limits for the method that exists number (A) to adjust to above-mentioned scope with respect to the ratio (A/B) of whole terminal numbers (B) with the phenyl end of polycarbonate resin, for example, in the scope that can obtain desired high molecular weight material, adjust the amount of carbonic diester and the ratio of the whole dihydroxy compound that are used for reaction; Or the polyreaction back segment by the degassing remaining monomer is scavenged into outside the reaction system; Or the stirring efficiency etc. of reaction machine that improves the polyreaction back segment can be adjusted to above-mentioned scope with respect to the ratio (A/B) of whole terminal numbers (B) with the number (A) that exists of phenyl end thus to improve speed of response.
For the ratio of the phenyl end in the polycarbonate resin, can utilize the NMR spectrometer, use the deuterochloroform that has added TMS as the mensuration solvent, by 1The mensuration of H-NMR spectrum is calculated.
In addition, the ratio from each dihydroxy compound structural unit of the formation polycarbonate resin that the usage ratio of other dihydroxy compound that have dihydroxy compound, the ester ring type dihydroxy compound of the bond structure of structural formula (1) and use as required is used according to the invention is suitably adjusted it.
(polymerizing catalyst)
As the polymerizing catalyst in the melt polymerization (transesterification catalyst), use alkali metal compound and/or alkali earth metallic compound.Also basic cpds such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound be can share with alkali metal compound and/or alkali earth metallic compound together complementaryly, but alkali metal compound and/or alkali earth metallic compound especially preferably only used.
As the alkali metal compound as polymerizing catalyst, for example can enumerate sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, saleratus, lithium bicarbonate, cesium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, the stearic acid caesium, sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride, the hydroboration caesium, phenyl-boron dihydroxide sodium, phenyl-boron dihydroxide potassium, the phenyl-boron dihydroxide lithium, the phenyl-boron dihydroxide caesium, Sodium Benzoate, potassium benzoate, lithium benzoate, the phenylformic acid caesium, Sodium phosphate dibasic, dipotassium hydrogen phosphate, phosphoric acid hydrogen two lithiums, phosphoric acid hydrogen two caesiums, disodium phenylphosphate, the phosphenylic acid dipotassium, phosphenylic acid two lithiums, phosphenylic acid two caesiums, sodium, potassium, lithium, the alkoxide of caesium, phenates, the disodium salt of dihydroxyphenyl propane, di-potassium, dilithium salt, two cesium salts etc.
As alkali earth metallic compound, can enumerate for example calcium hydroxide, hydrated barta, magnesium hydroxide, strontium hydroxide, Calcium hydrogen carbonate, barium bicarbonate, Magnesium hydrogen carbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesiumcarbonate, Strontium carbonate powder, lime acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, Magnesium Stearate, strontium stearate etc.These alkali metal compounds and/or alkali earth metallic compound can be used alone, also can be also with two or more.
Concrete example as the alkaline boron compound that share with alkali metal compound and/or alkali earth metallic compound, can enumerate sodium salt, sylvite, lithium salts, calcium salt, barium salt, magnesium salts or the strontium salt etc. of tetramethyl-boron, tetraethyl-boron, tetrapropyl boron, tetrabutyl boron, trimethylammonium ethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethyl benzyl boron, triethyl phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl-boron, methyl triphenyl boron, butyl triphenyl boron etc.
As the alkaline phosphating compound, for example can enumerate triethyl phosphine, three n-propyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, tributylphosphine Huo quaternary alkylphosphonium salt etc.
As alkaline ammonium compound, for example can enumerate Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylammonium ethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl ammonium hydroxide, triethyl benzylic hydrogens ammonium oxide, triethyl phenyl ammonium hydroxide, tributyl benzylic hydrogens ammonium oxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl ammonium hydroxide etc.
As amine compound, can enumerate for example 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethyl amino yl pyridines, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, glyoxal ethyline, quinolylamine etc.These basic cpds also can be used alone, also can be also with two or more.
In the situation of using alkali metal compound and/or alkali earth metallic compound, to be converted into the amount of metal, with respect to the used whole dihydroxy compound of 1 molar reactive, the consumption of above-mentioned polymerizing catalyst is generally 0.01～100 micromole, be preferably 0.5～50 micromole, more preferably 1～25 micromolar scope.When the consumption of polymerizing catalyst is very few, can not get the polymerization activity to polycarbonate resin necessity of making desired molecular weight, on the other hand, when the consumption of polymerizing catalyst is too much, the tone of resulting polycarbonate resin worsens, produce by product, the generation of mobile reduction and gel increases, and is difficult to the polycarbonate of manufacturing objective quality.
When making the polycarbonate resin of the present invention's use, the dihydroxy compound of the above-mentioned bond structure with structural formula (1) both can be supplied with solid form, also can supply with molten state to heat the back, can also supply with the form of the aqueous solution.
The ester ring type dihydroxy compound also is both can supply with solid form, also can supply with molten state to heat the back, as long as this ester ring type dihydroxy compound is water-soluble material, can also supply with the form of the aqueous solution.Dihydroxy compound for other also is so same.If these raw material dihydroxy compound are supplied with the form of molten state or the aqueous solution, have when then industry is made and be easy to the advantage of measuring and carrying.
Among the present invention, in the presence of polymerizing catalyst, have the dihydroxy compound of bond structure of structural formula (1) and ester ring type dihydroxy compound and other dihydroxy compound that use as required and the method that carbonic diester reacts and implement with the multistage operation more than 2 stages usually.
Specifically, the temperature that is reflected at 140～220 ℃ (preferred 150～200 ℃) in the 1st stage is implemented 0.1～10 hour (preferred 0.5～3 hour).After the 2nd stage, the pressure of reaction system is slowly reduced and temperature of reaction is raise from the pressure in the 1st stage, simultaneously the aromatic monohydroxy compounds such as phenol that produce are discharged to outside the reaction system, the pressure of end reaction system is below the 200Pa, temperature is 210～280 ℃, carries out polycondensation thus.
In the decompression process in the polycondensation, importantly control the balance of the pressure in temperature and the reaction system.When particularly the either party of temperature or pressure changed too quickly, unreacted monomer distillation came out, and the mol ratio of dihydroxy compound and carbonic diester is changed, and the polymerization degree reduces sometimes.
For example, use Isosorbide and 1, under the situation of 4-cyclohexanedimethanol as dihydroxy compound, 1, the 4-cyclohexanedimethanol is that 50 moles of % are when above with respect to the mol ratio of whole dihydroxy compound, 1, the 4-cyclohexanedimethanol is easy to be come out by straight run distillation with the form of monomer, so the pressure in reaction system is under the decompression about 13kPa, when being risen with the speed of rising in per 1 hour below 40 ℃, temperature reacts, and then under the pressure that drops to about 6.67kPa, temperature is raise with the speed of rising in per 1 hour below 40 ℃, final pressure below 200Pa, carry out polycondensation under 200 ℃ to 250 ℃ the temperature, can obtain the polycarbonate resin that the polymerization degree has fully improved like this, so this is preferred.
With respect to whole dihydroxy compound, 1, the mol ratio of 4-cyclohexanedimethanol is less than under the situation of 50 moles of %, particularly this mol ratio is under the following situation of 30 moles of %, viscosity occurring sharply rises, so for example the pressure in reaction system is under the decompression that reaches about 13kPa, react in the time of with per 1 hour heat-up rate rising temperature below 40 ℃, again under pressure is reduced to pressure about 6.67kPa, react in the time of with per 1 hour heat-up rate (being preferably per 1 hour heat-up rate more than 50 ℃) rising temperature more than 40 ℃, final under the decompression below the 200Pa, carry out polycondensation under 220 to 290 ℃ the temperature, carry out to obtain the polycarbonate resin that the polymerization degree has fully improved like this, thereby this is preferred.The form of reaction can be arbitrary method of the combination of batch-type, continous way or batch-type and continous way.
(content of aromatic monohydroxy compound)
In addition, in above-mentioned dihydroxy compound and the polycondensation of carbonic diester, generated with by-product form and to have had or not had the aromatic monohydroxy compound that carbonatoms is the alkyl below 5.
In the present embodiment, the optimization polycarbonate resin contains, and to have or do not have carbonatoms be that the content of the aromatic monohydroxy compound of the alkyl below 5 is below the 700ppm, and more preferably content is below the 500ppm, and special preferred content is below the 300ppm.
But, containing the above-mentioned aromatic monohydroxy compound about 10ppm in the polycarbonate resin that the present invention uses, this is inevitable remaining amount.
Having or do not have carbonatoms herein, is that the aromatic monohydroxy compound of the alkyl below 5 means and do not comprise that aftermentioned adds the antioxidants such as for example hindered phenol of polycarbonate resin like that to.
As having or do not have the concrete example that carbonatoms is the aromatic monohydroxy compound of the alkyl below 5, for example can enumerate phenol, cresols, tert.-butyl phenol, adjacent normal-butyl phenol, a normal-butyl phenol, align butylphenol, adjacent isobutyl-phenol, an isobutyl-phenol, to isobutyl-phenol, o-tert-butylphenol, a tert.-butyl phenol, p-tert-butylphenol, adjacent n-pentyl phenol, a n-pentyl phenol, align amyl phenol, 2,6-DI-tert-butylphenol compounds, 2,5-DI-tert-butylphenol compounds, 2,4-DI-tert-butylphenol compounds, 3,5-DI-tert-butylphenol compounds etc.
Be that the method that the content of the aromatic monohydroxy compound of the alkyl below 5 is adjusted to below the 700ppm has no particular limits for the carbonatoms that has or do not have that polycarbonate resin is contained, can enumerate following method usually.
For example, in polycondensation, make the reinforced ratio of dihydroxy compound and carbonic diester near 1; Increase polycondensation; Effectively above-mentioned aromatic monohydroxy compound is discharged to outside the reactor that carries out polycondensation; Use horizontal reactor to come full-bodied reaction solution is applied predetermined shearing force in the second half section of polycondensation, outgas simultaneously; Make water and above-mentioned aromatic monohydroxy compound azeotropic etc. by water filling devolatilization operation.
In the polycarbonate resin that the present invention uses, have or do not have carbonatoms and be the content of aromatic monohydroxy compound of the alkyl below 5 when too much, impair the color harmony transparency, for example, the tendency that becomes the material that is not suitable as optical material is arranged.In addition, thermotolerance reduces, tone variation after for some time.
[2] poly carbonate resin composition
The polycarbonate resin that can use the present invention to use is made the poly carbonate resin composition that wherein is added with acidic cpd, phosphorus series compound.
Herein, with respect to 100 mass parts polycarbonate resins, the combined amount of each mixture is as follows: at least a acidic cpd is 0.00001 weight part～0.1 weight part, be preferably 0.0001 weight part～0.01 weight part, 0.0002 weight part～0.001 weight part more preferably; At least a phosphorus series compound is 0.001 weight part～1 weight part, be preferably 0.001 weight part～0.1 weight part, 0.001 weight part～0.05 weight part more preferably.
If the combined amount of acidic cpd is very few, when then carrying out injection molding, can not fully suppress painted sometimes under the elongated situation of the resin residence time.In addition, if the combined amount of acidic cpd is too much, then the hydrolytic resistance of resin obviously reduces sometimes.
If the combined amount of phosphorus series compound is very few, when then carrying out injection molding, can not fully suppress painted sometimes under the elongated situation of the resin residence time.In addition, if the combined amount of phosphorus series compound is too much, then the hydrolytic resistance of resin obviously reduces sometimes.
(acidic cpd)
As acidic cpd, can enumerate for example hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, phosphinous acid, polyphosphoric acid, hexanodioic acid, xitix, aspartic acid, nonane diacid, adenylic acid, phenylformic acid, formic acid, valeric acid, citric acid, oxyacetic acid, L-glutamic acid, pentanedioic acid, styracin, succsinic acid, acetic acid, tartrate, oxalic acid, to toluenesulfinic acid, tosic acid, naphthene sulfonic acid, niacin, picric acid, pyridine carboxylic acid, phthalic acid, terephthalic acid, propionic acid, benzene sulfinic acid, Phenylsulfonic acid, propanedioic acid, Bronsted acid and ester classes thereof such as toxilic acid.In these acidic cpd or derivatives thereofs, preferred sulfonic acid class or its ester class, wherein preferred especially tosic acid, methyl tosylate, butyl p-toluenesulfonate.
The compound of the alkaline ester exchange catalysts that uses in the polycondensation as the above-mentioned polycarbonate resin of neutralization, these acidic cpds can add in the manufacturing process of polycarbonate resin.
(phosphorus series compound)
As phosphorus series compound, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and these ester etc.By adding phosphorus series compound, can prevent the painted of polycarbonate resin.
As concrete compound, can enumerate for example triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three decyl phosphorous acid esters, the trioctylphosphine phosphorous acid ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,2-methylene radical two (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, two (nonyl phenyl) pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, the Tributyl phosphate ester, triethyl phosphate, trimethyl phosphate, triphenyl, the adjacent xenyl phosphoric acid ester of phenylbenzene list, dibutyl phosphate, the dioctyl phosphoric acid ester, the di-isopropyl phosphoric acid ester, 4,4 '-biphenylene diphosphinic acid four (2,4-di-tert-butyl-phenyl) ester, the phosphenylic acid dimethyl esters, the phosphenylic acid diethyl ester, phosphenylic acid dipropyl etc.
Among these, preferred three nonyl phenyl phosphites, the trimethyl phosphate, three (2 of using, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and phosphenylic acid dimethyl esters.These phosphorus series compounds can use more than a kind or 2 kinds.
(other antioxidant)
Except above-mentioned acidic cpd, phosphorus series compound, can also add antioxidant in the poly carbonate resin composition of the present invention.
As antioxidant, can enumerate for example tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate), glycerine-3-stearyl thiopropionate, triethylene glycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for tetramethylolmethane-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxyl-benzylphosphonic acid ester diethyl ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 4,4 '-biphenylene di 2 ethylhexyl phosphonic acid four (2, the 4-di-tert-butyl-phenyl) ester, 3,9-two { 1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl }-2,4,8, in 10-four oxaspiros (5, the 5) undecane etc. one or more.
Among these acidic cpds, the aromatic monohydroxy compound that preferably to have 1 above carbonatoms be the alkyl substituent more than 5, specifically, preferred octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester }, 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-trimethylammonium-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene etc.
About the combined amount that to have 1 above carbonatoms be the aromatic monohydroxy compound of the alkyl substituent more than 5 of further adding in the poly carbonate resin composition, with respect to 100 weight part polycarbonate resins, above-mentioned aromatic monohydroxy compound is 0.001 weight part～1 weight part, be preferably 0.01 weight part～0.5 weight part, 0.02 weight part～0.3 weight part more preferably.
When the combined amount of antioxidant was very few, the painted inhibition during sometimes to moulding was insufficient.In addition, if the combined amount of antioxidant is too much, then the dirt settling to metal pattern increases during injection molding, and the dirt settling when perhaps carrying out the moulding of film by extrusion moulding on roller increases, thereby causes the appearance of goods may be impaired.
In addition, in the scope of not damaging purpose of the present invention, also can in poly carbonate resin composition of the present invention, mix releasing agent, during with further raising melt molding from the release property of mould separating.As such releasing agent, the natural animal such as high-grade aliphatic ester, beeswax that can enumerate higher fatty acid, monohydroxy-alcohol or polyvalent alcohol is that natural oils such as natural plant wax, solid paraffin such as wax, carnauba wax are natural coal measures wax such as wax, montanin wax, olefines wax, silicone oil, organopolysiloxane etc.
As higher fatty acid, preferred carbonatoms is 10～30 saturated fatty acid.As such saturated fatty acid, can enumerate tetradecanoic acid, lauric acid, palmitinic acid, stearic acid, docosoic etc.
As high-grade aliphatic ester, preferred carbonatoms is 1～20 monobasic or polyvalent alcohol with carbonatoms is the part ester of 10～30 saturated fatty acid or ester entirely.As part ester or the full ester of described monobasic or polyvalent alcohol and saturated fatty acid, can enumerate glyceryl monostearate, stearic acid two glyceryl ester, glycerol stearate, stearic acid list sorbitol ester, stearyl stearate docosoic direactive glyceride docosoic 20 diester, pentaerythritol monostearate, pentaerythritol tetrastearate, tetramethylolmethane four pelargonates, propylene glycol monostearate, the stearic acid octadecyl ester, cetyl palmitate, butyl stearate, Laurate methyl, Wickenol 111, diphenic acid biphenyl ester (PVC Off エ ニ Le PVC Off エ ネ one ト), sorbitan monostearate, stearic acid-2-ethylhexyl etc.Wherein, preferably use glyceryl monostearate, glycerol stearate, pentaerythritol tetrastearate, docosoic 20 diester.
These releasing agents can be used alone, and also can two or more mixing use.Be 100 weight parts with polycarbonate resin, the content of described releasing agent is preferably 0.0001～2 weight part.
Can in the scope of the goal of the invention of not damaging the application, in poly carbonate resin composition of the present invention, contain static inhibitor.As static inhibitor, for example can enumerate polyether ester amides, Zerol, Witco 1298 Soft Acid ammonium salt, ten dialkyl benzene sulfonic acid phosphonium salts, maleic anhydride direactive glyceride, maleic anhydride two glyceryl ester etc.
Can in the scope of the goal of the invention of not damaging the application, in poly carbonate resin composition of the present invention, contain UV light absorber, photostabilizer.Specifically can enumerate for example 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole, 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-2H-benzotriazole, 2,2 '-to phenylene two (1,3-benzoxazine-4-ketone) etc.With respect to polycarbonate resin 100 weight parts, the content of stablizer is preferably 0.01～2 weight part.
Can mix bluing agent in the polycarbonate resin that the present invention uses, with the lens yellowing due to elimination polymkeric substance or the UV light absorber.As bluing agent, just can use so long as can be used for the material of polycarbonate resin in the past, there is not special requirement.Usually, the anthraquinone based dye obtains easily and becomes preferred bluing agent.
As concrete bluing agent, can enumerate for example general solvent violet 13[CA.No by name (Colour index number) 60725], general solvent purple 31 by name [CA.No 68210], general solvent violet 33[CA.No 60725 by name], general solvent blue 94[CA.No 61500 by name], general solvent violet 36[CA.No 68210 by name], general solvent blue 97[by name Beyer Co., Ltd " the Macrolex Violet RR " that make] and general solvent blue 45[CA.No61110 by name] typical example.These bluing agents can be used alone, and also can two or morely share.When being 100 weight parts with Copolycarbonate, mix 0.1 * 10 usually -5～2 * 10 -4The bluing agent of the ratio of weight part.
When making poly carbonate resin composition of the present invention, can be with mentioned component simultaneously or mix to make with mixing machines such as tumbler mixer, V-Mixer, Nautamixer, Banbury mixer, mill, forcing machines in any order.In addition, in the scope of not damaging purpose of the present invention, can also contain normally used nucleator, fire retardant, inorganic filler, modified impact agent, whipping agent in the resin combination, dye pigment etc.
In the present embodiment, obtained carrying out the polycarbonate resin moldings that the moulding of above-mentioned polycarbonate resin or poly carbonate resin composition becomes.Forming method to polycarbonate resin moldings has no particular limits, preferred injection moulding.
[3] blooming
Use polycarbonate resin of the present invention, can obtain blooming by film processed.In addition, stretch by the described blooming that film processed is obtained, can make phase retardation film.As film-forming method, can enumerate existing known extrusion by melting, solution casting method etc.
Need to prove, raw material as above-mentioned blooming, except polycarbonate resin of the present invention, can also be with by dihydroxyphenyl propane, other polycarbonate resins that bisphenol Z etc. obtain, through 9,9-two (4-hydroxy phenyl) fluorenes, 9,9-two (3-methyl-4-hydroxy phenyl) fluorenes, polycarbonate resin and the vibrin of modifications such as 9,9-two (3-ethyl-4-hydroxy phenyl) fluorenes, polyethylene terephthalate, polybutylene terephthalate, poly-naphthalene dicarboxylic acids ester, poly-cyclohexane dicarboxylic acid cyclohexanedimethyleterephthalate ester, the composition more than a kind or 2 kinds in other the resin such as vibrin such as poly terephthalic acid cyclohexanedimethanoester ester.
Phase retardation film is the phase retardation film that is made of 1 polymer alignment film, it is characterized in that, it satisfies following condition (i)～(iv), and more big the closer to long wavelength side to the phase differential of 630nm at wavelength 450nm.
(i) (below be called " the 1st monomeric unit ") and polymer with the anisotropic high polymer monomer of negative specific refractory power unit (below be called " the 2nd monomeric unit ") constitute to have the anisotropic high polymer monomer of positive specific refractory power unit by containing;
(ii) based on the high molecular Re450/Re550 of the 1st monomeric unit than little (wherein, " Re450 " expression " this high molecular phase differential under the wavelength 450nm " of high molecular Re450/Re550 based on the 2nd monomeric unit; " Re550 " expression " 550 times these high molecular phase differential of wavelength ");
(iii) has positive specific refractory power anisotropy;
(iv) the absolute value by photoelastic coefficient is 20 * 10 -12Pa -1Following polymer constitutes.
The polycarbonate resin of the application of the invention can easily be realized above-mentioned condition.
The thickness of blooming is generally 30 μ m～200 μ m, is preferably 50 μ m～150 μ m.In addition, the phase difference value of the film that film processed obtains is preferably below the 20nm, more preferably below the 10nm.The phase difference value of film is excessive, and the face content at phase difference value when then stretching to make phase retardation film is prone to big fluctuation.
The drawing process of blooming can adopt known vertically, laterally in unilateral stretching, the drawing process such as two-way stretch that stretch respectively of direction in length and breadth of either direction.In addition, can also implement special two-way stretch, the specific refractory power of controlling diaphragm on three-dimensional.
Preferably carry out in the scope of the second-order transition temperature-20 of pleurodiaphragmatic in terspace material ℃～+ 40 ℃ the stretching condition aspect that phase retardation film is made.Preferred scope is the scope of pleurodiaphragmatic in terspace material second-order transition temperature-10 ℃～+ 20 ℃.Compare with the second-order transition temperature of polycarbonate resin, draft temperature is crossed when hanging down, and the phase differential of stretched film increases, and in order to obtain desired phase differential, must reduce draw ratio, causes the fluctuation of the phase differential in the face to become big easily.On the other hand, compare with second-order transition temperature, when draft temperature was too high, the phase differential of the film that obtains diminished, and in order to obtain desired phase differential, must increase draw ratio, and suitable stretching condition scope narrows down.
Phase retardation film can be used as various liquid crystal indicator polarizers.Under the situation of phase retardation film for the colorimetric compensation purposes of stn liquid crystal display unit, its phase difference value is selected to the scope of 2000nm at 400nm usually.In addition, use under the situation of phase retardation film as 1/2 wavelength plate, its phase difference value is selected to the scope of 400nm at 200nm.Use under the situation of phase retardation film as 1/4 wavelength plate, its phase difference value is selected to the scope of 200nm at 90nm.As 1/4 wavelength plate and preferred phase difference value is 100nm～180nm.Phase retardation film can use separately, also can make up more than 2 and to use, and can also be used in combination with other films etc.
Phase retardation film can be fitted by the polaroid lamination of tackiness agent and known iodine system or dyestuff system.When carrying out lamination, need the slow axis of the polarizing axis of polaroid and phase retardation film be remained on specific angle according to purposes and carry out lamination.In addition, can also be with phase retardation film as 1/4 wavelength plate, with it and the polaroid lamination is fitted and as the circular polarization tabula rasa.In this case, keep the polarizing axis of polaroid and the slow axis of phase retardation film substantially to keep 45 ° of relative angles and lamination usually.In addition, can also be with phase retardation film as the polarized light protective membrane that constitutes polaroid.In addition, the colorimetric compensation plate of phase retardation film as the stn liquid crystal display unit can also be fitted itself and polaroid lamination, thus serve as the elliptical polarization tabula rasa.
[4]＜mineral filler 〉
In addition, the polycarbonate resin that uses the present invention to use has prepared the poly carbonate resin composition that wherein is mixed with mineral filler.With respect to 100 weight part polycarbonate resins, the combined amount of mineral filler is 1 weight part～100 weight parts, is preferably 3 weight parts～50 weight parts.When the combined amount of mineral filler was very few, reinforced effects was little; When combined amount is too much, the easy variation of outward appearance.
As mineral filler, can enumerate for example Calucium Silicate powder such as glass fibre, glass milled fiber, glass flake, granulated glass sphere, carbon fiber, silicon-dioxide, aluminum oxide, titanium oxide, calcium sulfate powder, gypsum, crystal whisker of gypsum, barium sulfate, talcum, mica, wollastonite; Carbon black, graphite, iron powder, copper powder, molybdenumdisulphide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, Stainless Steel Fibre, potassium titanate fiber, whisker etc.Among these, the preferred glass fibers shape is filled material, the glass powdery is filled material, glass sheet filling material; The carbon fiber shape is filled material, the carbon dust shape is filled material, carbon plate shape filling material; Various whiskers, mica, talcum.More preferably glass fibre, glass flake, glass milled fiber, carbon fiber, wollastonite, mica, talcum.
In addition, in the mineral filler, as glass fibre, glass milled fiber, as long as it is the fiber that is used for thermoplastic resin at present, just all can use.Preferred especially non-alkali glass (E glass).The diameter of glass fibre is preferably 6 μ m～20 μ m, more preferably 9 μ m～14 μ m.When the diameter of glass fibre is too small, cause the reinforced effects deficiency easily.In addition, when diameter is excessive, easily products appearance is produced detrimentally affect.
In addition, as glass fibre, can enumerate the chopped strand that preferably is cut into length 1mm～6mm; Preferred powder is broken into the commercially available glass milled fiber of length 0.01mm～0.5mm.These can use separately or both mix use.
In order to improve the adaptation with polycarbonate resin, can utilize silane coupling agents such as aminosilane, epoxy silane etc. that the glass fibre that the present invention uses is implemented surface treatment, perhaps in order to improve processing, the glass fibre that can utilize acrylic resin, polyurethane series resin etc. that the present invention is used is implemented to assemble and is handled.
As granulated glass sphere, as long as it is the granulated glass sphere that is used for thermoplastic resin at present, just all can use.Wherein, preferred non-alkali glass (E glass).The vpg connection of granulated glass sphere, preferable particle size 10 μ m～50 μ m's is spherical.
As glass flake, can enumerate lepidiod glass flake.The maximum diameter of the glass flake behind the mixed polycarbonate resin is generally below the 1000 μ m, is preferably 1 μ m～500 μ m, and the slenderness ratio ratio of thickness (maximum diameter with) be more than 5, be preferably more than 10, more preferably more than 30.
Carbon fiber is not particularly limited, for example can enumerate with acrylic fibre, oil or carbon be special pitch, cellulosic fibre, xylogen etc. be the fired manufacturing of raw material, carbon fiber such as fire-resistant, carbonaceous, graphite matter.The mean value of the length-to-diameter ratio of carbon fiber (fiber length/fiber footpath) is preferably more than 10, more preferably more than 50.When the mean value of length-to-diameter ratio was too small, the electroconductibility of poly carbonate resin composition, intensity, rigidity were tending towards reducing.The footpath of carbon fiber is 3 μ m～15 μ m, in order to adjust above-mentioned length-to-diameter ratio, can use arbitrary shapes such as chopped strand, rove fiber, milled fiber.Carbon fiber can use to mix more than a kind or 2 kinds and use.
In the scope of the characteristic of not damaging poly carbonate resin composition of the present invention, in order to strengthen the affinity with polycarbonate resin, can be to surface treatments such as carbon fiber embodiment such as epoxy finishes, carbamate processing, oxide treatment.
In the present embodiment, interpolation period, the addition means of the mineral filler that the subtend polycarbonate resin mixes are not particularly limited.As interpolation period, for example make under the situation of polycarbonate resin with ester-interchange method, can enumerate interpolation when polyreaction stops; In addition, no matter adopt any polymerization, all can enumerate when the medium polycarbonate resin of mixing process of polycarbonate resin and other mixture is in molten state and add; Use that forcing machine etc. mixes with the polycarbonate resin of solid states such as particle or powder, interpolation etc. when mixing.As addition means, it can be the method to the direct mixing of polycarbonate resin or mixing mineral filler; Also can add with the master batch form of using the high density that a spot of polycarbonate resin or other resin etc. and mineral filler make.
[5]＜fire retardant 〉
In addition, also prepared the poly carbonate resin composition that in the polycarbonate resin that the present invention uses, is mixed with fire retardant.The combined amount of fire retardant can be selected according to the kind of fire retardant, the degree of flame retardant resistance.In the present embodiment, with respect to 100 weight part polycarbonates, fire retardant is 0.01 weight part～30 weight parts, and preferred range is 0.02 weight part～25 weight parts.By mixing fire retardant, can obtain the poly carbonate resin composition of excellent in flame retardance.
As fire retardant, for example can enumerate P contained compound flame retardant, halogen contained compound flame retardant, metal organic sulfonate flame retardant, silicon-containing compound flame retardant etc.In the present embodiment, can from these classifications, select at least a fire retardant to use.These fire retardants may be used alone in combination of one kind or two or more kinds.
As the P contained compound flame retardant, for example can enumerate phosphoric acid ester based compound, phosphine nitrile based compound, red phosphorus, encapsulated red phosphorus, poly-phosphate based compound etc.With respect to 100 weight part polycarbonate resins, the combined amount of P contained compound flame retardant is preferably 0.1 weight part～20 weight parts.When combined amount is very few, be difficult to obtain enough flame retardant resistances, and thermotolerance takes place and reduces in combined amount easily when too much.
As the halogen contained compound flame retardant, for example can enumerate tetrabromo-bisphenol, tribromophenol, brominated aromatic triazine, tetrabromo-bisphenol epoxy oligomer, tetrabromo-bisphenol epoxy polymer, decabromodiphynly oxide, tribromo allyl ethers, tetrabromobisphenol A carbonic ester oligopolymer, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, brominated Polystyrene, hexabromocyclododecane etc.
With respect to 100 weight part polycarbonate resins, the combined amount of halogen contained compound flame retardant is 0.1 weight part～20 weight parts.When the combined amount of halogen contained compound flame retardant is very few, be difficult to obtain enough flame retardant resistances, and combined amount is when too much, then physical strength reduces, and sometimes fire retardant separate out the reason that can become variable color.
As the metal organic sulfonate flame retardant, for example can enumerate aliphatic sulfonic metal-salt, aromatic sulphonic acid metal-salt, perfluoroalkane hydrocarbon-metal organic sulfonate etc.As the metal in these metal-salts, be preferably the metal of periodictable the 1st family, the metal of periodictable the 2nd family etc.Specifically, be basic metal such as lithium, sodium, potassium, rubidium, caesium; Alkaline-earth metals such as calcium, strontium, barium; Beryllium, magnesium.
In the metal organic sulfonate flame retardant, from the angle of flame retardant resistance and thermostability, optimization aromatic sulfone metal organic sulfonate, perfluoroalkane hydrocarbon-metal organic sulfonate etc.
As aromatic series sulfone metal organic sulfonate, optimization aromatic sulfone sulfonic acid alkali metal salts, aromatic series sulfone sulfonic acid alkali earth metal salt.These fire retardants can be polymkeric substance.Concrete example as aromatic series sulfone metal organic sulfonate, can enumerate the sodium salt of sulfobenzide-3-sulfonic acid for example, the sylvite, 4 of sulfobenzide-3-sulfonic acid, the sodium salt, 4 of 4 '-dibromo phenylbenzene-sulfone-3-sulfonic acid, the sylvite of 4 '-dibromo phenylbenzene-sulfone-3-sulfone, 4-the chloro-4 '-nitro sulfobenzide-calcium salt of 3-sulfonic acid, sulfobenzide-3, the disodium salt of 3 '-disulfonic acid, sulfobenzide-3, the di-potassium of 3 '-disulfonic acid etc.
As perfluoroalkane hydrocarbon-metal organic sulfonate, an alkali metal salt of preferred perfluoroalkane hydrocarbon-sulfonic acid, the alkali earth metal salt of perfluoroalkane hydrocarbon-sulfonic acid etc.In addition, more preferably have sulfonic acid alkali metal salts that carbonatoms is 4～8 perfluoroalkane alkyl, to have carbonatoms be sulfonic acid alkali earth metal salt of 4～8 perfluoroalkane alkyl etc.
As the concrete example of perfluoroalkane hydrocarbon-metal organic sulfonate, can enumerate tetraethyl-ammonium salt of for example perfluorinated butane-sodium sulfonate, perfluorinated butane-potassium sulfonate, perfluoro-methyl butane-sodium sulfonate, perfluoro-methyl butane-potassium sulfonate, PFO-sodium sulfonate, PFO-potassium sulfonate, perfluorinated butane-sulfonic acid etc.
With respect to 100 weight part polycarbonates, the combined amount of metal organic sulfonate flame retardant is preferably 0.01～5 weight part.The combined amount of metal organic sulfonate flame retardant is very few, then is difficult to obtain enough flame retardant resistances, and combined amount is too much, then causes thermostability to reduce easily.
As the silicon-containing compound flame retardant, the substituting group of for example can enumerate silicone varnish, being combined with Siliciumatom by aromatic hydrocarbyl and carbonatoms be silicone resin, main chain that the aliphatic alkyl more than 2 is formed be have the silicone compounds of aromatic series base in branched structure and the organo-functional group that contains, the surface of SiO 2 powder supports the silicone powder of the polydiorganosiloxane polymkeric substance that has or do not have functional group, organopolysiloxane-Copolycarbonate etc.Among these, preferred silicone varnish.
As silicone varnish, for example can enumerate mainly by 2 functional-type unit [R0 2SiO] and 3 functional-type unit [R0SiO 1.5] constitute and contain 1 functional-type unit [R0 sometimes 3SiO 0.5] and/or 4 functional-type unit [SiO 2] the lower solution shape silicone resin of molecular weight.Herein, R0 is that carbonatoms is that more than one substituent carbonatoms is arranged is 1～12 alkyl for 1～12 alkyl or replacement.As substituting group, can enumerate epoxy group(ing), amino, hydroxyl and vinyl etc.By changing the kind of R0, can improve the consistency with matrix resin.
As silicone varnish, can enumerate solvent-free silicone varnish, contain the silicone varnish of solvent etc.In the present embodiment, preferred not solvent-laden silicone varnish.Silicone varnish can be made by for example hydrolysis of alkylalkoxy silanes such as alkyltrialkoxysilaneand, dialkyl dialkoxy silicane, trialkyl organoalkoxysilane, tetraalkoxysilane.Mol ratio by adjusting these raw materials, hydrolysis rate etc. can be controlled structure (degree of crosslinking) and the molecular weight of molecule.In addition, according to creating conditions, might residual organoalkoxysilane, but remain in the composition, the hydrolytic resistance of polycarbonate resin can reduce sometimes, so preferred residual organoalkoxysilane be on a small quantity or noresidue.
The viscosity of silicone varnish is preferably below 300 centistokes, more preferably below 250 centistokes, more preferably below 200 centistokes.The viscosity of silicone varnish is excessive, and then flame retardant resistance is not enough sometimes.
With respect to 100 weight part polycarbonate resins, the combined amount of silicon-containing compound flame retardant is preferably 0.1～10 weight part.The combined amount of silicon-containing compound flame retardant is very few, then is difficult to obtain enough flame retardant resistances, and combined amount is too much, and then thermotolerance easily reduces.
In the present embodiment, in order to realize higher flame retardant resistance, preferably share anti-dripping and use tetrafluoroethylene.Anti-dripping is dispersed in the polymkeric substance easily with tetrafluoroethylene, and polymkeric substance is bonded to each other makes fibrous material easily.Can enumerate for example Teflon (registered trademark) 6J, Teflon (registered trademark) 30J (fluorine chemistry Co., Ltd. of Mitsui Du Pont), POLYFLON F201L (big aurification Industrial Co., Ltd) etc. as the commercially available tetrafluoroethylene of the anti-usefulness of dripping.
With respect to 100 weight part polycarbonate resins, prevent that the combined amount of dripping with tetrafluoroethylene is preferably 0.01 weight part～2.0 weight parts.Anti-drip very few with the combined amount of tetrafluoroethylene, the effect deficiency of dripping of the fusion when then preventing from burning, if combined amount is too much, the easy variation of moulding product outward appearance then.
In addition, in the scope of not damaging effect of the present invention, can in poly carbonate resin composition of the present invention, add the various additives of the amount that shows its effect.As additive, can enumerate for example stablizer, UV light absorber, releasing agent, tinting material, static inhibitor.In addition, in order to obtain other various uses, desired performance, can also the benzene mixed vinylite, thermoplastic resin such as polyester based resin; Thermoplastic elastomer; Inorganic fillers such as glass fibre, glass flake, granulated glass sphere, carbon fiber, wollastonite, Calucium Silicate powder, aluminium borate whisker etc.
Blending means, the mixing of the polycarbonate resin that present embodiment is used and above-mentioned additive etc. are not particularly limited period, for example, as mixing period, can be in polymerization process or polyreaction add when stopping, can also under the state of the medium polycarbonate melt of mixing process of polycarbonate etc., add.In addition, can also mix the back with the polycarbonate of solid states such as particle or powder carries out mixing with forcing machine etc.
[6]＜UV light absorber 〉
In addition, in the present embodiment, can prepare the poly carbonate resin composition that in the polycarbonate resin that the present invention uses, is mixed with UV light absorber.The combined amount of UV light absorber can be selected according to the kind of UV light absorber.In the present embodiment, with respect to 100 weight part polycarbonates, UV light absorber is 0.005 weight part～5 weight parts.
Herein, as UV light absorber, so long as have the compound of ultraviolet absorption ability, just be not particularly limited.In the present embodiment, preferably has the compound of absorption at wavelength 200nm～240nm.In addition, preferably, to the specific absorbance ε of the light of wavelength 200nm～240nm greater than 10000mL/ (gcm), be preferably the above compound of 15,000mL/ (gcm).
Expression can be measured according to JIS K0115 " photometric analysis of extinction general rule " as the absorbancy of the ultraviolet absorption ability of UV light absorber.In addition, specific absorbance ε is difficult to the mole indicated concentration, so the present embodiment note is made mL/ (gcm).Be as the criterion with above-mentioned JIS K0115 in addition.
The mensuration of＜molar absorptivity 〉
In the present embodiment, measure molar absorptivity by following method.
Based on JIS K0115 " photometric analysis of extinction general rule ", in vial, in the about 10mg UV light absorber of 10ml acetonitrile dissolving.Therefrom take out 0.1ml and put into another vial, further add the 9.9ml acetonitrile it is dissolved.With pack into the quartz colorimetric utensil of optical length 10mm of this solution, (Japanese light splitting society makes, V-570) to use ultraviolet-visible pectrophotometer, mode determination Abs, sensitivity is set in Medium, to measure wavelength 190～800nm, in the measuring space absorbance A of bandwidth 2nm.The absorbance A of molar absorptivity ε by being used in each wavelength divided by the optical length L of the volumetric molar concentration c of solution and cuvette amass obtain.In addition, the volumetric molar concentration c of solvent obtains divided by the molecular weight of UV light absorber by the concentration with solution.For the molar absorptivity ε of the UV light absorber of obtaining, preferred molar absorptivity (ε at wavelength 210nm place among the present invention 210) with scope from wavelength 250nm to wavelength 350nm the maximum value (ε of molar absorptivity 250-350) ratio (ε 210/ ε 250-350) less than 1.75, be more preferably less than 1.73, be preferably less than 1.72 especially.
In the present embodiment, as the compound with ultraviolet absorption ability, can enumerate organic compound, mineral compound.Wherein, organic compound is guaranteed the affinity of itself and polycarbonate resin easily, and evenly disperses easily, so be preferred.
Molecular weight to organic compound with ultraviolet absorption ability is not particularly limited.Molecular weight is generally more than 200, is preferably more than 250.And be generally below 600, be preferably below 450, more preferably below 400.Molecular weight is too small, and then there is the possibility that causes that the UV resistant performance reduces in the long-term chien shih time spent.Molecular weight is excessive, and then there is the possibility that the transparency of resin combination reduces in the long-term chien shih time spent.
As preferred UV light absorber, can enumerate benzotriazole based compound, benzophenone based compound, triazine based compound, benzoic ether (salt) based compound, hindered amine based compound, salol based compound, cyanoacrylate based compound, malonic ester based compound, oxanilide based compound etc.Wherein, preferably use triazine based compound, malonic ester based compound, oxanilide based compound.These compounds can use separately also and can share more than 2 kinds.
Example more specifically as the benzotriazole based compound, can enumerate 2-(2 '-hydroxyl-3 '-methyl-5 '-hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-methyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's dodecylphenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-methyl-5 '-uncle's dodecylphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, methyl-3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) propionic ester etc.
As the triazine based compound, can enumerate 2-[4-[(2-hydroxyl-3-dodecyl oxygen base propyl group) the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazine, 2,4-two (2,4-3,5-dimethylphenyl)-6-(the different octyloxyphenyl of 2-hydroxyl-4-)-s-triazine, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and the 5-[(hexyl) the oxygen base]-phenol (vapour Ba-Jia Ji society manufacturing, Tinuvin1577FF) etc.
As the dihydroxy benaophenonel based compound, can enumerate 2,2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2-hydroxyl-4-octyloxy benzophenone etc.
As the cyanoacrylate based compound, can enumerate ethyl-2-cyano group-3,3-diphenylacrylate ester, 2 '-ethylhexyl-2-cyano group-3,3-diphenylacrylate ester etc.
As the malonic ester based compound, can enumerate 2-(1-aryl alkylene) malonic ester class etc.Wherein, preferred propanedioic acid [(4-p-methoxy-phenyl)-methylene radical]-dimethyl esters (manufacturing of Clariant society, HostavinPR-25), 2-(to the anisole methylene radical) propanedioic acid dimethyl esters.
As the oxanilide based compound, can enumerate 2-ethyl-2 '-oxyethyl group-oxanilide (manufacturing of Clariant society, SanduvorVSU) etc.
Among these, preferred 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-[4-[(2-hydroxyl-3-dodecyl propoxy-) the oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazine, 2,2 ', 4,4 '-tetrahydroxybenzophenone.
Blending means, the mixing of the polycarbonate resin that present embodiment is used and above-mentioned additive etc. are not particularly limited period.For example, as mixing period, can be in polymerization process or polyreaction add when stopping, can also under the state of the medium polycarbonate melt of mixing process of polycarbonate etc., add.In addition, after can also mixing with the polycarbonate of solid states such as particle or powder, carry out mixing with forcing machine etc.
When making poly carbonate resin composition of the present invention, can be with mentioned component simultaneously or mix to make with mixing machines such as tumbler mixer, V-Mixer, Nautamixer, Banbury mixer, mill, forcing machines in any order.In addition, in the scope of not damaging purpose of the present invention, can also contain normally used nucleator, fire retardant, inorganic filler, modified impact agent, whipping agent in the resin combination, dye pigment etc.
[7]＜thermoplastic resin 〉
In addition, in the present embodiment, can be manufactured on the poly carbonate resin composition that is mixed with thermoplastic resin in the polycarbonate resin that the present invention uses.Combined amount to polycarbonate resin and thermoplastic resin has no particular limits, and the scope in the present embodiment is polycarbonate resin 10 weight parts～90 weight parts and thermoplastic resin 90 weight parts～10 weight parts.
As thermoplastic resin, for example can enumerate aromatic polyester resins such as polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid cyclohexanedimethanoester ester herein; Saturated polyesters such as aliphatic polyester based resin such as poly(lactic acid), polybutylene succinate, poly-cyclohexane dicarboxylic acid cyclohexanedimethanoester ester are resin; The bis-phenol that is obtained by various bisphenols such as dihydroxyphenyl propane, bisphenol Z is polycarbonate resin; By 3 (4), the polycarbonate-based resin of ester ring type that ester ring type glycol such as 8 (9)-two (hydroxymethyl) three ring [5.2.1.02,6] decane obtain; By 3,9-two (1,1-dimethyl-2-hydroxyethyl)-2,4,8, the aliphatic polycarbonate that heterocycle glycol such as 10-four oxaspiros [5,5] undecane obtain is polycarbonate-based resins such as resin; 6, fatty polyamides such as 66,46,12 are resin; Semiaromatic polyamide compositions such as 6T, 6I, 9T are polyamide-based resins such as resin; Polystyrene resin, high-impact polystyrene are that resin, vinyl cyanide/phenylethylene resin series (AS), acrylonitrile/butadiene/styrene are phenylethylene resin series such as resin (ABS), hydrogenation ABS resin (AES), crystallinity syndiotactic polystyrene resin; Acrylic resin such as PMMA, MBS; Low density, middle density, high density polyethylene(HDPE), ethylene/methacrylic acid ester copolymer (EMA), ethylene (EVA), ethylene/methacrylic acid glycidyl ester copolymer polyethylene copolymers such as (E/GMA) are resin; Polypropylene-based resin, 4-methyl-amylene-1-resin, cyclic olefin polymer (COP), cyclic olefine copolymer (gathering) ethylene series resins such as (COC); Thermoplastic resin or these mixtures such as polyacetal resin, polyamide-imide resin, polyethersulfone resin, polyimide resin, polyphenylene oxide resin, polyphenylene sulfide, Polyphenylene Sulfone resin, polyether-ether-ketone resin, liquid crystalline polyester resin, TPU(Thermoplastic polyurethanes), polyvinyl chloride (PVC) RESINS, fluoro-resin.
These thermoplastic resins can use a kind, or mix more than 2 kinds and use, and can suitably select to use according to characteristics such as using the required thermotolerance of order, reagent resistance, formability.In addition, can also carry out graft modification or the use of end modified back with unsaturated compounds such as maleic anhydrides.
Blending means, the mixing of the polycarbonate resin that present embodiment is used and above-mentioned additive etc. are not particularly limited period.For example, as mixing period, can be in polymerization process or polyreaction add when stopping, can also under the state of the mixing medium polycarbonate melt of polycarbonate etc., add.In addition, after can also mixing with the polycarbonate of solid states such as particle or powder, carry out mixing with forcing machine etc.
When making poly carbonate resin composition of the present invention, can be with mentioned component simultaneously or mix to make with mixing machines such as tumbler mixer, V-Mixer, Nautamixer, Banbury mixer, mill, forcing machines in any order.In addition, in the scope of not damaging purpose of the present invention, can also contain normally used nucleator, fire retardant, inorganic filler, modified impact agent, whipping agent in the resin combination, dye pigment etc.
Embodiment
Below, the present invention will be described in more detail by embodiment.But the present invention is not limited to the embodiment shown in following.
Hereinafter, carry out the physicals of polycarbonate resin and poly carbonate resin composition, the evaluation of characteristic by following method.
(1) reduced viscosity
Use Ubbelohde viscometer (central physics and chemistry DT-504 type processed automatic viscometer), use 1: 1 mixed solvent of phenol and sym.-tetrachloroethane as solvent, measure for 30.0 ℃ ± 0.1 ℃ in temperature.The concentration fine setting is 1.00g/dl.
In 120 ℃ of stirred samples, dissolved the back mensuration that is used for of cooling with 30 minutes.
The time of passing through t by solvent 0, solution the time of passing through t, obtain relative viscosity η according to following formula Rel,
η rel＝t/t 0(g·cm -1·sec -1)
By relative viscosity η Rel, obtain specific viscosity η according to following formula Sp
η sp＝(η-η 0)/η 0＝η rel-1
Use specific viscosity η SpDivided by concentration c (g/dl), obtain reduced viscosity (conversion viscosity) η according to following formula Red
η red＝η sp/c
η RedNumerical value is more high, and molecular weight is more big.
(2) form and aspect are measured
Use colour examining colour-difference-metre (" ZE-2000 " that Japanese electric look society makes), utilize the illuminant-C penetrant method to measure 3 valuess of look, calculate yellowness index (YI) value as the index of yellow variable color by following formula.
Yellowness index YI=100 * (1.28X-1.06Z)/Y
(3) hydrolytic resistance
For through with the mixing particle that obtains of twin screw extruder, carry out pressure cooking test test; At 110 ℃ (1.5 * 10 5Pa) leave standstill 24 hours.After the test, sample is at 100 ℃, 1.3 * 10 3 Dry 5 hours of Pa, remove moisture after, the reduced viscosity separately of sample before and after the test is measured, calculate the reduced viscosity conservation rate according to following formula.
Reduced viscosity conservation rate (%)=(reduced viscosity before test back reduced viscosity/test) * 100
(4) injection molding evaluation (conventional moulding Δ YI, bad order product rate, bad, the metal pattern dirt settling of the demoulding)
For through with the mixing particle that obtains of twin screw extruder, use injection moulding machine (Sumitomo Heavy Industries, Ltd makes MINIMAT 8/7A), implement 100 moulding injection at 240 ℃, after obtaining the flat-plate molded product of 30mm * 30mm * 2mmt, for form and aspect, measure above-mentioned YI (note is made " the mixing product YI of additive ").
Conventional moulding Δ YI is following calculating.In aftermentioned like that to unmixed acidic cpd in previously prepared 4 kinds of polycarbonate resins (PC Resin A, PC resin B, PC resin C, PC resin D) etc. and the flat-plate molded product that moulding obtains measure, be benchmark with the YI that so obtains (note is done " not adding additive product YI "), calculate according to following formula.
The mixing product YI-of conventional moulding Δ YI ≡ additive does not add additive product YI
Herein, 3 kinds of polycarbonate resin not interpolation additive product YI aspects separately, the PC Resin A is benchmark with the YI of embodiment 13, the PC resin B is benchmark with the YI of embodiment 16, PC resin D is benchmark with the YI of comparative example 10, what use except PC resin C is the PC resin C-1, and other measuring are similarly to Example 13 used the YI that obtains separately.
The following calculating of bad order product rate (%): calculate bad order product quantity such as gray bar, blackstreak by following formula with respect to the ratio of the quantity of whole moulding product.
Bad order product rate ≡ bad order product quantity/whole moulding product quantity
Bad and the metal pattern dirt settling about the demoulding, for through with the mixing particle that obtains of twin screw extruder, to carry out 4 hours preparation dry granules at 80 ℃ is the flat board of 60mm * 60mm * 3mmt with JSW's J75EII type processed injection moulding machine at the condition compacted under of 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature, each forming materials 100 times injection has or not the dirt settling amount of the fixation side metal pattern after the bad generation of the demoulding and the moulding 100 times in the visual observation moulding.
(5) evaluation (Δ YI is detained in moulding) is detained in moulding
For through with the mixing particle that obtains of twin screw extruder, use injection moulding machine (Sumitomo Heavy Industries, Ltd makes MINIMAT 8/7A), 240 ℃ of barrel temperatures, carry out the moulding product (conventional moulding product) of 7 moulding injections and the resin delay moulding product that 7 moulding of enforcement are injected after 10 minutes (delay moulding product) that in shaper, maintain the original state (240 ℃) in the presence of by ordinary method, after obtaining 30mm * 30mm * 2mmt flat-plate molded product, form and aspect for each moulding product, measure above-mentioned YI, after obtaining each mean value before and after being detained, calculate moulding according to following formula and be detained Δ YI.
Moulding is detained Δ YI=and is detained the conventional moulding product of moulding product YI-YI
(6) terminal group structural analysis
Utilize NMR spectrometer (Bruker society makes AVANCE DRX400), use the deuterochloroform that is added with TMS as measuring solvent, measure 1H-NMR spectrum.
Belong to the terminal group shown in the above-mentioned structural formula (2) (note is made " phenyl end ") at the detected peak of chemical shift 7.3ppm～7.5ppm that with TMS is benchmark, similarly for other whole ends, respectively by each area ratio at the peak that belongs to, after calculating each terminal number of per 100 repeating units in the polymkeric substance, calculate the terminal ratio of phenyl according to following formula.
The terminal ratio (%) of phenyl=(terminal group formula (1) exists number/whole ends to have number) * 100
(7) extruded film evaluation
Will be mixing with twin screw extruder at the polycarbonate resin sample of 80 ℃ of vacuum-dryings after 5 hours, the particle that obtains is extruded at 240 ℃ with the single shaft forcing machine that front end has the T-mould, use 95 ℃ casting roll chilling then, obtain the stretching sheet of the about 100 μ m of thickness, estimate in the following order.
The bright spot foreign matter
Two polaroids are arranged to quadrature (cross Nicols), and shielding sees through light, places the film sample of making between two polaroids.Polaroid uses the glass protecting sheet.From the one-sided rayed of carrying out, add up every 1cm from offside with opticmicroscope (50 times) 2The quantity of the bright spot in the scope more than the diameter 0.01mm.
◎: bright spot quantity is 0～30
Zero: 31～50
△: 51～80
*: 81～100
* *: is more than 101
Roller contaminative (sheet formability)
Use single screw extrusion machine and sheet mould, carry out the moulding of the sheet of the about 100 μ m of thickness, visual observation volatile component this moment is estimated with following standard to the degree of adhesion of roller minute surface.
◎: adhering to of volatile component is few
Zero: adhering to of volatile component is common
△: adhering to of volatile component is many
*: the adhering to very of volatile component
(8) residual phenol amount
After resin particle is dissolved in trichloromethane, further adds methyl alcohol and carry out redeposition and handle.After its supernatant liquor centrifugation, filter with strainer, it is quantitative to implement phenol with HPLC then, calculates residual quantity.
(HPLC quantitative conditions)
Device: the Agilent science and technology agilent of society's (strain) 1100
Analytical column: Northeast chemistry (strain) Mightysil RP-18
Elutriant: 0.2% aqueous acetic acid/methyl alcohol gradient
Detect wavelength: 280nm
Post groove temperature: 40 ℃
(9) photoelastic coefficient
Use has been made up the device of the double refraction detection device that is made of He-Ne laser apparatus, polarized light device, compensating plate, analyzer, photodetector and oscillating mode determination of viscoelasticity device (Rheology Co makes DVE-3) and has been measured (specifically can will Vol.19 referring to Japanese rheology, p93-97 (1991)).
Same when carrying out the roller contamination evaluating, use single screw extrusion machine and sheet mould, the sheet of the about 100 μ m of formation thickness, cut out the sample of wide 5mm, length 20mm from sheet, be fixed in the determination of viscoelasticity device, in 25 ℃ room temperature, with the frequency measurement storage modulus E ' of 96Hz.Simultaneously, make the laser of ejaculation successively by polarized light device, sample, compensating plate, analyzer, pick up with photodetector (photodiode), pass through lock-in amplifier, at the waveform of angular frequency or 2 ω, obtain its amplitude and with respect to the phase differential of strain, and obtain strain optical coefficient O '.At this moment, the direction of polarized light device and analyzer is quadrature, and the prolonging direction that is adjusted into separately with respect to sample becomes π/4 angles.
Use storage modulus E ' and strain optical coefficient O ', obtain photoelastic coefficient C by following formula.
C＝O’/E’
(10) content (levels of residual monomers) of residual carbon acid diesters amount and the dihydroxy compound of the bond structure with structural formula (1)
After the 1.0g resin particle is dissolved in the 10ml trichloromethane, further add 20ml methyl alcohol, carry out redeposition and handle.For filtrate, use nitrogen dissolves again with the 1ml acetonitrile after concentrating and doing admittedly.With GC (gas chromatograph) carry out diphenyl carbonate quantitatively and have structural formula (1) bond structure dihydroxy compound quantitatively after, calculate residual quantity.
(GC/FID quantitative conditions)
Device: Co., Ltd. of Agilent science and technology society makes HP6890
Analytical column: GL science Co., Ltd. makes TC-1
Oven temperature: 100 ℃ * 1min. → 10 ℃/min. → 240 ℃ → 15 ℃/min. → 320 ℃ * 5min.
Detector: flame ionization ditector
Detector temperature: 325 ℃
Vector gas: He 1ml/min.
Sample injection rate: 1 μ l
In addition, below 10ppm, because the quantitative accuracy reduction, so note is made 10ppm.
The distillation of＜Isosorbide 〉
It is as follows to be used for containing the distillating method of Isosorbide of manufacturing of polycarbonate resin A, B of heterocycle herein.
After Isosorbide put into distil container, begin decompression at leisure, heat then, dissolve for about 100 ℃ in interior temperature.In interior temperature 160 ℃ begin slip out thereafter.The pressure of this moment is 133Pa～266Pa.After obtaining fore-running, implement distillation at 160 ℃～170 ℃ of interior temperature, 150 ℃～157 ℃ of tower top temperatures, 133Pa.Distillation charges into argon gas after stopping, and returns normal pressure.The distillation product that obtain are cooled off pulverizing under argon gas stream, obtain the Isosorbide of purifying through distillation.This Isosorbide together is encapsulated in the long-pending bag of aluminium lamination with AGELESS (gas chemistry society of Mitsubishi makes) under nitrogen gas stream, and the room temperature sealing is preserved.
(embodiment 1～embodiment 7)
(containing the manufacturing of the polycarbonate resin A-1 of heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part tristane dimethanols (being designated hereinafter simply as " TCDDM "), 117,957 weight part diphenyl carbonates and 2.2 * 10 through the Isosorbide of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
Add each additive with twin screw extruder continuously by the composition shown in the table 1; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the polycarbonate resin A-1 that contains heterocycle (note is made " PC Resin A-1 ") of Isosorbide/TCDDM=70/30 (mol% ratio).
Provided the polycarbonate resin A-1's that contains heterocycle among Fig. 1 (A) and Fig. 1 (B) 1The H-NMR spectrogram.Fig. 1 (B) is near the enlarged view of the part (6.2～7.8ppm) of Fig. 1 (A).
(containing the manufacturing of the polycarbonate resin B-1 of heterocycle)
Relative 73,070 weight part Isosorbides drop into 109,140 weight part diphenyl carbonates and 2.0 * 10 to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
Add each additive with twin screw extruder continuously by the composition shown in the table 1; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously, utilize tablets press to obtain containing the particle (note is made " PC resin B-1 ") of the polycarbonate resin B-1 of heterocycle.
(containing the manufacturing of the polycarbonate resin C-1 of heterocycle)
Relative 59,630 weight parts drop into 25,218 weight part 1,4 cyclohexane dimethanols (being designated hereinafter simply as " CHDM "), 124,867 weight part diphenyl carbonates (DPC) and 2.4 * 10 through the Isosorbide (ISB) of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
Add each additive with twin screw extruder continuously by the composition shown in the table 1; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the polycarbonate resin C-1 that contains heterocycle (note is made " PC resin C-1 ") of Isosorbide (ISB)/CHDM=70/30 (mol% ratio).
(comparative example 1～comparative example 6)
For comparative example 1,2, use the following polycarbonate resin A-2 that obtains (note is made " PC Resin A-2 "): make when containing the polycarbonate resin A-1 of heterocycle, the diphenyl carbonate amount of using is 115,688 weight parts, operate equally with embodiment in addition, the ratio of the phenyl end of this polycarbonate resin A-2 is less than 20%.
For comparative example 3,4, use the following polycarbonate resin B-2 that obtains (note is made " PC resin B-2 "): make when containing the polycarbonate resin B-1 of heterocycle, the diphenyl carbonate amount of using is 107,103 weight parts, operate equally with embodiment in addition, the ratio of the phenyl end of this polycarbonate resin B-2 is less than 20%.
For comparative example 5,6, use the following polycarbonate resin C-2 that obtains (note is made " PC resin C-2 "): make when containing the polycarbonate resin C-1 of heterocycle, the diphenyl carbonate amount of using is 122,994 weight parts, operate equally with embodiment in addition, the ratio of its phenyl end is less than 20%.
The results are shown in Table 1.In addition, monomer, antioxidant, the acidic cpd of record are as follows in the table 1.
(monomer)
ISB: Isosorbide
TCDDM: tristane dimethanol
BPA: dihydroxyphenyl propane
CHDM:1, the 4-cyclohexanedimethanol
(antioxidant)
IRGANOX 259:1,6-hexylene glycol-two { 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester } (manufacturing of Ciba society)
1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol esters (manufacturing of Ciba society) of IRGANOX
ADKSTAB PEP-4C: two (nonyl phenyl) pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s manufacturing)
ADKSTAB PEP-8: distearyl-pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s manufacturing)
ADKSTAB PEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacturing)
168: three (2,4-di-tert-butyl-phenyl) phosphorous acid esters (Asahi Denka Co., Ltd.'s manufacturing) of IRGAFOS
(acidic cpd)
Butyl p-toluenesulfonate: Tokyo changes into Co., Ltd. and makes
Figure BDA0000063054310000491
By the result shown in the table 1 as can be known, have from the ratio of the structural unit of Isosorbide, tristane dimethanol (dihydroxy compound with structural formula (1)) and phenyl end little in the PC of the scope more than 20% Resin A-1, PC resin B-1, PC resin C-1 (embodiment 1～embodiment 7) conventional moulding Δ YI and the moulding value of being detained Δ YI in injection molding is estimated, be in appearance painted less, material that the transparency is excellent.
On the other hand, the ratio of phenyl end is big in the value of being detained Δ YI less than PC Resin A-2, PC resin B-2, the moulding of PC resin C-2 (comparative example 1～comparative example 6) in injection molding is estimated of 20% scope, painted many on these material appearance, damaged the transparency.
(embodiment 8～embodiment 16)
Use contains the polycarbonate resin A-1 (PC Resin A-1) of heterocycle, the polycarbonate resin B-1 (PC resin B-1) that contains heterocycle, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by proportioning shown in the table 2, carry out various evaluations for the poly carbonate resin composition of preparing.The results are shown in Table 2.In addition, the photoelastic coefficient of the sample that uses among the embodiment 8 is 9 * 10 -12Pa -1
By the result shown in the table 2 as can be known, having from the structural unit of Isosorbide, tristane dimethanol and the terminal ratio of phenyl (%) is that not only conventional moulding Δ YI and moulding delay Δ YI are little for PC Resin A-1, PC resin B-1 20% or more, and particularly under the content of residual phenol is situation below the 700ppm, bad order product rate (%) during injection molding is estimated is little, and the value that Δ YI is detained in moulding is also little, is the excellent material of the transparency.
In addition, compare with the situation (embodiment 13,16) of unmixed antioxidant, owing to mix antioxidant (embodiment 8～12,14), moulding is detained Δ YI and is significantly reduced.
(embodiment 17,18)
Use the following polycarbonate resin A-3 that contains heterocycle that obtains (note is made " PC Resin A-3 ") among the embodiment 17,18: in twin screw extruder, change into and only carry out the vacuum devolatilization and do not carry out water filling, operation similarly to Example 1 in addition.
Use contains the polycarbonate resin A-3 (PC Resin A-3) of heterocycle, above-mentioned antioxidant, acidic cpd, prepares poly carbonate resin composition by the proportioning shown in the table 3, and the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 3.
(comparative example 7～comparative example 11)
Use the following polycarbonate resin A-4 that contains heterocycle that obtains (note is made " PC Resin A-4 ") in the comparative example 7: make when containing the polycarbonate resin A-1 of heterocycle, the diphenyl carbonate amount of using is 115,688 weight parts, and, in twin screw extruder, change into and only carry out the vacuum devolatilization and do not carry out water filling, in addition operation equally.
(not containing the manufacturing of the polycarbonate resin D-1 of heterocycle)
Comparative example 8,10 uses the polycarbonate resin D-1 that does not contain heterocycle of following manufacturing.
Relative 91,200 weight part dihydroxyphenyl propanes drop into 89,024 weight part diphenyl carbonates and 4.0 * 10 to reaction vessel -2Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 250 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
Add each additive with twin screw extruder continuously by the composition shown in the table 3; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously, do not contained the particle (note is made " PC resin D-1 ") of the polycarbonate resin D-1 of heterocycle with tablets press.
Comparative example 9,11 uses the following polycarbonate resin D-2 that obtains (note is made " PC resin D-2 "): change in twin screw extruder and only carry out the vacuum devolatilization and do not carry out water filling, in addition to operate equally with comparative example 8.
In addition, in the comparative example 7～11, change over the composition shown in the table 3, obtain polycarbonate resin with identical operations in addition.
With embodiment similarly, use antioxidant, acidic cpd to prepare poly carbonate resin composition according to the proportioning shown in the table 3, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 3.In addition, the photoelastic coefficient of the sample that uses in the comparative example 11 is 80 * 10 -12Pa -1
Figure BDA0000063054310000541
By the result shown in the table 3 as can be known, even polycarbonate resin of the present invention has the structural unit of peculiar chemical structure, but under the situation of terminal ratio (%) less than 20% of phenyl (comparative example 7), the value that Δ YI is detained in the moulding of this material is big, has damaged the transparency during moulding.
In addition, embodiment each other relatively the time as can be known, the content of residual phenol surpasses the polycarbonate resin A of 700ppm, and (embodiment 17,18) the bad order product rate (%) in injection molding is estimated is than higher, and the value of the moulding of this material delay Δ YI is also bigger, and the transparency has been subjected to infringement during moulding.
On the other hand, under having from the situation of the polycarbonate resin D of the structural unit of dihydroxyphenyl propane (comparative example 8～comparative example 11), at the condition of not using antioxidant (comparative example 8,9) under, even residual phenol amount is controlled below 700ppm, can not improve moulding and be detained Δ YI, the improvement degree of the rate of variation, and bad order on the contrary is also little.Therefore, the roller adhesion amount is not greatly improved yet.In addition, even use the condition (comparative example 10,11) of antioxidant, the improvement degree that Δ YI, bad order rate are detained in conventional moulding Δ Y, moulding is all little, and the roller adhesion amount does not significantly improve yet.
Relative therewith, the influence of the residual phenol that polycarbonate resin of the present invention is subjected to is big, by residual phenol amount is controlled to below the 700ppm, can improve conventional moulding Δ Y, moulding delay Δ YI, bad order rate, roller adhesion amount, especially largely improve bad order rate and roller adhesion amount.
(embodiment 19～embodiment 29)
(containing the manufacturing of the polycarbonate resin A-5 of heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part TCDDM, 117,957 weight part diphenyl carbonates and 2.2 * 10 through the Isosorbide of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
Then, after 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, molten resin is discharged from the relief outlet of container bottom, then on one side it is supplied with continuously to spectacle oar formula polymerization machine (Hitachi Co., Ltd's manufacturing), be detained 1 hour at 240 ℃ on one side, when with this setting polymerization being carried out the phenol that produces extracted out outside container.Then, will be supplied with continuously to the twin screw extruder with 3 venting ports and water injection equipment by the polycarbonate melt resin that the outlet of spectacle oar formula polymerization machine is discharged.Add each additive with twin screw extruder continuously by the composition shown in the table 1; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the copolymerized panlite A-5 (note is made " PC Resin A-5 ") of Isosorbide/TCDDM=70/30 (mol% ratio).
(the polycarbonate resin B-3 that contains heterocycle)
Relative 73,070 weight part Isosorbides drop into 109,140 weight part diphenyl carbonates and 2.0 * 10 to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, molten resin is discharged from the relief outlet of container bottom, then on one side it is supplied with continuously to spectacle oar formula polymerization machine (Hitachi Co., Ltd's manufacturing), be detained 1 hour at 240 ℃ on one side, when with this setting polymerization being carried out the phenol that produces extracted out outside container.
Next, will be supplied with continuously to the twin screw extruder with 3 venting ports and water injection equipment by the polycarbonate melt resin that the outlet of spectacle oar formula polymerization machine is discharged.Add each additive with twin screw extruder continuously by the composition shown in the table 4; after utilizing each exhaust oral area with low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the copolymerized panlite B-3 (note is made " PC resin B-3 ") of Isosorbide/TCDDM=70/30 (mol% ratio).
In addition, embodiment 29 use following obtain obtain PC Resin A-4: make when containing the polycarbonate resin A-1 of heterocycle, the diphenyl carbonate amount of using is 115,688 weight parts (DPC decrement), and in twin screw extruder, change into and only carry out the vacuum devolatilization and not water filling is similarly carried out in addition.
Use PC Resin A-1, PC Resin A-4, PC Resin A-5, PC resin B-1, PC resin B-3, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in the table 4, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 4.
[table 4]
Figure BDA0000063054310000571
By the result shown in the table 4 as can be known, having from the structural unit of Isosorbide, tristane dimethanol and the terminal ratio of phenyl (%) is under the situation more than 20%, not only conventional moulding Δ YI and moulding delay Δ YI is little, and the content of residual carbon acid diesters is that the following PC Resin A-1 of 0.1ppm～60ppm, PC Resin A-4, PC Resin A-5, PC resin B-1, the bad order product rate (%) of PC resin B-3 in injection molding is estimated are little, and the value of moulding delay Δ YI is also little, is the excellent material of the transparency.
In addition, compare with the situation (embodiment 26,28) of unmixed antioxidant, owing to mix antioxidant (embodiment 19～25,27,29), moulding is detained Δ YI and is significantly reduced.
(embodiment 30～embodiment 33)
In twin screw extruder, only carry out the vacuum devolatilization when use making the polycarbonate resin A-1 that contains heterocycle among the embodiment 30,31 and PC Resin A-3 that not water filling obtains.
Use the following polycarbonate resin A-6 that contains heterocycle that obtains (note is made " PC Resin A-6 ") among the embodiment 32: make when containing the polycarbonate resin A-1 of heterocycle, the diphenyl carbonate amount of using is 120,225 weight parts, and in twin screw extruder, only carry out the vacuum devolatilization and do not carry out water filling.
Use the following polycarbonate resin B-4 that obtains (note is made " PC resin B-4 ") among the embodiment 33: when manufacturing contains the polycarbonate resin B-1 of heterocycle, in twin screw extruder, only carry out the vacuum devolatilization and do not carry out water filling.
Use PC Resin A-3, PC Resin A-6, PC resin B-4, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in the table 5, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 5.
(comparative example 12～comparative example 16)
Use polycarbonate resin D-1 in the comparative example 12,15,16.
Use the following polycarbonate resin D-2 that obtains (note is made " PC resin D-2 ") in the comparative example 13,14: when making polycarbonate resin D-1, in twin screw extruder, only carry out the vacuum devolatilization and do not carry out water filling.Use PC resin D-1, PC resin D-2, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in the table 5, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 5.
Figure BDA0000063054310000591
By the result shown in the table 5 as can be known, composition (comparative example 12～16) contains the polycarbonate resin that does not contain from the structural unit of the dihydroxy compound of the bond structure with structural formula (1), even the terminal ratio of phenyl is more than 20%, the photoelastic coefficient of composition (comparative example 12～16) is also big, poor quality.
In addition, polycarbonate resin A (embodiment 30～33) is even have structural unit from Isosorbide, tristane dimethanol, the content of residual carbon acid diesters is also greater than 60ppm, embodiment compares as can be known each other, the bad order product rate (%) of polycarbonate resin A (embodiment 30～33) in injection molding is estimated is big, and moulding is detained Δ YI value greatly, and the transparency of this material is poor.
In addition, have from the bad order product rate (%) of the PC resin D-1 of the structural unit of dihydroxyphenyl propane and PC resin D-2 (comparative example 12～16) and moulding and be detained balanced differences between the Δ YI.
(embodiment 34～embodiment 39)
Use contains the polycarbonate resin A-1 (PC Resin A-1) of heterocycle, the polycarbonate resin A-5 (PC Resin A-5) that contains heterocycle, the polycarbonate resin B-1 (PC resin B-1) that contains heterocycle, the polycarbonate resin B-3 (PC resin B-3) that contains heterocycle, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in the table 6, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 6.
(comparative example 17～comparative example 20)
Use PC Resin A-4 in comparative example 17, the comparative example 18; Comparative example 19, comparative example 20 use polycarbonate resin B-5 (note is made " PC resin B-5 "), polycarbonate resin B-5 is following obtaining: in the manufacturing of the polycarbonate resin B-1 that contains heterocycle, use 104,860 weight part diphenyl carbonates, and in twin screw extruder, change into and only carry out the vacuum devolatilization and do not carry out water filling, carry out the manufacturing identical operations with the polycarbonate resin B-1 that contains heterocycle in addition, obtain described PC resin B-5, the content of its Isosorbide is 60ppm.
Use the above-mentioned polycarbonate resin A-1 that contains heterocycle (PC Resin A-1), A-4, A-5, polycarbonate resin B-1 (PC resin B-1), B-3, B-5, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in the table 6, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 6.
Figure BDA0000063054310000611
By the result shown in the table 6 as can be known, PC Resin A-1, PC Resin A-5 and PC resin B-1, PC resin B-3 (embodiment 34～embodiment 39) have the structural unit from Isosorbide, tristane dimethanol (dihydroxy compound with structural formula (1)), and the terminal ratio of phenyl is more than 20%, the content of Isosorbide (levels of residual monomers) is below the 60ppm, their bad order product rates (%) in injection molding is estimated are low, and the value of moulding delay Δ YI is little, in appearance painted few of these materials, the transparency is excellent.In addition, during extruded film was estimated, the dirt settling amount on roller, number of defects were also few, can stably carry out the film manufacturing.
On the other hand, the Isosorbide of PC Resin A-4, PC resin B-5 (comparative example 17～comparative example 20) or the content (levels of residual monomers) of tristane dimethanol are greater than 60ppm, bad order product rate (%) in injection molding is estimated is big, and moulding is detained Δ YI value greatly, in appearance painted of these materials have damaged the transparency more.In addition, in extruded film is estimated, also can be observed the dirt settling amount on roller, the tendency that the defective number average is many slightly, stability was poor slightly during film was made.
(embodiment 40～embodiment 46)
Use contains the polycarbonate resin A-7 (note is made " PC Resin A-7 ") of heterocycle, above-mentioned antioxidant, following releasing agent, prepares poly carbonate resin composition by the proportioning shown in the table 7, and the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 7.Described PC Resin A-the 7th, following obtaining: the heating tank temperature in the 2nd stage when manufacturing is contained the polycarbonate resin A-1 (PC Resin A-1), PC Resin A-2, PC Resin A-3 of heterocycle, the above-mentioned polycarbonate resin A-1 that contains heterocycle (PC Resin A-1) is set at 280 ℃, in addition, similarly carry out with the manufacturing of PC Resin A-1, obtain PC Resin A-7.
(releasing agent)
NAA-180: stearic acid (NOF Corp's manufacturing)
Gold medal powder (go one Le デ Application Block ラ Application De パ ウ ダ one): cera alba (manufacturing of three wooden chemistry Industrial Co., Ltd)
Solid paraffin 155: solid paraffin (Japanese smart wax Co., Ltd. make)
[table 7]
Figure BDA0000063054310000631
By the result shown in the table 7 as can be known, poly carbonate resin composition (embodiment 40～embodiment 46) has used the ratio of phenyl end at the polycarbonate resin of the scope more than 20%, and any one is excellent at least among its injection molding evaluation and the Δ YI.
In addition, by the polycondensation of Isosorbide (ISB), tristane dimethanol (TCDDM) and diphenyl carbonate (DPC) obtain and above-mentioned structural formula (2) shown in terminal group (two key end) be under the situation below 7%, Δ YI is little, and the content of residual monomer is under the following situation of 60ppm, Δ YI is littler, is painted few elite clone.Particularly under the situation that contains the following residual carbon acid diesters of 60ppm, except above-mentioned advantage, also have and no matter whether contain the elite clone that releasing agent all is metal pattern hardly staining metals.
＜be mixed with the poly carbonate resin composition of inorganic filler 〉
The preparation of＜polycarbonate resin 〉
(the polycarbonate resin A-8 that contains heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part tristane dimethanols (being designated hereinafter simply as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 * 10 through the Isosorbide (ISB) of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
In twin screw extruder; add each additive continuously by the composition shown in the table 8; pass through each exhaust oral area simultaneously with lower molecular weight thing water filling devolatilizations such as phenol; carry out granulation by tablets press then, obtain the polycarbonate resin A-8 that contains heterocycle (note is made " PC Resin A-8 ") of Isosorbide (ISB)/TCDDM=70/30 (mol% ratio).
The physical property evaluation of＜poly carbonate resin composition 〉
(injection molding)
Will be predrying 4 hours at 80 ℃ with the particle of the polycarbonate resin of the mixing preparation of twin screw extruder, next, this particle and various additive are put in the injection moulding machine (JSW's J75EII type processed), condition in 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature is carried out injection molding, makes various test films.
(modulus in flexure)
For the test film that uses the injection moulding machine preparation, the bend test method of stipulating according to ISO 178 carries out three point bending test.
(metal pattern dirt settling)
For each poly carbonate resin composition, under above-mentioned injection molding condition, respectively inject the moulding of the flat board of 100 length 60mm * wide 60mm * thickness 3mm, have or not the dirt settling amount of fixation side metal pattern after the bad generation of the demoulding and the moulding in the visual observation moulding.
(Δ YI is detained in moulding)
For each poly carbonate resin composition, in above-mentioned injection molding condition, change shaping cycle into 300 seconds, respectively inject the moulding of the flat board of 10 length 60mm * wide 60mm * thickness 3mm in addition with identical condition, the preparation test film.
Then, for each test film of preparation, utilize light splitting colour-difference meter (the Japanese electric look manufacturing SE-2000 of Industrial Co., Ltd), measure yellowness index (YI) value (300 second cycle moulding product YI) with the illuminant-C reflection method.
Carry out yellowness index (YI) value (45 second cycle moulding product YI) of injection molding test film by this 300 second cycle moulding product YI with 45 seconds shaping cycles, calculate moulding by following formula and be detained Δ YI.
Δ YI=(300 second cycle moulding product YI)-(45 second cycle moulding product YI) is detained in moulding
(embodiment 47～49)
Use the polycarbonate resin A-9 (note is made " PC Resin A-9 ") that contains heterocycle among the embodiment 49, it is following obtaining: in the manufacturing of above-mentioned PC Resin A-8, in twin screw extruder, change into and only carry out the vacuum devolatilization and do not carry out water filling, carry out same operation in addition, obtain described PC Resin A-9.
Use contains polycarbonate resin A-8 (PC Resin A-8), PC Resin A-9, following antioxidant, the following inorganic filler of heterocycle, prepare poly carbonate resin composition by the proportioning shown in the table 8, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 8.
(comparative example 21,22)
Use the polycarbonate resin A-10 (note is made " PC Resin A-10 ") that contains heterocycle in the comparative example 22, it is following obtaining: in the manufacturing of PC Resin A-8, the diphenyl carbonate amount is changed into 115,688 weight parts, carry out same operation in addition.
Use the above-mentioned polycarbonate resin A-8 that contains heterocycle (PC Resin A-8), following antioxidant, following inorganic filler, prepare poly carbonate resin composition by the proportioning shown in the table 8, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 8.
(antioxidant)
(1) 1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol esters (manufacturing of Ciba society) of IRGANOX
(2) ADKSTAB PEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacturing)
(3) 168: three (2,4-di-tert-butyl-phenyl) phosphorous acid esters (Asahi Denka Co., Ltd.'s manufacturing) of IRGAFOS
(inorganic filler)
(1) glass fibre: glass strand ECS03T-571 (Nippon Electric Glass Co., Ltd's manufacturing) (2) carbon fiber: Pyrofil Chopped Fiber TR06U (Mitsubishi Rayon Co., Ltd's manufacturing)
[table 8]
Figure BDA0000063054310000661
By the result shown in the table 8 as can be known, poly carbonate resin composition obtains by the polycondensation between Isosorbide (ISB), tristane dimethanol (TCDDM) and the diphenyl carbonate (DPC), and the ratio of the phenyl end shown in the above-mentioned structural formula (2) is in the scope more than 20%, and when described poly carbonate resin composition contains 1 weight part～100 weight part inorganic fillers (embodiment 47～49), said composition has high modulus in flexure, and at least one side of moulding delay Δ YI and metal pattern dirt settling is excellent.As can be known, the residual carbon acid diesters that contains is under the following situation of 60ppm when particularly comparing between the embodiment, and this material is especially excellent, and its metal pattern dirt settling is especially few, the modulus in flexure height.
＜be mixed with the poly carbonate resin composition of fire retardant 〉
The preparation of＜polycarbonate resin 〉
(the polycarbonate resin A-11 that contains heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part tristane dimethanols (being designated hereinafter simply as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 * 10 through the Isosorbide (ISB) of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is supplied with the polycarbonate resin of molten state continuously to the twin screw extruder with 3 venting ports and water injection equipment by the outlet of polymerization machine.
In twin screw extruder; add each additive continuously by the composition shown in the table 9; simultaneously at each exhaust oral area with lower molecular weight thing water filling devolatilizations such as phenol; carry out granulation by tablets press then, obtain the polycarbonate resin A-11 that contains heterocycle (note is made " PC Resin A-11 ") of Isosorbide (ISB)/TCDDM=70/30 (mol% ratio).
The physical property evaluation of＜poly carbonate resin composition 〉
(injection molding)
Will be predrying 4 hours at 80 ℃ with the particle of the polycarbonate resin of the mixing preparation of twin screw extruder, next, this particle and various additive are put in the injection moulding machine (JSW's J75EII type processed), condition in 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature is carried out injection molding, makes various test films.
(incendivity)
For through with the mixing particle that obtains of twin screw extruder, will be at 80 ℃ of particles after predrying 4 hours with the condition of JSW's J75EII type processed injection moulding machine in 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature, based on the UL94 standard, carry out the moulding of the combustion test sheet of 1.5mmt.Carry out testing vertical flammability in the UL94 standard with the test film that obtains.
(embodiment 50～52)
Among the embodiment 52, use contains the polycarbonate resin A-12 (note is made " PC Resin A-12 ") of heterocycle, it is following obtaining: in the manufacturing of above-mentioned PC Resin A-11, change in twin screw extruder and only carry out the vacuum devolatilization and do not carry out water filling, carry out same operation in addition.
Use contains polycarbonate resin A-11 (PC Resin A-11), PC Resin A-12, following antioxidant, the following fire retardant of heterocycle, prepare poly carbonate resin composition by the proportioning shown in the table 9, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 9.
(comparative example 23,24)
In the comparative example 24, use the polycarbonate resin A-13 (note is made " PC Resin A-13 ") contain heterocycle, it is following obtaining: in the manufacturing of PC Resin A-11, the temperature of the heating tank in the 2nd stage is changed to 280 ℃.
Use above-mentioned the polycarbonate resin A-11 that contains heterocycle (PC Resin A-11), PC Resin A-13, following antioxidant, following fire retardant, prepare poly carbonate resin composition by the proportioning shown in the table 9, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 9.
(antioxidant)
(1) 1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol esters (manufacturing of Ciba society) of IRGANOX
(2) ADKSTAB PEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacturing)
(3) 168: three (2,4-di-tert-butyl-phenyl) phosphorous acid esters (Asahi Denka Co., Ltd.'s manufacturing) of Irgafos
(fire retardant)
(1) SPS-100: phosphazene compound (Otsuka Chemical Co., Ltd makes)
(2) PX-200: aromatic condensation phosphoric acid ester (Daihachi Chemical Industry Co., Ltd.'s manufacturing)
[table 9]
Figure BDA0000063054310000691
By the result shown in the table 9 as can be known, poly carbonate resin composition obtains by the polycondensation between Isosorbide (ISB), tristane dimethanol (TCDDM) and the diphenyl carbonate (DPC), and the ratio of the phenyl end shown in the above-mentioned structural formula (2) is more than 20%, when the fire retardant that contains is 0.01 weight part～30 weight parts (embodiment 50～52), the moulding delay Δ YI of this polycarbonate compositions is little, painted few, and flame retardant resistance is also excellent.In addition, embodiment is compared to each other as can be known, the residual carbon acid diesters that contains is that the following poly carbonate resin composition (embodiment 50,51) of 60ppm is more excellent material, and the metal pattern dirt settling does not increase yet.
＜be mixed with the poly carbonate resin composition of UV light absorber 〉
The preparation of＜polycarbonate resin 〉
(Production Example 1: the polycarbonate resin R-1 that contains heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part tristane dimethanols (being designated hereinafter simply as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 * 10 through the Isosorbide (ISB) of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is exported the polycarbonate resin R-1 (following note is made " PC resin R-1 ") that obtains molten state by the polymerization machine.
(Production Example 2: the polycarbonate resin R-2 that contains heterocycle)
For the operation in the 2nd stage of Production Example 1, the heating tank temperature is changed to 280 ℃ from 240 ℃, in addition, similarly carry out with Production Example 1, obtain polycarbonate resin R-2 (following note is made " PC resin R-2 ").
(Production Example 3: the polycarbonate resin R-3 that contains heterocycle)
Change the DPC amount of Production Example 1 into 115,688 weight parts, replace 117,957 weight parts, and similarly change the heating tank temperature into 280 ℃ from 240 ℃ as the operation in the 2nd stage with Production Example 2, carry out equally with Production Example 1 in addition, obtain polycarbonate resin R-3 (following note is made " PC resin R-3 ").
(Production Example 4: the polycarbonate resin R-4 that contains heterocycle)
Relative 73,070 weight part Isosorbides (ISB) drop into 109,140 weight part diphenyl carbonates (DPC) and 2.0 * 10 to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction is exported the polycarbonate resin R-4 (following note is made " PC resin R-4 ") that obtains molten state by the polymerization machine.
(Production Example 5: the polycarbonate resin R-5 that contains heterocycle)
As the operation in the 2nd stage of Production Example 4, the heating tank temperature is changed to 280 ℃ from 240 ℃, in addition, carry out equally with Production Example 1, obtain polycarbonate resin R-5 (following note is made " PC resin R-5 ").
(Production Example 6: the polycarbonate resin R-6 that contains heterocycle)
Change the DPC amount of Production Example 4 into 107,102 weight parts replace 109,140 weight parts, same with Production Example 2, as the operation in the 2nd stage, the heating tank temperature is changed to 280 ℃ from 240 ℃, in addition, carry out equally with Production Example 1, obtain polycarbonate resin R-6 (following note is made " PC resin R-6 ").
The physical property evaluation of＜poly carbonate resin composition 〉
(injection molding)
Will be predrying 4 hours at 80 ℃ with the particle of the polycarbonate resin of the mixing preparation of twin screw extruder, next, this particle and various additive are put in the injection moulding machine (JSW's J75EII type processed), condition in 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature is carried out injection molding, makes various test films.
(photostabilization evaluation)
By light splitting colour-difference meter (the Japanese electric look manufacturing SE-2000 of Industrial Co., Ltd), with the illuminant-C reflection method each test film of preparation is measured yellowness index (YI) value (initial stage YI).
Then, use the weather-proof machine of metal (the Metaling Weather MeterM6T that SUGA trier Co., Ltd. makes), at radiation illumination 1.5kW/m 2, 63 ℃ of temperature in the groove, humidity 50% time implement 20 hours radiation treatment to each test film, measures yellowness index (YI) value (YI after the test) thereafter.
Δ YI=(YI after the test)-(initial stage YI)
(being detained stability)
Glass tubing to the band arm adds the 30g polycarbonate resin, and is airtight after replacing with nitrogen, soaks 8 hours in 250 ℃ oil bath.Thereafter, the reduced viscosity of measuring polycarbonate resin (is soaked back reduced viscosity (η Red) ').Then, with soaking back reduced viscosity (η Red) ' divided by the reduced viscosity (η that soaks preceding polycarbonate resin Red), obtain this ratio (unit: %).
(embodiment 53～embodiment 65)
Use contain heterocycle polycarbonate resin R-1 (PC resin R-1), contain heterocycle polycarbonate resin R-2 (PC resin R-2), contain heterocycle polycarbonate resin R-3 (PC resin R-3), contain the polycarbonate resin R-4 (PC resin R-4) of heterocycle, following antioxidant, following acidic cpd, following UV light absorber, prepare poly carbonate resin composition by the proportioning shown in the table 10, the poly carbonate resin composition of preparing is carried out various evaluations.
Each resin and mixture are supplied with to the twin screw extruder with 3 venting ports and water injection equipment, utilize each exhaust oral area with lower molecular weight thing water filling devolatilizations such as phenol after, carry out granulation by tablets press.The results are shown in Table 10.
(comparative example 25～comparative example 28)
Use contain heterocycle polycarbonate resin R-2 (PC resin R-2), contain heterocycle polycarbonate resin R-3 (PC resin R-3), contain the polycarbonate resin R-6 (PC resin R-6) of heterocycle, following acidic cpd, following UV light absorber, prepare poly carbonate resin composition by proportioning shown in the table 11, the poly carbonate resin composition of preparing is carried out various evaluations.The results are shown in Table 11.
(antioxidant)
(1) 1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol esters (manufacturing of Ciba society) of IRGANOX
(2) ADKSTAB PEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacturing)
(3) 168: three (2,4-di-tert-butyl-phenyl) phosphorous acid esters (Asahi Denka Co., Ltd.'s manufacturing) of Irgafos
(acidic cpd)
PTSB: butyl p-toluenesulfonate (Tokyo changes into Co., Ltd. and makes)
(UV light absorber)
(1) (Ciba society makes UV-1:2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-((hexyl) oxygen base)-phenol, TINUVIN1577FF: molecular weight 425)
(2) UV-2:N-(2-ethoxyl phenenyl)-N '-(4-ethylphenyl)-oxalamide (manufacturing of Clariant Japan society, HostavinVSU)
(3) UV-3:4-anisole methylene radical dimethyl malonate (manufacturing of Clariant Japan society, HostavinPR-25)
(4) (Ciba society makes UV-4:2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, TINUVIN329: molecular weight 323)
(5) UV-5: (api corporation society makes salol, salol: molecular weight 214)
(6) UV-6:2-cyano group-3, (BASF Japan society makes the 3-diphenyl-ethyl acrylate, Uvinul3035: molecular weight 277)
In addition, employed UV light absorber is at the molar absorptivity (ε at wavelength 210nm place 210) and at the molar absorptivity (ε of wavelength 250nm to wavelength 350nm 250-350) in the ratio (ε of maximum value 210/ ε 250-350) as follows.
(1)UV-1：(ε 210/ε 250-350)＝0.85
(2)UV-2：(ε 210/ε 250-350)＝1.52
(3)UV-3：(ε 210/ε 250-350)＝0.43
(4)UV-4：(ε 210/ε 250-350)＝1.69
(5)UV-5：(ε 210/ε 250-350)＝4.12
(6)UV-6：(ε 210/ε 250-350)＝1.78
Figure BDA0000063054310000731
[table 11]
Figure BDA0000063054310000741
By result shown in table 10, the table 11 as can be known, the polycarbonate that poly carbonate resin composition uses the polycondensation by Isosorbide (ISB), tristane dimethanol (TCDDM) and diphenyl carbonate (DPC) to obtain, and when this polycarbonate has the terminal group shown in the above-mentioned structural formula (2) (phenyl end) (embodiment 53～65), the Δ YI in photostabilization is estimated is little for this poly carbonate resin composition, painted few, be the material of photostabilization excellence.
＜mixed the poly carbonate resin composition of thermoplastic resin 〉
The preparation of＜polycarbonate resin 〉
(Production Example 7: the polycarbonate resin R-7 that contains heterocycle)
Relative 54,220 weight parts drop into 31,260 weight part tristane dimethanols (being designated hereinafter simply as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 * 10 through the Isosorbide (ISB) of distillation to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion; stopped reaction; exported by the polymerization machine; the polycarbonate resin of relative 100 weight part molten states; supply with 0.0006 weight part butyl p-toluenesulfonate as acidic cpd to the twin screw extruder with 3 venting ports and water injection equipment; after each exhaust oral area is with lower molecular weight thing water filling devolatilizations such as phenol, obtain containing the polycarbonate resin R-7 (following note is made " PC resin R-7 ") of heterocycle, utilize tablets press to carry out granulation.
The reduced viscosity of the particle that obtains is 0.571dl/g, and terminal with all terminal ratio of two keys is 5.6%, the ratio of phenyl end is 64%.
(Production Example 8: the polycarbonate resin R-8 that contains heterocycle)
Operation as the 2nd stage of Production Example 7 changes to 280 ℃ with the heating tank temperature by 240 ℃, in addition, carries out equally with Production Example 1, obtains polycarbonate resin R-8 (following note is made " PC resin R-8 ").Reduced viscosity is that terminal with all terminal ratio of 0.554dl/g, two key is 5.5%, the ratio of phenyl end is 63%.
(Production Example 9: the polycarbonate resin R-9 that contains heterocycle)
Change the DPC amount of Production Example 7 into 115,688 weight parts replace 117,957 weight parts, same with Production Example 8, as the operation in the 2nd stage, the heating tank temperature is changed to 280 ℃ from 240 ℃, and do not add pTSB as acidic cpd, in addition, carry out equally with Production Example 1, obtain polycarbonate resin R-9 (following note is made " PC resin R-9 ").Reduced viscosity is that terminal with all terminal ratio of 0.561dl/g, two key is 4.9%, the ratio of phenyl end is 10%.
(Production Example 10: the polycarbonate resin R-10 that contains heterocycle)
Relative 73,070 weight part Isosorbides (ISB) drop into 109,140 weight part diphenyl carbonates (DPC) and 2.0 * 10 to reaction vessel -1Weight part is as the cesium carbonate of catalyzer, and under nitrogen atmosphere, the operation as the 1st stage of reacting is heated to 150 ℃ with the heating tank temperature, makes material dissolution (about 15 minutes) as required when stirring.
Next, with 40 minutes with pressure from the atmospheric depressurized to 13.3kPa, and make the heating tank temperature be elevated to 190 ℃ with 40 minutes, simultaneously the phenol that produces is retracted to outside the reaction vessel.
After 15 minutes, as the operation in the 2nd stage, made the heating tank temperature be elevated to 240 ℃ with 30 minutes 190 ℃ of maintenances in the entire reaction container.After beginning to heat up 10 minutes, making the pressure in the reaction vessel with 30 minutes is below the 0.200kPa, and the phenol of generation is distillated.After reaching predetermined stirring moment of torsion; stopped reaction; exported by the polymerization machine; the polycarbonate resin of relative 100 weight part molten states; supply with 0.0006 weight part pTSB as acidic cpd to the twin screw extruder with 3 venting ports and water injection equipment; after each exhaust oral area carries out the water filling devolatilization of lower molecular weight things such as phenol, obtain containing the polycarbonate resin R-10 (following note is made " PC resin R-10 ") of heterocycle, utilize tablets press to carry out granulation.Reduced viscosity is that terminal with all terminal ratio of 0.562dl/g, two key is 6.3%, the ratio of phenyl end is 60%.
(Production Example 11: the polycarbonate resin R-11 that contains heterocycle)
Operation as the 2nd stage of Production Example 10 changes to 280 ℃ with the heating tank temperature by 240 ℃, in addition, similarly carries out with Production Example 10, obtains polycarbonate resin R-11 (following note is made " PC resin R-11 ").Reduced viscosity is that terminal with all terminal ratio of 0.548dl/g, two key is 6.7%, the ratio of phenyl end is 58%.
(Production Example 12: the polycarbonate resin R-12 that contains heterocycle)
Change the DPC amount of Production Example 10 into 107,102 weight parts replace 109,140 weight parts, same with Production Example 9, as the operation in the 2nd stage, the heating tank temperature is changed to 280 ℃ from 240 ℃, and do not add pTSB as acidic substance, in addition, carry out equally with Production Example 10, obtain polycarbonate resin R-12 (following note is made " PC resin R-12 ").Reduced viscosity is that terminal with all terminal ratio of 0.554dl/g, two key is 5.5%, the ratio of phenyl end is 11%.
Employed thermoplastic resin is as follows.
Polybutylene terephthalate resin (PBT) (manufacturing of engineering plastics society of Mitsubishi, trade(brand)name NOVADURAN5010)
Amorphism pet resin (PETG) (manufacturing of eastman chemical Japan society, trade(brand)name EASTAR PETG 6763)
Bisphenol-a polycarbonate (PC) (manufacturing of engineering plastics society of Mitsubishi, trade(brand)name NOVAREX 7022J)
High density polyethylene(HDPE) (HDPE) (Japanese polyethylene society makes, trade(brand)name NOVATEC HD HF410)
(antioxidant)
Employed antioxidant is as follows.
A-1: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester (manufacturing of Ciba society, IRGANOX1010)
A-2: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites (manufacturing of ADEKA society, ADKSTAB PEP-36)
The physical property evaluation of＜poly carbonate resin composition 〉
(injection molding)
Will be predrying 4 hours at 80 ℃ with the particle of the polycarbonate resin of the mixing preparation of twin screw extruder, next, this particle and various additive are put in the injection moulding machine (JSW's J75EII type processed), condition in 230 ℃ of barrel temperatures, shaping cycle 45 seconds, 60 ℃ of metal pattern temperature is carried out injection molding, makes various test films.
(tone of sheet (YI))
(society of JSW makes the particle that each embodiment, comparative example are obtained, form: the sheet that J75EII) obtains 60mm * 4mmt under 230 ℃ of barrel temperatures, 90 ℃ of conditions of metal pattern temperature with injection moulding machine.The sheet that obtains is measured yellowness index (YI) value as the index of yellow variable color with light splitting colour-difference meter (the Japanese electric look manufacturing ZE-2000 of Industrial Co., Ltd) with the illuminant-C reflection method.
(delay thermostability)
Glass tubing to the band arm adds the 30g resin, and is airtight after replacing with nitrogen, soaks 8 hours in 250 ℃ oil bath.With the reduced viscosity after soaking divided by the reduced viscosity before soaking.
(embodiment 66～embodiment 72)
With proportioning shown in the table 12, polycarbonate resin, antioxidant, thermoplastic resin are extruded under the condition of 230 ℃ of barrel temperatures, propeller speed 200rpm, discharge-amount 1kg/h with the twin-screw mixer machine that has de-gassing vessel (manufacturing of TECHNOVEL society, KZW-15-30MG), obtained particle.According to above-mentioned evaluation method, the color harmony of measuring sheet is detained thermostability.The results are shown in Table 12.
(comparative example 29～comparative example 32)
With the proportioning shown in the table 13, similarly carry out mixingly with embodiment 66, obtain particle.Evaluation result sees Table 13.
[table 12]
Figure BDA0000063054310000771
[table 13]
Figure BDA0000063054310000781
By result shown in table 12, the table 13 as can be known, the polycarbonate resin that poly carbonate resin composition uses is that the polycondensation by Isosorbide (ISB), tristane dimethanol (TCDDM) and diphenyl carbonate (DPC) obtains, and with respect to whole terminal numbers, phenyl end shown in the above-mentioned structural formula (2) is more than 20% when (embodiment 66～72), the tone aspect of sheet, yellow variable color is little, and each other more as can be known, it is to be detained the also material of excellence of stability by the polycarbonate compositions that has used thermoplastic resin of the same race.
Above describe the present invention in detail and with reference to specific embodiment, but for a person skilled in the art, obviously can carry out various variations or modification not breaking away from the spirit and scope of the present invention.The application is based on the Japanese patent application of submitting on November 28th, 2008 (Japanese Patent Application 2008-305648), the Japanese patent application (Japanese Patent Application 2008-305651) that on November 28th, 2008 submitted to, the Japanese patent application (Japanese Patent Application 2008-305665) that on November 28th, 2008 submitted to, the Japanese patent application (Japanese Patent Application 2008-305687) that on November 28th, 2008 submitted to, the Japanese patent application (Japanese Patent Application 2009-144171) that on June 17th, 2009 submitted to, the Japanese patent application (Japanese Patent Application 2009-144775) that on June 17th, 2009 submitted to, the Japanese patent application (Japanese Patent Application 2009-144776) that on June 17th, 2009 submitted to, the Japanese patent application (Japanese Patent Application 2009-144779) that on June 17th, 2009 submitted to, the application of the Japanese patent application (Japanese Patent Application 2009-144780) that on June 17th, 2009 submitted to, this form of sentencing reference is introduced this specification sheets with its content.
Utilizability on the industry
According to the present invention, can access the excellent polycarbonate resin of thermotolerance, the transparency and contain the poly carbonate resin composition of this polycarbonate resin.

Claims (29)

1. polycarbonate resin, described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), it is characterized in that, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%;
[changing 1]
Figure FDA00002977984100011
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1);
[changing 2]
Figure FDA00002977984100012
2. polycarbonate resin as claimed in claim 1 is characterized in that, described polycarbonate resin contains the dihydroxy compound of the bond structure that has following structural formula (1) below the 60ppm;
[changing 3]
Figure FDA00002977984100013
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1).
3. polycarbonate resin as claimed in claim 1 is characterized in that, described polycarbonate resin contains the carbonic diester shown in the following following general formula (3) of 60ppm;
[changing 4]
Figure FDA00002977984100014
In the general formula (3), A 1, A 2Be to have substituting group or do not have substituent carbonatoms to be 1～18 1 valency fatty group or to have substituting group or do not have substituent 1 valency aromatic series base, A 1And A 2Identical or different.
4. polycarbonate resin according to claim 1 is characterized in that this polycarbonate resin contains the following aromatic monohydroxy compound of 700ppm, and it is alkyl below 5 that this aromatic monohydroxy compound has or do not have carbonatoms.
5. polycarbonate resin as claimed in claim 1 is characterized in that, the dihydroxy compound with bond structure of described structural formula (1) has heterocyclic radical.
6. polycarbonate resin as claimed in claim 5 is characterized in that, the dihydroxy compound with bond structure of described structural formula (1) is the compound with the heterocyclic radical shown in the following general formula (4);
[changing 9]
Figure FDA00002977984100021
7. polycarbonate resin as claimed in claim 1 is characterized in that, second-order transition temperature is more than 90 ℃.
8. polycarbonate resin as claimed in claim 1, it is characterized in that described polycarbonate resin also contains from being selected from by aliphatics dihydroxy compound, ester ring type dihydroxy compound, oxyalkylene group glycol, bis-phenol, having a structural unit of at least a compound in the group that the glycol of cyclic acetal structure forms.
9. a poly carbonate resin composition is characterized in that, described composition contains the lipid acid of each described polycarbonate resin of 100 weight part claims 1～8 and 0.0001 weight part～2 weight parts.
10. poly carbonate resin composition as claimed in claim 9 is characterized in that, described composition contains the natural system wax of each described polycarbonate resin of 100 weight part claims 1～8 and 0.0001 weight part～2 weight parts.
11. poly carbonate resin composition as claimed in claim 9, it is characterized in that described composition contains each described polycarbonate resin of 100 weight part claims 1～8 and 0.0001 weight part～2 weight parts and is selected from least a compound in olefines wax, the silicone oil.
12. poly carbonate resin composition as claimed in claim 9 is characterized in that, described composition contains each described polycarbonate resin of 100 weight part claims 1～8 and 0.00001 weight part～0.1 weight part acidic cpd.
13. poly carbonate resin composition as claimed in claim 9 is characterized in that, described composition contains each described polycarbonate resin of 100 weight part claims 1～8 and 0.001 weight part～1 weight part phosphorus series compound.
14. poly carbonate resin composition as claimed in claim 9, it is characterized in that described composition contains each described polycarbonate resin of 100 weight part claims 1～8,0.00001 weight part～at least a acidic cpd of 0.1 weight part and 0.001 weight part～at least a phosphorus series compound of 1 weight part.
15. poly carbonate resin composition as claimed in claim 9, it is characterized in that described composition contains each described polycarbonate resin of 100 weight part claims 1～8,0.001 weight part～1 weight part aromatic monohydroxy compound that to have 1 above carbonatoms be the alkyl substituent more than 5.
16. poly carbonate resin composition as claimed in claim 9 is characterized in that, described composition contains each described poly carbonate resin composition of 100 weight part claims 1～8 and 0.000001 weight part～1 weight part bluing agent.
17. a blooming is characterized in that, it contains each described polycarbonate resin of claim 1～8.
18. a polycarbonate resin moldings is characterized in that, it obtains by each described polycarbonate resin of claim 1～8 or each described poly carbonate resin composition of claim 9～16 are carried out moulding.
19. polycarbonate resin moldings as claimed in claim 18 is characterized in that, described polycarbonate resin moldings obtains by the injection moulding moulding.
20. a poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part～100 weight part mineral fillers,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%;
[changing 11]
Figure FDA00002977984100031
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1);
[changing 12]
Figure FDA00002977984100041
21. a poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 0.01 weight part～30 parts by weight of flame retardant,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%;
[changing 17]
Figure FDA00002977984100042
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1);
[changing 18]
Figure FDA00002977984100043
22. poly carbonate resin composition as claimed in claim 21 is characterized in that, fire retardant is to be selected from least a in the group of being made up of P contained compound flame retardant, halogen contained compound flame retardant.
23. a poly carbonate resin composition is characterized in that, it contains 100 weight part polycarbonate resins and 0.005 weight part～5 weight part UV light absorber,
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%;
[changing 23]
Figure FDA00002977984100051
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1);
[changing 24]
Figure FDA00002977984100052
24. poly carbonate resin composition as claimed in claim 23 is characterized in that, described UV light absorber at the ratio of the molar absorptivity at wavelength 210nm place and the maximum value of molar absorptivity from wavelength 250nm to wavelength 350nm less than 1.75.
25., it is characterized in that described UV light absorber is to be selected from least a in the group of being made up of triazine based compound, oxanilide based compound, malonic ester based compound as claim 23 or 24 described poly carbonate resin compositions.
26. a poly carbonate resin composition is characterized in that, it contains 10 weight parts～90 weight part polycarbonate resins (a) and 90 weight parts～10 weight part thermoplastic resins (b),
Described polycarbonate resin contains the structural unit from dihydroxy compound at least, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in the following structural formula (2) exist number (A) with respect to the ratio (A/B) of whole terminal numbers (B) in the scope more than 20%;
[changing 29]
Figure FDA00002977984100053
Wherein, hydrogen bonding atom not on the Sauerstoffatom in the structural formula (1);
[changing 30]
Figure FDA00002977984100054
27. poly carbonate resin composition as claimed in claim 26 is characterized in that, thermoplastic resin (b) is that to be selected from phenylethylene resin series, saturated polyester resin, bis-phenol be at least a in polycarbonate resin, polyolefin-based resins and the acrylic resin.
28. a polycarbonate resin moldings is characterized in that, it carries out moulding to each described poly carbonate resin composition of claim 20～27 and obtains.
29. polycarbonate resin moldings as claimed in claim 28 is characterized in that, polycarbonate resin moldings carries out moulding by injection moulding and obtains.
CN2009801466415A 2008-11-28 2009-11-27 Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article Active CN102224182B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310285560.1A CN103351463B (en) 2008-11-28 2009-11-27 Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

Applications Claiming Priority (19)

Application Number Priority Date Filing Date Title
JP2008-305651 2008-11-28
JP2008-305665 2008-11-28
JP2008305665 2008-11-28
JP2008305648 2008-11-28
JP2008305687 2008-11-28
JP2008-305648 2008-11-28
JP2008-305687 2008-11-28
JP2008305651 2008-11-28
JP2009-144780 2009-06-17
JP2009144779 2009-06-17
JP2009-144775 2009-06-17
JP2009-144171 2009-06-17
JP2009144171 2009-06-17
JP2009-144779 2009-06-17
JP2009144775 2009-06-17
JP2009144776 2009-06-17
JP2009-144776 2009-06-17
JP2009144780 2009-06-17
PCT/JP2009/070060 WO2010061929A1 (en) 2008-11-28 2009-11-27 Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201310285560.1A Division CN103351463B (en) 2008-11-28 2009-11-27 Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

Publications (2)

Publication Number Publication Date
CN102224182A CN102224182A (en) 2011-10-19
CN102224182B true CN102224182B (en) 2013-08-07

Family

ID=42225798

Family Applications (2)

Application Number Title Priority Date Filing Date
CN2009801466415A Active CN102224182B (en) 2008-11-28 2009-11-27 Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article
CN201310285560.1A Active CN103351463B (en) 2008-11-28 2009-11-27 Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201310285560.1A Active CN103351463B (en) 2008-11-28 2009-11-27 Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

Country Status (3)

Country Link
JP (2) JP6164790B2 (en)
CN (2) CN102224182B (en)
WO (1) WO2010061929A1 (en)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5448264B2 (en) * 2009-11-19 2014-03-19 三菱化学株式会社 Polycarbonate resin film and transparent film
JP5978554B2 (en) * 2009-12-22 2016-08-24 三菱化学株式会社 Polycarbonate resin composition and molded product
JP5978555B2 (en) * 2010-01-07 2016-08-24 三菱化学株式会社 Polycarbonate resin composition and molded product thereof
CN101885907A (en) * 2010-07-09 2010-11-17 深圳市科聚新材料有限公司 Polycarbonate modified material used in sunshade board of LED lamp and preparation method thereof
JP5918939B2 (en) * 2010-07-14 2016-05-18 三菱化学株式会社 Polycarbonate resin composition, and molded article, film, plate, injection molded article using the same
JP2012067294A (en) * 2010-08-25 2012-04-05 Mitsubishi Chemicals Corp Polycarbonate resin composition and molding
JP5652056B2 (en) * 2010-08-26 2015-01-14 三菱化学株式会社 Resin composition and resin molded body
JP5786556B2 (en) * 2010-08-26 2015-09-30 三菱化学株式会社 Manufacturing method of resin molded products
EP2634218A4 (en) * 2010-10-29 2016-11-02 Mitsubishi Chem Corp Resin composition and film, plate and injection molding obtained by molding same
JP2012102287A (en) * 2010-11-12 2012-05-31 Mitsubishi Chemicals Corp Glass fiber reinforced polycarbonate resin composition and molded article
JP5958025B2 (en) * 2011-03-31 2016-07-27 三菱化学株式会社 Polycarbonate resin composition, polycarbonate resin molded article, and light reflecting member
JP5695986B2 (en) * 2011-07-01 2015-04-08 花王株式会社 Method for producing polyether polycarbonate
JP2013049847A (en) * 2011-08-03 2013-03-14 Mitsubishi Chemicals Corp Automotive interior
JP2013049846A (en) * 2011-08-03 2013-03-14 Mitsubishi Chemicals Corp Sound-insulating member
JP2013203933A (en) * 2012-03-29 2013-10-07 Mitsubishi Chemicals Corp Polycarbonate resin composition and molded article
JP2013209582A (en) * 2012-03-30 2013-10-10 Mitsubishi Chemicals Corp Molded body
TWI609046B (en) 2012-11-05 2017-12-21 出光興產股份有限公司 Polycarbonate resin composition and molded article
JP6349849B2 (en) * 2014-03-26 2018-07-04 三菱ケミカル株式会社 Polycarbonate resin
JP2015187204A (en) * 2014-03-26 2015-10-29 三菱化学株式会社 Extrusion molded product formed of polycarbonate resin
JP6030814B1 (en) * 2015-02-10 2016-11-24 住化スタイロンポリカーボネート株式会社 Polycarbonate resin composition and molded product
KR20170139029A (en) * 2015-04-21 2017-12-18 미쯔비시 케미컬 주식회사 Polycarbonate resin film
CN105440624B (en) * 2015-05-27 2019-05-07 金发科技股份有限公司 A kind of polycarbonate compositions and preparation method thereof
WO2017119404A1 (en) * 2016-01-06 2017-07-13 帝人株式会社 Polycarbonate resin, production method therefor, and film
JP6913438B2 (en) * 2016-03-02 2021-08-04 三菱ケミカル株式会社 Manufacturing method of polycarbonate resin film
JP2017165892A (en) * 2016-03-17 2017-09-21 三菱ケミカル株式会社 Transparent resin film
JP6320645B2 (en) 2016-05-16 2018-05-09 株式会社ポラテクノ Polarizing member and head-up display device including the same
JP6759871B2 (en) * 2016-08-31 2020-09-23 三菱ケミカル株式会社 A method for producing a film having a negative thickness retardation (Rth).
JP6229782B2 (en) * 2016-10-18 2017-11-15 三菱ケミカル株式会社 Polycarbonate resin composition and molded product
WO2018199033A1 (en) * 2017-04-28 2018-11-01 出光興産株式会社 Glass filler-containing polycarbonate resin composition, and molded body thereof
JP7115845B2 (en) * 2017-12-14 2022-08-09 帝人株式会社 POLYCARBONATE RESIN COMPOSITION AND OPTICAL FILM MADE THEREOF
KR20210136993A (en) * 2019-03-12 2021-11-17 닛토덴코 가부시키가이샤 Polarizing plate with retardation film and retardation layer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1127265A (en) * 1994-09-21 1996-07-24 三菱化学株式会社 Process for producing aromatic polycarbonate
CN1345348A (en) * 1999-04-07 2002-04-17 通用电气公司 Optical quality polycarbonates with reduced static charge and method for making same
WO2004111106A1 (en) * 2003-06-16 2004-12-23 Teijin Limited Polycarbonate and process for producing the same
WO2008093860A1 (en) * 2007-02-02 2008-08-07 Teijin Limited Polycarbonate resin and method for producing the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072364B2 (en) * 1986-06-16 1995-01-18 帝人化成株式会社 Method for melt extrusion of polycarbonate
JP3718094B2 (en) * 2000-01-20 2005-11-16 三菱化学株式会社 Method for producing aromatic polycarbonate
JP2004315747A (en) * 2003-04-18 2004-11-11 Mitsubishi Gas Chem Co Inc Aromatic-aliphatic copolycarbonate resin
CN1911629A (en) * 2005-08-12 2007-02-14 荆门市鑫源包装有限公司 High transparency polycarbonate film and sheet material production technology
US8865855B2 (en) * 2006-06-19 2014-10-21 Mitsubishi Chemical Corporation Polycarbonate copolymer and method of producing the same
WO2008133343A1 (en) * 2007-04-25 2008-11-06 Teijin Limited Polycarbonate resin composition
JP5001110B2 (en) * 2007-10-04 2012-08-15 帝人株式会社 Polycarbonate resin and method for producing the same
EP3061782A1 (en) * 2007-12-13 2016-08-31 Mitsubishi Chemical Corporation Processes for producing polycarbonate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1127265A (en) * 1994-09-21 1996-07-24 三菱化学株式会社 Process for producing aromatic polycarbonate
CN1345348A (en) * 1999-04-07 2002-04-17 通用电气公司 Optical quality polycarbonates with reduced static charge and method for making same
WO2004111106A1 (en) * 2003-06-16 2004-12-23 Teijin Limited Polycarbonate and process for producing the same
WO2008093860A1 (en) * 2007-02-02 2008-08-07 Teijin Limited Polycarbonate resin and method for producing the same

Also Published As

Publication number Publication date
JP2015221915A (en) 2015-12-10
CN103351463A (en) 2013-10-16
JP2011021172A (en) 2011-02-03
JP6164790B2 (en) 2017-07-19
CN102224182A (en) 2011-10-19
JP6245240B2 (en) 2017-12-13
CN103351463B (en) 2016-01-06
WO2010061929A1 (en) 2010-06-03

Similar Documents

Publication Publication Date Title
CN102224182B (en) Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article
JP6108651B2 (en) Polycarbonate resin composition, optical film, and polycarbonate resin molded product
TWI441850B (en) Polycarbonate copolymer and production method thereof
CN101356233B (en) Aromatic polycarbonate resin composition for lightguide plate, and lightguide plate
US8481625B2 (en) Polycarbonate resin composition, and molded object, film, plate, and injection-molded article obtained by molding the same
KR101460825B1 (en) Polycarbonate resin composition
TWI462948B (en) Copolymerized carbonates and optical lenses
CN103380176B (en) Poly carbonate resin composition and products formed
JP5635227B2 (en) Light diffusing polycarbonate resin composition
JP6609896B2 (en) Polycarbonate resin composition and molded product
US10526446B2 (en) Polycarbonate resin composition, method for producing same, and molded object
KR101948369B1 (en) Polycarbonate resin
CN115516005A (en) Polycarbonate resin, and optical lens and optical film using same
CN107849344B (en) Polycarbonate resin compound
CN102015827B (en) Polycarbonate resin having ultraviolet absorbing capability, resin composition and optical material
CN114026176A (en) Molded article comprising polycarbonate-based resin composition
JP2011241277A (en) Copolycarbonate
CN107709458B (en) Polycarbonate resin composition, method for producing same, and molded article
CN107709459B (en) Polycarbonate resin composition, method for producing same, and molded article
CN107922720B (en) Polycarbonate resin composition, method for producing same, and molded article
CN117500862A (en) Polycarbonate resin and preparation method thereof
TW202116866A (en) Polycarbonate resin composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: MITSUBISHI CHEMICAL Corp.

Address before: Tokyo, Japan

Patentee before: MITSUBISHI RAYON Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20170919

Address after: Tokyo, Japan

Patentee after: MITSUBISHI RAYON Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: MITSUBISHI CHEMICAL Corp.