CN103351463B

CN103351463B - Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

Info

Publication number: CN103351463B
Application number: CN201310285560.1A
Authority: CN
Inventors: 安藤正人; 田中智彦; 佐佐木一雄; 横木正志
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Rayon Co Ltd
Priority date: 2008-11-28
Filing date: 2009-11-27
Publication date: 2016-01-06
Anticipated expiration: 2029-11-27
Also published as: JP2011021172A; JP6245240B2; JP2015221915A; CN102224182A; CN102224182B; CN103351463A; JP6164790B2; WO2010061929A1

Abstract

The invention provides a kind of polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings, described polycarbonate resin has excellent thermotolerance and the transparency, and described polycarbonate resin contains the structural unit from specific dihydroxy compound.The present invention relates to a kind of polycarbonate resin, it is characterized in that, it is ratio (A/B) scope more than 20% that there is number (A) and whole end number (B) of the polycarbonate resin at least containing the dihydroxy compound from the bond structure with following structural formula (1), the terminal group shown in following structural formula (2).Wherein, the Sauerstoffatom in structural formula (1) not with bonded hydrogen atoms. 。

Description

Polycarbonate resin, poly carbonate resin composition, blooming and polycarbonate resin moldings

The application is divisional application, and the application number of its original application is 200980146641.5, and the applying date is on November 27th, 2009, and denomination of invention is " 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 the polycarbonate resin etc. of the structural unit had from specific dihydroxy compound.

Background technology

In recent years, about using the polycarbonate resin of raw material obtained by Biological resources, having document to describe and using plant origin monomer---Isosorbide, by obtaining the technology (see patent documentation 1) of polycarbonate with the transesterify of diphenyl carbonate.Patent documentation 2 describes polycarbonate resin Isosorbide and dihydroxyphenyl propane copolymerization obtained.Patent documentation 3 describes by improving the outspoken nature of polycarbonate resin with Isosorbide and aliphatic diol copolymerization.

Look-ahead technique document

Patent documentation

Patent documentation 1: English Patent the 1st, 079, No. 686 specification sheetss

Patent documentation 2: the clear 56-055425 publication of Japanese Laid-Open

Patent documentation 3: No. 2004/111106th, International Publication

Summary of the invention

On the other hand, compared with the existing aromatic copolycarbonate from petroleum, the polycarbonate resin being used as the Isosorbide of plant origin monomer to obtain thermotolerance, transparent in unsatisfactory.Further, when also there is melt molding, there is xanthochromia, be difficult to the problem being used as transparent component, optics.

The object of the present invention is to provide a kind of containing from the thermotolerance of the structural unit of specific dihydroxy compound, the polycarbonate resin of transparency excellence and the composition containing this polycarbonate resin.

Following polycarbonate resin, poly carbonate resin composition, blooming, polycarbonate resin moldings can be provided by the present invention.

<1> polycarbonate resin, described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), it is characterized in that, the terminal group shown in following structural formula (2) there is ratio (A/B) scope more than 20% of number (A) relative to whole end number (B).

[changing 1]

(not bonded hydrogen atoms on the Sauerstoffatom wherein, in structural formula (1).)

[changing 2]

The polycarbonate resin of <2> as described in <1>, it is characterized in that, described polycarbonate resin contains the dihydroxy compound that below 60ppm has the bond structure of following structural formula (1).

[changing 3]

The polycarbonate resin of <3> as described in <1> or <2>, it is characterized in that, described polycarbonate resin contains the carbonic diester shown in the following general formula of below 60ppm (3).

[changing 4]

(in general formula (3), A ¹, A ²be with substituting group or without substituent carbonatoms be 1 ~ 18 1 valency fatty group or with substituting group or without substituent 1 valency aromatic series base, A ¹and A ²identical or different.)

<4> is polycarbonate resin as described in any one of <1> ~ <3>, it is characterized in that, this polycarbonate resin contains below 700ppm aromatic monohydroxy compound, and this aromatic monohydroxy compound has or do not have the alkyl that carbonatoms is less than 5.

<5> polycarbonate resin, it is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and the feature of described polycarbonate resin is

Containing below 700ppm aromatic monohydroxy compound, this aromatic monohydroxy compound has or does not have the alkyl that carbonatoms is less than 5.

[changing 5]

<6> polycarbonate resin, it is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), the feature of described polycarbonate resin is, the content of the carbonic diester shown in following general formula (3) is 0.1ppm ~ 60ppm.

[changing 6]

[changing 7]

The polycarbonate resin of <7> as described in <6>, it is characterized in that, the remaining content with the dihydroxy compound of the bond structure of described structural formula (1) is below 60ppm.

<8> polycarbonate resin, it is at least containing the structural unit from dihydroxy compound, and this dihydroxy compound has the bond structure of following structural formula (1), it is characterized in that,

The content with the dihydroxy compound of the bond structure of described structural formula (1) is below 60ppm.

[changing 8]

The polycarbonate resin of <9> as described in any one of <1> ~ <8>, it is characterized in that, the dihydroxy compound with the bond structure of described structural formula (1) has heterocyclic radical.

The polycarbonate resin of <10> as described in any one of <1> ~ <9>, it is characterized in that, the dihydroxy compound with the bond structure of described structural formula (1) is the compound with the heterocyclic radical shown in following general formula (4).

[changing 9]

The polycarbonate resin of <11> as described in any one of <5> ~ <8>, it is characterized in that, the terminal group shown in following structural formula (2) there is ratio (A/B) scope more than 20% of number (A) relative to whole end number (B).

[changing 10]

The polycarbonate resin of <12> as described in any one of <1> ~ <11>, is characterized in that, second-order transition temperature is more than 90 DEG C.

The polycarbonate resin of <13> as described in any one of <1> ~ <12>, it is characterized in that, described polycarbonate resin is also containing the structural unit from least one compound be selected from the group that is made up of aliphatics dihydroxy compound, ester ring type dihydroxy compound, oxyalkylene group glycol, bis-phenol, the glycol with cyclic acetal structure.

<14> poly carbonate resin composition, it is characterized in that, described composition contains the lipid acid of polycarbonate resin described in 100 any one of weight part <1> ~ <13> and 0.0001 weight part ~ 2 weight part.

The poly carbonate resin composition of <15> as described in <14>, it is characterized in that, described composition contains the natural system wax of polycarbonate resin described in 100 any one of weight part <1> ~ <13> and 0.0001 weight part ~ 2 weight part.

The poly carbonate resin composition of <16> as described in <14> or <15>, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part <1> ~ <13> and 0.0001 weight part ~ 2 weight part and is selected from least one compound in olefines wax, silicone oil.

The poly carbonate resin composition of <17> as described in any one of <14> ~ <16>, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part <1> ~ <13> and 0.00001 weight part ~ 0.1 weight part acidic cpd.

The poly carbonate resin composition of <18> as described in any one of <14> ~ <17>, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part <1> ~ <13> and 0.001 weight part ~ 1 weight part phosphorus series compound.

The poly carbonate resin composition of <19> as described in any one of <14> ~ <18>, it is characterized in that, described composition contains polycarbonate resin, 0.00001 weight part ~ 0.1 weight part at least one acidic cpd and 0.001 weight part ~ 1 weight part at least one phosphorus series compound described in 100 any one of weight part <1> ~ <13>.

The poly carbonate resin composition of <20> as described in any one of <14> ~ <19>, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part <1> ~ <13>, aromatic monohydroxy compound that 0.001 weight part ~ 1 weight part is the alkyl substituent of more than 5 with more than 1 carbonatoms.

The poly carbonate resin composition of <21> as described in any one of <14> ~ <20>, it is characterized in that, described composition contains poly carbonate resin composition described in 100 any one of weight part <1> ~ <13> and 0.000001 weight part ~ 1 weight part bluing agent.

<22> blooming, it is characterized in that, it contains the polycarbonate resin described in any one of <1> ~ <13>.

<23> polycarbonate resin moldings, it is characterized in that, it carries out shaping obtaining by by the polycarbonate resin described in any one of <1> ~ <13> or the poly carbonate resin composition described in any one of <14> ~ <21>.

The polycarbonate resin moldings of <24> as described in <23>, is characterized in that, described polycarbonate resin moldings obtains by injection moulding is shaping.

<25> poly carbonate resin composition, is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part ~ 100 parts by weight of inorganic filler,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the terminal group shown in following structural formula (2) there is ratio (A/B) scope more than 20% of number (A) relative to whole end number (B).

[changing 11]

[changing 12]

<26> poly carbonate resin composition, is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part ~ 100 parts by weight of inorganic filler,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains below 700ppm has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl of less than 5.

[changing 13]

<27> poly carbonate resin composition, is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part ~ 100 parts by weight of inorganic filler,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, 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 following general formula (3) is 0.1ppm ~ 60ppm.

[changing 14]

[changing 15]

<28> poly carbonate resin composition, is characterized in that, it contains 100 weight part polycarbonate resins and 1 weight part ~ 100 parts by weight of inorganic filler,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the content with the dihydroxy compound of the bond structure of following structural formula (1) is below 60ppm.

[changing 16]

<29> 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,

[changing 17]

[changing 18]

The poly carbonate resin composition of <30> as described in <29>, it is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

<31> 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 is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), further, described polycarbonate resin contains below 700ppm and has or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl of less than 5.

[changing 19]

The poly carbonate resin composition of <32> as described in <31>, it is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

<33> poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.01 weight part ~ 30 parts by weight of flame retardant,

[changing 20]

[changing 21]

The poly carbonate resin composition of <34> as described in <33>, it is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

<35> poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.01 weight part ~ 30 parts by weight of flame retardant,

[changing 22]

The poly carbonate resin composition of <36> as described in <35>, it is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

<37> poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part ~ 5 weight part UV light absorber,

[changing 23]

[changing 24]

The poly carbonate resin composition of <38> as described in <37>, it is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

The poly carbonate resin composition of <39> as described in <37> or <38>, it is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

<40> poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part ~ 5 weight part UV light absorber,

[changing 25]

The poly carbonate resin composition of <41> as described in <40>, it is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

The poly carbonate resin composition of <42> as described in <40> or <41>, it is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

<43> 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,

[changing 26]

[changing 27]

The poly carbonate resin composition of <44> as described in <43>, it is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

The poly carbonate resin composition of <45> as described in <43> or <44>, it is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

<46> poly carbonate resin composition, it contains 100 weight part polycarbonate resins and 0.005 weight part ~ 5 weight part UV light absorber,

[changing 28]

The poly carbonate resin composition of <47> as described in <46>, it is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

The poly carbonate resin composition of <48> as described in <46> or <47>, it is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

<49> poly carbonate resin composition, is characterized in that, it contains 10 weight part ~ 90 weight part polycarbonate resin (a) and 90 weight part ~ 10 weight parts thermoplastic resin (b),

[changing 29]

[changing 30]

The poly carbonate resin composition of <50> as described in <49>, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

<51> poly carbonate resin composition, is characterized in that, it contains 10 weight part ~ 90 weight part polycarbonate resin (a) and 90 weight part ~ 10 weight parts thermoplastic resin (b),

[changing 31]

The poly carbonate resin composition of <52> as described in <51>, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

<53> poly carbonate resin composition, is characterized in that, it contains 10 weight part ~ 90 weight part polycarbonate resin (a) and 90 weight part ~ 10 weight parts thermoplastic resin (b),

[changing 32]

[changing 33]

The poly carbonate resin composition of <54> as described in <53>, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

<55> poly carbonate resin composition, is characterized in that, it contains 10 weight part ~ 90 weight part polycarbonate resin (a) and 90 weight part ~ 10 weight parts thermoplastic resin (b),

[changing 34]

The poly carbonate resin composition of <56> as described in <55>, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

<57> polycarbonate resin moldings, it is characterized in that, it is that the poly carbonate resin composition described in any one of <25> ~ <56> is carried out shaping obtaining.

The polycarbonate resin moldings of <58> as described in <57>, it is characterized in that, polycarbonate resin moldings carries out shaping obtaining by injection moulding.

Thermotolerance, the polycarbonate resin of transparency excellence and the poly carbonate resin composition containing this polycarbonate resin can be obtained according to the present invention.

Accompanying drawing explanation

What [Fig. 1] showed is the polycarbonate resin A-1's containing heterocycle ¹h-NMR collection of illustrative plates.

Embodiment

Below working of an invention mode is specifically described.It should be noted that, the present invention is not limited to following embodiment, can carry out various change during enforcement in the scope of its main points.In addition, the accompanying drawing used, for illustration of present embodiment, does not represent the size of its reality.In addition, in the present invention, if no special instructions, ppm represents the part by weight of the standard substance relative to object.

[1] polycarbonate resin

The polycarbonate resin that the present invention uses has at least containing the structure from the structural unit of dihydroxy compound, and this dihydroxy compound has the bond structure of following structural formula (1).

[changing 35]

(dihydroxy compound)

As the dihydroxy compound of bond structure with structure above (1), such as can enumerate 9, 9-bis-(4-(2-hydroxyl-oxethyl) phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-isopropyl phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-isobutyl phenenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-cyclohexyl phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3-phenyl) fluorenes, 9, 9-bis-(4-(2-hydroxyl-oxethyl)-3, 5-3,5-dimethylphenyl) fluorenes, 9, 9-bis-(4-(2-the hydroxyl-oxethyl)-3-tertiary butyl-6-aminomethyl phenyl) fluorenes, 9, 9-bis-(4-(3-hydroxyl-2, 2-dimethyl propoxy-) phenyl) illustrated at side chain, there is aromatic series base and there is at main chain the compound of the ether being bonded in aromatic series base such as fluorenes, the oxyalkylene group glycols that Diethylene Glycol, triethylene glycol, Tetraglycol 99 etc. are illustrated, two [4-(2-hydroxyl-oxethyl) phenyl] methane, two [4-(2-hydroxyl-oxethyl) phenyl] ditane, two [4-(2-hydroxyl-oxethyl) phenyl] ethane of 1,1-, two [4-(2-hydroxyl-oxethyl) the phenyl]-1-diphenylphosphino ethane of 1,1-, two [4-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-, two [4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl] propane of 2,2-, two [3,5-dimethyl-4-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-, two [4-(2-hydroxyl-oxethyl) phenyl]-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene of 1,1-, Isosorbide-5-Nitrae-bis-[4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene of 1,3-, 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-methylpentane of 2,2-, two [4-(2-hydroxyl-oxethyl) phenyl] octane of 2,2-, two [4-(2-hydroxyl-oxethyl) phenyl] decane of 1,1-, two [the bromo-4-of 3-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-, two (hydroxy alkoxy Ji Fangji) paraffinic that two [3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-etc. are illustrated, 1, two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene, 1 of 1-, two (hydroxy alkoxy Ji Fangji) loop chain alkanes that two [3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene of 1-, 1,1-two [4-(2-hydroxyl-oxethyl) phenyl] pentamethylene etc. are illustrated, 4,4 '-two (2-hydroxyl-oxethyl) diphenyl ether, 4, the dihydroxyalkoxy diaryl ethers that 4 '-two (2-hydroxyl-oxethyl)-3,3 '-dimethyl diphenyl ether etc. are illustrated, 4,4 '-two (2-hydroxyethoxyphenyl) sulfide, 4, two hydroxy alkoxy base aromatic yl sulfide classes that 4 '-bis-[4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfide etc. are illustrated, 4,4 '-two (2-hydroxyethoxyphenyl) sulfoxide, 4, two hydroxy alkoxy base aryl sulfoxid es classes that 4 '-bis-[4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfoxide etc. are illustrated, 4,4 '-two (2-hydroxyethoxyphenyl) sulfone, 4, two hydroxy alkoxy base aryl sulfones that 4 '-bis-[4-(2-dihydroxyl oxyethyl group)-3-aminomethyl phenyl] sulfone etc. are illustrated, 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] benzene, 1 of 3-, two [2-[4-(2-hydroxyl-oxethyl) phenyl] propyl group] benzene, 4 of 4-, 4 '-two (2-hydroxyl-oxethyl) biphenyl, 1, two [4-(2-hydroxyl-oxethyl) phenyl]-5, the 7-dimethyladamantanes of 3-, the dihydroxy compound shown in following general formula (4) are the dihydroxy compound with heterocyclic radical of representative, with 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-base)-2-methylpropane-1-alcohol, 3,9-bis-(2-hydroxyl-1,1-dimethyl ethyl)-2,4,8,10-tetra-oxaspiro [5,5] the spiroglycol class such as undecane, these can be used alone, but also two or more combinationally uses.

Wherein, the dihydroxy compound shown in preferred following general formula (4).

[changing 36]

As the dihydroxy compound shown in above-mentioned general formula (4), such as, can enumerate, be in the Isosorbide of the relation of steric isomer, isomannite, different idose.These can be used alone a kind, but also two or more combinationally uses.Among these dihydroxy compound, from the aspect of the easiness obtaining and manufacture, optical characteristics, formability, the Isosorbide most preferably obtained through dehydrating condensation by the Sorbitol Powder of the various starch manufactures of aboundresources, easily acquisition.

It should be noted that Isosorbide is easily oxidized at leisure by oxygen.Therefore, when the process when preservation, manufacture, in order to prevent the decomposition caused by oxygen, not importantly being mixed into moisture and using reductor or carry out in a nitrogen atmosphere.After Isosorbide is oxidized, can produce with formic acid is the resolvent of representative.Such as, when using the Isosorbide containing these resolvents to manufacture polycarbonate resin, obtained polycarbonate resin is caused to occur painted or cause physicals to be obviously deteriorated.In addition, it also has impact to polyreaction sometimes, can not obtain the polymkeric substance of high molecular, so be not preferred.In addition, interpolation prevents the stablizer of the generation of formic acid under such circumstances, and some stabilizer type can cause the polycarbonate resin obtained occur painted or cause physicals to be obviously deteriorated.As stablizer, reductive agent, antacid can be used.Wherein, as reductive agent, can sodium borohydride, lithium borohydride etc. be enumerated, as antacid, can an alkali metal salts such as sodium hydroxide be enumerated.Due to basic metal or polymerizing catalyst, so when adding such an alkali metal salt, if excessive interpolation, then polyreaction can not be controlled, so be not preferred.It should be noted that, in this specification sheets, the term " basic metal " used and " alkaline-earth metal " are identical with the implication of " group II metal " with " the 1st race's metal " in long period type periodictable (NomenclatureofInorganicChemistryIUPACRecommendations2005) respectively.

In order to obtain the Isosorbide of oxygen-freeization resolvent, can distill Isosorbide as required.In addition, in order to prevent the oxidation of Isosorbide, decomposition and with the addition of stablizer when, also can distill Isosorbide as required.In this case, the distillation of Isosorbide can be simple distillation, can be also continuous still battery, be not particularly limited this.About distillation, under the inert gas atmosphere such as argon, nitrogen, implement underpressure distillation.By carrying out such distillation to Isosorbide, the high purity Isosorbide that formic acid content is below 20ppm, special below 5ppm can be obtained.

In addition, about formic acid content measuring method in Isosorbide, ion chromatograph is used to measure by following order.

Accurately take 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, with the standard test specimen peak consistent with retention time for formic acid, according to peak area, utilize absolute standard curve method, carry out quantitative.

Ion chromatograph uses the DX-500 type of Dionex society, and detector uses electrical conductivity degree detector.About measuring column, Dionex society manufactures guard column and uses AG-15, and separator column uses AS-15.Mensuration sample is injected the sample loop of 100 μ l, use 10mM-NaOH as elutriant, continue to measure in flow velocity 1.2ml/min, thermostatic bath temperature 35 DEG C.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 ester ring type dihydroxy compound except the above-mentioned structural unit carrying out the dihydroxy compound shown in self-drifting (4).

Ester ring type dihydroxy compound is had no particular limits, usually can enumerate the compound containing 5 ring structures or 6 ring structures.When ester ring type dihydroxy compound is 5 rings, 6 ring structure, the thermotolerance of obtained polycarbonate resin can be improved.6 ring structures can be chair form or boat formula by covalently immobolization.

Carbonatoms contained by ester ring type dihydroxy compound is generally less than 70, is preferably less than 50, more preferably less than 30.When carbonatoms is too much, thermotolerance increases, but synthesis becomes difficulty, or purification becomes difficulty, there is the trend of cost up.Carbonatoms is less, more easily purifies, and easily obtains.

As the ester ring type dihydroxy compound containing 5 ring structures or 6 ring structures, following general formula (II) or the ester ring type dihydroxy compound shown in (III) specifically can be enumerated.

HOCH ₂-R ¹-CH ₂OH(II)

HO-R ²-OH(III)

(wherein, in formula (II), formula (III), R ¹, R ²represent that carbonatoms is the ring alkylidene group of 4 ~ 20)

As the cyclohexanedimethanol belonging to the ester ring type dihydroxy compound shown in above-mentioned general formula (II), it comprises R in general formula (II) ¹for following general formula (IIa) (in formula, R ³represent that carbonatoms is the alkyl of 1 ~ 12) shown in various isomer under structure situation.As such compound, specifically 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol etc. can be enumerated.

[changing 37]

As the Tricyclodecane Dimethanol, the pentacyclopentadecane dimethanol that belong to the ester ring type dihydroxy compound shown in above-mentioned general formula (II), it comprises R in general formula (II) ¹for the various isomer shown in following general formula (IIb) (in formula, n represents 0 or 1).

[changing 38]

As the naphthalane dimethanol or the three ring tetradecane dimethanols that belong to the ester ring type dihydroxy compound shown in above-mentioned general formula (II), it comprises R in general formula (II) ¹for the various isomer shown in following general formula (IIc) (in formula, m represents 0 or 1).As such compound, 2,6-naphthalane dimethanol, 1,5-naphthalane dimethanol, 2,3-naphthalane dimethanols etc. specifically can be enumerated.

[changing 39]

In addition, as the norcamphane dimethanol belonging to the ester ring type dihydroxy compound shown in above-mentioned general formula (II), it comprises R in general formula (II) ¹for the various isomer shown in following general formula (IId).As such compound, 2,3-norcamphane dimethanol, 2,5-norcamphane dimethanols etc. specifically can be enumerated.

[changing 40]

As the diamantane dimethanol belonging to the ester ring type dihydroxy compound shown in general formula (II), it comprises R in general formula (II) ¹for the various isomer shown in following general formula (IIe).As such compound, 1,3-diamantane dimethanol etc. specifically can be enumerated.

[changing 41]

In addition, as the cyclohexanediol belonging to the ester ring type dihydroxy compound shown in above-mentioned general formula (III), it comprises R in general formula (III) ²for following general formula (IIIa) (R in formula ³represent the carbonatoms alkyl that is 1 ~ 12) shown in various isomer.As such compound, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-methyl isophthalic acid specifically can be enumerated, 4-cyclohexanediol etc.

[changing 42]

As the three ring decanediols, five rings five decanediol that belong to the ester ring type dihydroxy compound shown in above-mentioned general formula (III), it comprises R in general formula (III) ²for the various isomer shown in following general formula (IIIb) (in formula, n represents 0 or 1).

[changing 43]

As the naphthalane glycol or three ring four decanediols that belong to the ester ring type dihydroxy compound shown in above-mentioned general formula (III), it comprises R in general formula (III) ²for the various isomer shown in following general formula (IIIc) (in formula, m represents 0 or 1).As such compound, 2,6-naphthalane glycol, 1,5-naphthalane glycol, 2,3-naphthalane glycol etc. specifically can be used.

[changing 44]

As the norcamphane glycol belonging to the ester ring type dihydroxy compound shown in above-mentioned general formula (III), it comprises R in general formula (III) ²for the various isomer shown in following general formula (IIId).As such compound, 2,3-norcamphane glycol, 2,5-norcamphane glycol etc. specifically can be used.

[changing 45]

As the diamantane glycol belonging to the ester ring type dihydroxy compound shown in above-mentioned general formula (III), it comprises R in general formula (III) ²for the various isomer shown in following general formula (IIIe).As such compound, 1,3-diamantane glycol etc. specifically can be used.

[changing 46]

Among the concrete example of above-mentioned ester ring type dihydroxy compound, particularly preferably cyclohexanedimethanol class, Tricyclodecane Dimethanol class, diamantane glycols, pentacyclopentadecane dimethanol class, from the viewpoint of easily obtaining, easily process, preferably 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-CHDM, Tricyclodecane Dimethanol.

It should be noted that, above-mentioned exemplary compounds is the 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 be used alone a kind, can be used in combination by two or more.

In the polycarbonate resin that the present invention uses, being not particularly limited containing proportional for the structural unit from the dihydroxy compound shown in above-mentioned general formula (4) and the structural unit from ester ring type dihydroxy compound, can select with arbitrary ratio.

Should be generally (structural unit carrying out the dihydroxy compound shown in self-drifting (4)) containing proportional: (structural unit from ester ring type dihydroxy compound)=(1:99) ~ (99:1) (% by mole), is particularly preferably (structural unit carrying out the dihydroxy compound shown in self-drifting (4)): (structural unit from ester ring type dihydroxy compound)=(10:90) ~ (90:10) (% by mole).

Compared with above-mentioned scope, the structural unit carrying out the dihydroxy compound shown in self-drifting (4) too much and very few from the structural unit of ester ring type dihydroxy compound time, polycarbonate resin is easily with color.On the contrary, the structural unit carrying out the dihydroxy compound shown in self-drifting (4) very few and too much from the structural unit of ester ring type dihydroxy compound time, the molecular weight of polycarbonate resin not easily increases.

(other dihydroxy compound)

In addition, the polycarbonate resin that the present invention uses can also structural unit containing other dihydroxy compound except coming the dihydroxy compound shown in self-drifting (4) and above-mentioned ester ring type dihydroxy compound.

As other such dihydroxy compound, such as, can enumerate aliphatics dihydroxy compound, oxyalkylene group glycol, bis-phenol, there is the glycol etc. of cyclic acetal structure.

As aliphatics dihydroxy compound, such as, can enumerate ethylene glycol, 1,3-PD, 1,2-PD, BDO, 1,3 butylene glycol, 1,2-butyleneglycol, 1,5-heptanediol, 1,6-hexylene glycol etc.

As bis-phenol, such as can enumerate 2, 2-bis-(4-hydroxy phenyl) propane [=dihydroxyphenyl propane], 2, 2-bis-(4-hydroxyl-3, 5-3,5-dimethylphenyl) propane, 2, 2-bis-(4-hydroxyl-3, 5-diethyl phenyl) propane, 2, 2-bis-(4-hydroxyl-(3, 5-phenylbenzene) phenyl) propane, 2, 2-bis-(4-hydroxyl-3, 5-dibromo phenyl) propane, 2, 2-bis-(4-hydroxy phenyl) pentane, 2, 4 '-dihydroxyl-ditane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, 1, 1-bis-(4-hydroxy phenyl) ethane, 3, 3-bis-(4-hydroxy phenyl) pentane, 1, 1-bis-(4-hydroxy phenyl) hexanaphthene etc.

In addition, as bis-phenol, such as two (4-hydroxy phenyl) sulfone, 2 can also be enumerated, 4 '-dihydroxy-diphenyl sulfone, two (4-hydroxy phenyl) sulfide, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-Dichlorodiphenyl ether, 4,4 '-dihydroxyl-2,5-diethoxy diphenyl ether, 9,9-bis-(4-(2-hydroxyl-oxethyl) phenyl) fluorenes, 9,9-bis-(4-(2-hydroxyl-oxethyl-2-methyl) phenyl) fluorenes, 9,9-bis-(4-hydroxy phenyl) fluorenes, 9,9-bis-(4-hydroxy-2-methyl phenyl) fluorenes.

In addition, as the glycol with cyclic acetal structure, such as, can enumerate the spiroglycol, dioxane glycol etc.

These other dihydroxy compound can use one kind or two or more.

By using other dihydroxy compound, the flexibility that can improve, improving thermotolerance, improve the effects such as formability.Especially, from other dihydroxy compound structural unit containing proportional too much time, make the performance of optical characteristics originally reduce sometimes.

Therefore, in the polycarbonate resin that the present invention uses, the total amount of the dihydroxy compound shown in preferred formula (4) and ester ring type dihydroxy compound is more than 90 % by mole relative to the ratio of the whole dihydroxy compound forming polycarbonate resin.

Particularly preferably the present invention use polycarbonate resin in dihydroxy compound be only made up of the dihydroxy compound shown in general formula (4) and ester ring type dihydroxy compound.

About the polymerization degree of the polycarbonate resin that the present invention uses, in the reduced viscosity measured as follows (hereinafter referred to as " polycarbonate resin reduced viscosity "), for more than 0.40dl/g, be particularly preferably the polymerization degree that 0.40dl/g ~ 2.0dl/g is such, further the preferred polymerization degree such in the scope of 0.45dl/g ~ 1.5dl/g.Being determined as follows of described reduced viscosity is carried out: use mixing solutions that the weight ratio of phenol and sym.-tetrachloroethane is 1:1 as solvent, be 1.00g/dl, measure polycarbonate resin lipid concentration fine setting temperature 20.0 DEG C ± 0.1 DEG C.

When the reduced viscosity of polycarbonate resin is too low, physical strength when being shaped to lens etc. easily reduces.In addition, when the reduced viscosity of polycarbonate resin is excessive, mobility when carrying out shaping reduces, and cycle characteristics is reduced, and the degree of birefringence of products formed easily becomes large.

The Abbe number of the polycarbonate resin that the present invention uses is preferably more than 50, is particularly preferably more than 55.This value is larger, then the wavelength dispersion of specific refractory power is less, and such as, aberration when using as simple lens diminishes, and easily obtains distincter image.Abbe number is less, then the wavelength dispersion of specific refractory power is larger, and when using as simple lens, aberration becomes large, and the fog-level of image becomes large.

5% thermal weight loss temperature of the polycarbonate resin that the present invention uses is preferably more than 340 DEG C, is particularly preferably more than 345 DEG C.5% thermal weight loss temperature is larger, then thermostability is higher, can stand to use at a higher temperature; 5% thermal weight loss temperature is less, then thermostability is lower, is difficult at high temperature use.In addition, control during manufacture allows that amplitude narrows, and is difficult to make.Moreover manufacture temperature and also can increase, during manufacture, span of control can be wider, so easily manufacture.

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 the masking such as solution-casting method obtains increases, when being stretched, the fluctuation of the phase differential caused in face increases by the small vibrations of tension force further.In addition, when pasting such phase retardation film, not only desired phase differential can be able to be caused to offset because of tension force when pasting, also the easy contraction etc. because of the polaroid after stickup causes phase difference value to change.Photoelastic coefficient is less, then the fluctuation of phase differential is less.

The preferred cantilever beam impact strength of polycarbonate resin that the present invention uses is 30J/m ²above.Cantilever beam impact strength is larger, then the intensity of formed body is higher, is more not easy to damage.

Gas generated (following, sometimes referred to as " gas generated ") of the polycarbonate resin that the present invention uses preferably at 110 DEG C on per unit area except phenol is 5ng/cm ²below, in addition, more preferably carrying out the gas generated of the dihydroxy compound beyond the dihydroxy compound shown in self-drifting (4) is 0.5ng/cm ²below.This is gas generated fewer, more can be applied to the purposes needing to avoid the impact producing gas, such as, preserve the housing etc. of the purposes of electronic unit such as semi-conductor, the in-built material purposes, family's electrical article etc. of buildings.

In addition, the present invention use the Abbe number of polycarbonate resin, 5% thermal weight loss temperature, photoelastic coefficient, cantilever beam impact strength, generation gas volume measuring method specifically as shown in embodiment one described later saves.

For the polycarbonate resin that the present invention uses, when being measured by differential scanning calorimeter (DSC), single second-order transition temperature can be observed.By adjusting kind, the proportioning of the dihydroxy compound shown in general formula (4) and ester ring type dihydroxy compound, the polycarbonate resin of the present invention's use can be obtained with the polymer form in about 45 DEG C ~ about 155 DEG C scopes with any second-order transition temperature according to purposes.

Such as, for the film purposes needing flexibility, preferably the second-order transition temperature of polycarbonate resin is adjusted to more than 45 DEG C, such as 45 ~ 100 DEG C.

Particularly for the formed body purposes such as bottle, bag requiring thermotolerance, the second-order transition temperature of polycarbonate resin is preferably adjusted to more than 90 DEG C, such as 90 ~ 130 DEG C.

In addition, when second-order transition temperature is more than 120 DEG C, the lens application of optics can be suitable as.That is, by using, there is the polycarbonate resin of such second-order transition temperature, even if also not easily deform under the such high-temperature high-humidity of temperature 85 DEG C, relative humidity 85%, the lens that the fluctuation of surface accuracy is little can be obtained.

(manufacture method of polycarbonate resin)

The polycarbonate resin that the present invention uses can be manufactured by existing known polymerization process.As polymerization process, any means in the melt phase polycondensation solution polymerization process of phosgene can be used, carbonic diester and oxy-compound being reacted.

Wherein, preferably under the existence of polymerizing catalyst, the melt phase polycondensation that the dihydroxy compound making the bond structure with structure above (1), other dihydroxy compound used as required and carbonic diester react.

(carbonic diester)

As the carbonic diester that melt phase polycondensation uses, the carbonic diester shown in following general formula (3) usually can be enumerated.These carbonic diesters can be used alone a kind, can be used in combination by two or more.

[changing 47]

As the carbonic diester shown in above-mentioned general formula (3), such as, can enumerate diphenyl carbonate, xylyl carbonate etc. and replace diphenyl carbonate; Methylcarbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc.

Among these, particularly preferably diphenyl carbonate, replacement diphenyl carbonate, diphenyl carbonate.

In above-mentioned melt phase polycondensation, relative to for react containing whole dihydroxy compound of dihydroxy compound of bond structure with structural formula (1), the molar ratio of the carbonic diester shown in general formula (3) used is 0.90 ~ 1.10, is more preferably 0.96 ~ 1.04.

When the mol ratio of the carbonic diester used in melt phase polycondensation is too small, the end OH base of manufactured polycarbonate resin increases, and the thermostability of polymkeric substance is deteriorated, and may can not get desired high molecular weight material.On the other hand, when the mol ratio of the carbonic diester used is excessive, under the same polymerization conditions, the speed of transesterification reaction reduces, and may be difficult to the polycarbonate resin of the molecular weight desired by manufacturing.In addition, carbonic diester amount remaining in manufactured polycarbonate resin may increase, when remaining carbonic diester may cause shaping or the peculiar smell of products formed.

From the viewpoint of such, the remaining content preferably in the polycarbonate resin that the present invention uses with the dihydroxy compound of the bond structure of structural formula (1) is below 60ppm, and more preferably below 50ppm, is particularly preferably below 30ppm.

When the remaining content with the dihydroxy compound of the bond structure of structural formula (1) in polycarbonate resin is too much, the thermostability of polymkeric substance is deteriorated, when injection molding, the dirt settling be attached on metal pattern increases simultaneously, carry out sheet, film extrusion moulding time, the amount of roller dirt settling increases, and there is the possibility causing appearance impaired.

In addition, in the polycarbonate resin that the present invention uses, the remaining content of the carbonic diester shown in preferred formula (3) is below 60ppm, is more preferably 0.1ppm ~ 60ppm, further preferred 0.1ppm ~ 50ppm, particularly preferably 0.1ppm ~ 30ppm.

When the content of the carbonic diester shown in general formula (3) in polycarbonate resin is too much, the dirt settling be attached to when injection molding on metal pattern increases, carry out sheet, film extrusion moulding time, the amount of roller dirt settling increases, exist cause appearance impaired possibility.

(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 (being sometimes denoted as below " phenyl end ") shown in following structural formula (2) of manufactured polycarbonate resin there is ratio (A/B) scope preferably more than 20% of number (A) relative to whole end number (B).

In addition, polycarbonate resin phenyl end there is ratio (A/B) the further preferred scope more than 25% of number (A) relative to whole end number (B), particularly preferably in the scope of more than 30%.

Phenyl end exist number (A) very few relative to the ratio (A/B) of whole end number (B) time, be under the condition of high temperature at polymeric reaction temperature, injecting forming temperature etc., there is the possibility of painted increase.

[changing 48]

The method that number (A) adjusts to above-mentioned scope relative to the ratio (A/B) of whole end number (B) that exists for the phenyl end by polycarbonate resin has no particular limits, such as, 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 for reacting; Or residual monomers is scavenged into outside reaction system by degassed by section after polymerization; Or the stirring efficiency etc. of reaction machine improving polyreaction back segment is to improve speed of response, the number (A) that exists of phenyl end can be adjusted to above-mentioned scope relative to the ratio (A/B) of whole end number (B) thus.

For the ratio of the phenyl end in polycarbonate resin, NMR spectrometer can be utilized, use the deuterochloroform that with the addition of TMS as mensuration solvent, pass through ¹the mensuration of H-NMR spectrum calculates.

In addition, there is the ratio from each dihydroxy compound structural unit of the dihydroxy compound of the bond structure of structural formula (1), ester ring type dihydroxy compound and the usage ratio of other dihydroxy compound that uses as required formation polycarbonate resin used according to the invention, it is suitably adjusted.

(polymerizing catalyst)

As the polymerizing catalyst (transesterification catalyst) in melt polymerization, use alkali metal compound and/or alkali earth metallic compound.Also together can secondarily share the basic cpds such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound, amine compound with alkali metal compound and/or alkali earth metallic compound, but particularly preferably only use alkali metal compound and/or alkali earth metallic compound.

As the alkali metal compound being used as polymerizing catalyst, such as sodium hydroxide can be enumerated, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, saleratus, lithium bicarbonate, cesium bicarbonate, sodium carbonate, salt of wormwood, Quilonum Retard, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, stearic acid caesium, sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride, hydroboration caesium, phenyl-boron dihydroxide sodium, phenyl-boron dihydroxide potassium, phenyl-boron dihydroxide lithium, phenyl-boron dihydroxide caesium, Sodium Benzoate, potassium benzoate, lithium benzoate, phenylformic acid caesium, Sodium phosphate dibasic, dipotassium hydrogen phosphate, phosphoric acid hydrogen two lithium, phosphoric acid hydrogen two caesium, disodium phenylphosphate, phosphenylic acid dipotassium, phosphenylic acid two lithium, phosphenylic acid two caesium, 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, such as 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. can be enumerated.These alkali metal compounds and/or alkali earth metallic compound can be used alone one, also can be used together two or more.

As the concrete example of the alkaline boron compound 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, trimethylethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethylbenzyl boron, triethyl phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyltriphenyl phosphonium boron, methyl triphenyl boron, butyl triphenyl boron etc.

As alkaline phosphating compound, such as, 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, such as, can enumerate Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphenyl ammonium hydroxide, butyl triphenyl ammonium hydroxide etc.

As amine compound, such as 4-aminopyridine, PA, 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. can be enumerated.These basic cpds also can be used alone one, also can be used together two or more.

When using alkali metal compound and/or alkali earth metallic compound, to be converted into the gauge of metal, the whole dihydroxy compound used relative to 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 of the polycarbonate resin necessity to the molecular weight desired by manufacture, on the other hand, when the consumption of polymerizing catalyst is too much, the tone of the polycarbonate resin obtained worsens, produce by product, mobility reduces and the generation of gel increases, and is difficult to the polycarbonate of manufacturing objective quality.

When manufacturing the polycarbonate resin of the present invention's use, the above-mentioned dihydroxy compound with the bond structure of structural formula (1) both can supply in solid form, also to supply with molten state after heating, can also can supply in form of an aqueous solutions.

Ester ring type dihydroxy compound is also both can supply in solid form, also to supply with molten state after heating, as long as this ester ring type dihydroxy compound is water-soluble material, can also can supply in form of an aqueous solutions.Dihydroxy compound for other is also so same.If these raw material dihydroxy compound supply with the form of molten state or the aqueous solution, then there is when industry manufactures the advantage being easy to measure and carry.

In the present invention, under the existence of polymerizing catalyst, there is the method that the dihydroxy compound of the bond structure of structural formula (1) and ester ring type dihydroxy compound and other dihydroxy compound used as required and carbonic diester react and usually implement with multistage operations more than 2 stages.

Specifically, the reaction in the 1st stage implements 0.1 ~ 10 hour (preferably 0.5 ~ 3 hour) in the temperature of 140 ~ 220 DEG C (preferably 150 ~ 200 DEG C).After 2nd stage, the pressure of reaction system is slowly reduced from the pressure in the 1st stage and temperature of reaction is raised, the aromatic monohydroxy compounds such as the phenol of generation are discharged to outside reaction system simultaneously, the pressure of end reaction system is below 200Pa, temperature is 210 ~ 280 DEG C, carries out polycondensation thus.

In decompression process in polycondensation, the balance of the pressure importantly in control temperature and reaction system.When either party of particularly temperature or pressure changes too quickly, unreacted monomer distillation out, makes the mol ratio of dihydroxy compound and carbonic diester change, and the polymerization degree reduces sometimes.

Such as, use Isosorbide and 1, when 4-cyclohexanedimethanol is as dihydroxy compound, 1, when 4-cyclohexanedimethanol is more than 50 % by mole relative to the mol ratio of whole dihydroxy compound, 1, 4-cyclohexanedimethanol is easy to the form of monomer by straight run distillation out, so the pressure in reaction system is under the decompression of about 13kPa, react while making temperature increase with the speed raising less than 40 DEG C for every 1 hour, and then under the pressure dropping to about 6.67kPa, temperature is raised with the speed raising less than 40 DEG C for every 1 hour, finally at the pressure of below 200Pa, polycondensation is carried out at the temperature of 200 DEG C to 250 DEG C, the polycarbonate resin that the polymerization degree substantially increases can be obtained like this, therefore this is preferred.

Relative to whole dihydroxy compound, 1, when the mol ratio of 4-cyclohexanedimethanol is less than 50 % by mole, when particularly this mol ratio is below 30 % by mole, occur that viscosity sharply rises, so the pressure such as in reaction system is until under reaching the decompression of about 13kPa, reacted while the heat-up rate raised temperature of less than 40 DEG C with every 1 hour, be reduced to the pressure of about 6.67kPa again at pressure under, reacted while the heat-up rate of more than 40 DEG C (being preferably every 1 hour heat-up rate of more than 50 DEG C) raised temperature with every 1 hour, final under the decompression of below 200Pa, polycondensation is carried out at the temperature of 220 to 290 DEG C, carry out obtaining the polycarbonate resin that the polymerization degree substantially increases like this, thus this is preferred.The form of reaction can be the either 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, generate with by-product form and there is or do not have the aromatic monohydroxy compound that carbonatoms is the alkyl of less than 5.

In present embodiment, contained by optimization polycarbonate resin to have or do not have carbonatoms be the content of the aromatic monohydroxy compound of the alkyl of less than 5 is below 700ppm, more preferably content is below 500ppm, and particularly preferably content is below 300ppm.

But the above-mentioned aromatic monohydroxy compound containing about 10ppm in the polycarbonate resin that the present invention uses, this is unavoidably remaining amount.

Herein, having or do not have carbonatoms is that the aromatic monohydroxy compound of the alkyl of less than 5 means not comprise and aftermentionedly adds the antioxidants such as the such as 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 of less than 5, such as 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 of less than 5 adjusts to below 700ppm has no particular limits for the carbonatoms that has or do not have contained by polycarbonate resin, usually can enumerate following method.

Such as, in polycondensation, make the feed ratio of dihydroxy compound and carbonic diester close to 1; Increase polycondensation; Effectively above-mentioned aromatic monohydroxy compound is discharged to outside the reactor carrying out polycondensation; Use horizontal reactor to apply predetermined shearing force to full-bodied reaction solution in the second half section of polycondensation, carry out degassed simultaneously; Water and above-mentioned aromatic monohydroxy compound azeotropic etc. is made by water filling devolatilization operation.

In the polycarbonate resin that the present invention uses, have or do not have carbonatoms be the content of the aromatic monohydroxy compound of the alkyl of less than 5 too much time, impair tone and the transparency, such as, have the tendency becoming the material being not suitable as optical material.In addition, thermotolerance reduces, and after for some time, tone is deteriorated.

[2] poly carbonate resin composition

The polycarbonate resin that the present invention can be used to use makes the poly carbonate resin composition being wherein added with acidic cpd, phosphorus series compound.

Herein, relative to 100 mass parts polycarbonate resins, the combined amount of each mixture is as follows: the acidic cpd of at least one is 0.00001 weight part ~ 0.1 weight part, is preferably 0.0001 weight part ~ 0.01 weight part, more preferably 0.0002 weight part ~ 0.001 weight part; The phosphorus series compound of at least one is 0.001 weight part ~ 1 weight part, is preferably 0.001 weight part ~ 0.1 weight part, more preferably 0.001 weight part ~ 0.05 weight part.

If the combined amount of acidic cpd is very few, then when carrying out injection molding, when the resin residence time is elongated, sometimes can not fully suppress painted.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, then when carrying out injection molding, when the resin residence time is elongated, sometimes can not fully suppress painted.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, such as hydrochloric acid can be enumerated, 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, the Bronsted acids such as toxilic acid and ester class thereof.In these acidic cpd or derivatives thereofs, preferred sulphonic acids or its ester class, wherein particularly preferably tosic acid, methyl tosylate, butyl p-toluenesulfonate.

As the compound neutralizing the alkaline ester exchange catalysts used in the polycondensation of above-mentioned polycarbonate resin, these acidic cpds can add in the manufacturing process of polycarbonate resin.

(phosphorus series compound)

As phosphorus series compound, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and these ester etc. can be enumerated.By adding phosphorus series compound, the painted of polycarbonate resin can be prevented.

As concrete compound, such as triphenyl phosphite can be enumerated, three (nonyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three decyl phosphorous acid esters, trioctylphosphite, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl diphenylphosphite, single decyl diphenyl phosphorous acid ester, single octyl diphenyl phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,2-methylene radical two (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, two (nonyl phenyl) pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, Tributyl phosphate ester, triethyl phosphate, trimethyl phosphate, triphenyl, the adjacent biphenyl phosphate of phenylbenzene list, dibutyl phosphate, dioctyl phosphoric acid ester, di-isopropyl phosphoric acid ester, 4,4 '-biphenylene diphosphinic acid four (2,4-di-tert-butyl-phenyl) ester, phosphenylic acid dimethyl esters, phosphenylic acid diethyl ester, phosphenylic acid dipropyl etc.

Among these, preferred use trisnonylphenyl phosphite, trimethyl phosphate, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two (2,4-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 one kind or two or more.

(other antioxidant)

Except above-mentioned acidic cpd, phosphorus series compound, in poly carbonate resin composition of the present invention, antioxidant can also be added.

As antioxidant, such as tetramethylolmethane four (3-mercaptopropionic acid ester) can be enumerated, tetramethylolmethane four (3-lauryl thiopropionate), glycerine-3-stearyl-thio propionic ester, triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-hexylene glycol-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], tetramethylolmethane-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 3,5-di-t-butyl-4-Hydroxy-benzvl phosphonic acid ester diethyl ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 4,4 '-biphenylene di 2 ethylhexyl phosphonic acid four (2,4-di-tert-butyl-phenyl) ester, one or more in two { 1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl }-2,4,8,10-tetra-oxaspiro (5,5) undecanes of 3,9-etc.

Among these acidic cpds, it is preferably the aromatic monohydroxy compound of the alkyl substituent of more than 5 with more than 1 carbonatoms, specifically, preferred octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester, 1,6-hexylene glycol-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene etc.

Be the combined amount of the aromatic monohydroxy compound of the alkyl substituent of more than 5 with more than 1 carbonatoms about what add further in poly carbonate resin composition, relative to 100 weight part polycarbonate resins, above-mentioned aromatic monohydroxy compound is 0.001 weight part ~ 1 weight part, is preferably 0.01 weight part ~ 0.5 weight part, more preferably 0.02 weight part ~ 0.3 weight part.

When the combined amount of antioxidant is very few, sometimes insufficient to painted inhibition time shaping.In addition, if the combined amount of antioxidant is too much, then during injection molding, the dirt settling of metal pattern is increased, or dirt settling when carrying out film shaping by extrusion moulding on roller increases, thus cause the appearance of goods may be impaired.

In addition, in the scope not damaging object of the present invention, also can mix releasing agent in poly carbonate resin composition of the present invention, from the release property of mould separating during to improve melt molding further.As such releasing agent, the natural coal measures wax such as natural oil system wax, montanin wax, olefines wax, silicone oil, the organopolysiloxanes etc. such as natural plant wax, the solid paraffins such as natural animal system wax, carnauba wax such as the high-grade aliphatic ester of higher fatty acid, monohydroxy-alcohol or polyvalent alcohol, beeswax can be enumerated.

As higher fatty acid, preferred carbonatoms is the saturated fatty acid of 10 ~ 30.As such saturated fatty acid, tetradecanoic acid, lauric acid, palmitinic acid, stearic acid, docosoic etc. can be enumerated.

As high-grade aliphatic ester, preferred carbonatoms be 1 ~ 20 unitary or polyvalent alcohol and carbonatoms be the part ester of the saturated fatty acid of 10 ~ 30 or full ester.As part ester or the full ester of described unitary or polyvalent alcohol and saturated fatty acid, glyceryl monostearate can be enumerated, 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 pelargonate, propylene glycol monostearate, stearic acid octadecyl ester, cetyl palmitate, butyl stearate, Laurate methyl, Wickenol 111, diphenic acid Biphenyl Ester (PVC Off ェニ Le PVC Off ェネート), sorbitan monostearate, stearic acid-2-ethylhexyl etc.Wherein, glyceryl monostearate, glycerol stearate, pentaerythritol tetrastearate, docosoic 20 diester is preferably used.

These releasing agents can be used alone one, and two or more may be used in combination.Be 100 weight parts with polycarbonate resin, the content of described releasing agent is preferably 0.0001 ~ 2 weight part.

Static inhibitor can be contained in poly carbonate resin composition of the present invention in the scope of goal of the invention not damaging the application.As static inhibitor, such as, 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.

UV light absorber, photostabilizer can be contained in poly carbonate resin composition of the present invention in the scope of goal of the invention not damaging the application.Specifically can enumerate such as 2-(2 '-hydroxyl-5 '-tertiary 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-bis-(α, α-dimethylbenzyl) phenyl]-2H-benzotriazole, 2,2 '-to phenylene two (1,3-benzoxazine-4-ketone) etc.Relative to polycarbonate resin 100 weight part, the content of stablizer is preferably 0.01 ~ 2 weight part.

Bluing agent can be mixed, to eliminate the lens yellowing caused by polymkeric substance or UV light absorber in the polycarbonate resin that the present invention uses.As bluing agent, as long as the material that may be used for polycarbonate resin just can use in the past, not special requirement.Usually, anthraquinone based dye easily obtains and becomes preferred bluing agent.

As concrete bluing agent, the typical example of such as general solvent violet by name 13 [CA.No (Colour index number) 60725], general solvent purple 31 by name [CA.No68210], general solvent violet 33 [CA.No60725] by name, general solvent blue 94 [CA.No61500] by name, general solvent violet 36 [CA.No68210] by name, general solvent blue 97 [" MacrolexVioletRR " that Beyer Co., Ltd manufactures] by name and general solvent blue by name 45 [CA.No61110] can be enumerated.These bluing agents can be used alone one, also can two or morely share.When being 100 weight part with Copolycarbonate, usually mix 0.1 × 10 ^-5~ 2 × 10 ^-4the bluing agent of the ratio of weight part.

When manufacturing poly carbonate resin composition of the present invention, can by mentioned component simultaneously or carry out mixing manufacturing with mixing machines such as tumbler mixer, V-Mixer, Nautamixer, Banbury mixer, mill, forcing machines in any order.In addition, do not damaging the scope of object of the present invention, in resin combination, can also normally used nucleator, fire retardant, inorganic filler, modified impact agent, whipping agent, dye pigment etc. contained.

In present embodiment, obtain the shaping formed polycarbonate resin moldings carrying out above-mentioned polycarbonate resin or poly carbonate resin composition.The forming method of polycarbonate resin moldings is had no particular limits, preferred injection moulding.

[3] blooming

Use polycarbonate resin of the present invention, can blooming be obtained by masking.In addition, stretched by the described blooming obtained masking, can phase retardation film be manufactured.As film-forming method, existing known extrusion by melting, solution-casting method etc. can be enumerated.

It should be noted that, as the raw material of 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-bis-(4-hydroxy phenyl) fluorenes, 9, 9-bis-(3-methyl-4-hydroxy phenyl) fluorenes, 9, the polycarbonate resin of the modifications such as 9-bis-(3-ethyl-4-hydroxy phenyl) fluorenes and vibrin, polyethylene terephthalate, polybutylene terephthalate, poly-naphthalene dicarboxylic acids ester, polycyclic hexane dicarboxylic acid cyclohexanedimethyleterephthalate ester, one kind or two or more composition in other the resin such as the vibrin such as polycyclohexylene's diformazan alcohol ester.

Phase retardation film is the phase retardation film be made up of 1 polymer alignment film, it is characterized in that, it meets following condition (i) ~ (iv), and larger the closer to long wavelength side at the phase differential of wavelength 450nm to 630nm.

I () is made up of the polymer containing the high polymer monomer unit (hereinafter referred to as " the 1st monomeric unit ") with positive refractive anisotrop and the high polymer monomer unit (hereinafter referred to as " the 2nd monomeric unit ") with negative refractive anisotrop;

(ii) based on the high molecular Re450/Re550 of the 1st monomeric unit than based on little (wherein, " Re450 " expression " under wavelength 450nm this high molecular phase differential " of the high molecular Re450/Re550 of the 2nd monomeric unit; " Re550 " expression " wavelength 550 times these high molecular phase differential ");

(iii) there is positive refractive anisotrop;

(iv) be 20 × 10 by the absolute value of photoelastic coefficient ^-12pa ^-1following polymer is formed.

The polycarbonate resin of the application of the invention, can easily realize above-mentioned condition.

The thickness of blooming is generally 30 μm ~ 200 μm, is preferably 50 μm ~ 150 μm.In addition, the phase difference value of the film that masking obtains is preferably below 20nm, is more preferably below 10nm.The phase difference value of film is excessive, then in the face of phase difference value, easily occur large fluctuation when carrying out stretching to make phase retardation film.

The drawing process of blooming can adopt known longitudinal, laterally in unilateral stretching, the in length and breadth direction of either direction carry out the drawing process such as the two-way stretch stretched respectively.In addition, special two-way stretch can also be implemented, the specific refractory power of controlling diaphragm in three-dimensional.

The stretching condition aspect that phase retardation film makes, preferably carries out in the scope of the second-order transition temperature-20 DEG C ~+40 DEG C of film raw material.Preferred scope is the scope of film base glass transition temperature-10 DEG C ~+20 DEG C.Compared with the second-order transition temperature of polycarbonate resin, when draft temperature is too low, the phase differential of stretched film increases, and in order to obtain desired phase differential, must reduce draw ratio, easily causes the fluctuation of the phase differential in face to become large.On the other hand, compared with second-order transition temperature, when draft temperature is too high, the phase differential of the film obtained diminishes, and in order to obtain desired phase differential, must increase draw ratio, and suitable stretching condition scope narrows.

Phase retardation film can be used as various liquid crystal indicator polarizer.When phase retardation film being used for the colorimetric compensation purposes of stn liquid crystal display unit, its phase difference value is selected in the scope of 400nm to 2000nm usually.In addition, when using phase retardation film as 1/2 wavelength plate, its phase difference value is selected in the scope of 200nm to 400nm.When using phase retardation film as 1/4 wavelength plate, its phase difference value is selected in the scope of 90nm to 200nm.As 1/4 wavelength plate, preferred phase difference value is 100nm ~ 180nm.Phase retardation film can be used alone, and also can combine more than 2 and use, and can also combinationally use 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, according to purposes, the polarizing axis of polaroid and the slow axis of phase retardation film are remained on specific angle and carry out lamination.In addition, using phase retardation film as 1/4 wavelength plate, itself and polaroid lamination can also be fitted and are used as circular polarization light board.In this case, the polarizing axis of polaroid and the slow axis of phase retardation film is usually kept substantially to keep 45 ° of relative angles and lamination.In addition, phase retardation film can also be used as the polarized light protective membrane forming polaroid.In addition, using the colorimetric compensation plate of phase retardation film as stn liquid crystal display unit, itself and polaroid lamination can also be fitted, thus serve as elliptical polarization tabula rasa.

[4] < mineral filler >

In addition, the polycarbonate resin using the present invention to use, has prepared the poly carbonate resin composition being wherein mixed with mineral filler.Relative to 100 weight part polycarbonate resins, the combined amount of mineral filler is 1 weight part ~ 100 weight part, is preferably 3 weight part ~ 50 weight parts.When the combined amount of mineral filler is very few, reinforced effects is little; When combined amount is too much, outward appearance is easily deteriorated.

As mineral filler, the Calucium Silicate powder such as 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 can be enumerated; 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, preferred glass fibers shape fills material, glass powdery fills material, glass laminate fills material; Carbon fiber shape fills material, carbon dust shape fills material, carbon plate shape fills material; Various whisker, mica, talcum.More preferably glass fibre, glass flake, glass milled fiber, carbon fiber, wollastonite, mica, talcum.

In addition, in mineral filler, as glass fibre, glass milled fiber, as long as it is at present for the fiber of thermoplastic resin, just all can use.Particularly preferably non-alkali glass (E glass).The diameter of glass fibre is preferably 6 μm ~ 20 μm, is more preferably 9 μm ~ 14 μm.When the diameter of glass fibre is too small, easily cause reinforced effects not enough.In addition, when diameter is excessive, easily detrimentally affect is produced to products appearance.

In addition, as glass fibre, the chopped strand being preferably cut into length 1mm ~ 6mm can be enumerated; Preferred powder is broken into the available glass milled fiber of length 0.01mm ~ 0.5mm.These can be used alone or both are used in combination.

In order to improve the adaptation with polycarbonate resin, the silane coupling agent such as aminosilane, epoxy silane etc. can be utilized to implement surface treatment to the glass fibre that the present invention uses, or in order to improve treatability, acrylic resin, polyurethane series resin etc. can be utilized to implement to assemble process to the glass fibre that the present invention uses.

As granulated glass sphere, as long as it is at present for the granulated glass sphere of thermoplastic resin, just all can use.Wherein, preferred non-alkali glass (E glass).The vpg connection of granulated glass sphere, preferable particle size 10 μm ~ 50 μm spherical.

As glass flake, lepidiod glass flake can be enumerated.The maximum diameter of the glass flake after mixed polycarbonate resin is generally less than 1000 μm, is preferably 1 μm ~ 500 μm, and the slenderness ratio ratio of thickness (maximum diameter with) is more than 5, is preferably more than 10, more preferably more than 30.

Carbon fiber is not particularly limited, such as, can enumerates with acrylic fibre, the special pitch of oil or carbon system, cellulosic fibre, xylogen etc. as carbon fibers such as raw material fired manufactured, fire-resistant, carbonaceous, graphite.The mean value of the length-to-diameter ratio (fiber length/fiber footpath) of carbon fiber is preferably more than 10, is more preferably more than 50.When the mean value of length-to-diameter ratio is too small, the electroconductibility of poly carbonate resin composition, intensity, rigidity are tending towards reducing.The footpath of carbon fiber is 3 μm ~ 15 μm, in order to adjust above-mentioned length-to-diameter ratio, can use the arbitrary shapes such as chopped strand, roving fibers, milled fiber.Carbon fiber can use one kind or two or more used in combination.

Not damaging the scope of characteristic of poly carbonate resin composition of the present invention, in order to strengthen the affinity with polycarbonate resin, can to carbon fiber embodiment as surface treatments such as epoxy finishes, carbamate process, oxide treatment.

In present embodiment, interpolation period, the addition means of the mineral filler of subtend polycarbonate resin mixing are not particularly limited.As adding period, such as, when manufacturing polycarbonate resin with ester-interchange method, can enumerate and add when polyreaction stops; In addition, no matter adopt any polymerization, all can enumerate and add when the medium polycarbonate resin of mixing process of polycarbonate resin and other mixture is in molten state; Use forcing machine etc. to mix with the polycarbonate resin of the solid state such as particle or powder, mixing time add.As addition means, can be directly mix or the method for mixing mineral filler to polycarbonate resin; Also can add with the master batch form of the high density using a small amount of polycarbonate resin or other resin etc. and mineral filler to make.

[5] < fire retardant >

In addition, the poly carbonate resin composition being mixed with fire retardant in the polycarbonate resin used in the present invention has also been prepared.The combined amount of fire retardant can be selected according to the degree of the kind of fire retardant, flame retardant resistance.In present embodiment, relative to 100 weight part polycarbonates, fire retardant is 0.01 weight part ~ 30 weight part, and preferred scope is 0.02 weight part ~ 25 weight part.By mixing fire retardant, the poly carbonate resin composition of excellent in flame retardance can be obtained.

As fire retardant, such as, can enumerate P contained compound flame retardant, halogen contained compound flame retardant, metal organic sulfonate flame retardant, silicon-containing compound flame retardant etc.In present embodiment, can from these classifications, at least one fire retardant be selected to use.These fire retardants may be used alone in combination of one kind or two or more kinds.

As P contained compound flame retardant, such as, can enumerate phosphoric acid ester based compound, phosphine nitrile based compound, red phosphorus, encapsulated red phosphorus, poly-phosphate based compound etc.Relative to 100 weight part polycarbonate resins, the combined amount of P contained compound flame retardant is preferably 0.1 weight part ~ 20 weight part.When combined amount is very few, be difficult to obtain enough flame retardant resistances, and when combined amount is too much, thermotolerance easily occurs and reduces.

As halogen contained compound flame retardant, such as, 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, ethylene two tetrabromo phthalimide, decabromodiphenylethane, brominated Polystyrene, hexabromocyclododecanes etc.

Relative to 100 weight part polycarbonate resins, the combined amount of halogen contained compound flame retardant is 0.1 weight part ~ 20 weight part.When the combined amount of halogen contained compound flame retardant is very few, be difficult to obtain enough flame retardant resistances, and when combined amount is too much, then physical strength reduces, and the precipitation of fire retardant can become the reason of variable color sometimes.

As metal organic sulfonate flame retardant, such as, 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 race, the metal etc. of periodictable the 2nd race.Specifically, be the basic metal such as lithium, sodium, potassium, rubidium, caesium; The alkaline-earth metals such as calcium, strontium, barium; Beryllium, magnesium.

In 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.As the concrete example of aromatic series sulfone metal organic sulfonate, the sylvite, 4 of the sodium salt of such as sulfobenzide-3-sulfonic acid, sulfobenzide-3-sulfonic acid can be enumerated, the sodium salt, 4 of 4 '-dibromo phenylbenzene-sulfone-3-sulfonic acid, the sylvite of 4 '-dibromo phenylbenzene-sulfone-3-sulfone, calcium salt, the sulfobenzide-3 of the chloro-4 '-nitro sulfobenzide of 4--3-sulfonic acid, the disodium salt of 3 '-disulfonic acid, the di-potassium etc. of sulfobenzide-3,3 '-disulfonic acid.

As perfluoroalkane hydrocarbon-metal organic sulfonate, an alkali metal salt of preferred perfluoroalkane hydrocarbon-sulfonic acid, the alkali earth metal salt etc. of perfluoroalkane hydrocarbon-sulfonic acid.In addition, more preferably there is sulfonic acid alkali metal salts that carbonatoms is the perfluoroalkane alkyl of 4 ~ 8, there is the sulfonic acid alkali earth metal salt etc. that carbonatoms is the perfluoroalkane alkyl of 4 ~ 8.

As the concrete example of perfluoroalkane hydrocarbon-metal organic sulfonate, the tetraethyl-ammonium salt etc. of such as 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 can be enumerated.

Relative 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, be then difficult to obtain enough flame retardant resistances, and combined amount is too much, then easily cause thermostability to reduce.

As silicon-containing compound flame retardant, such as, can enumerate silicone varnish, silicone resin that aliphatic alkyl that the substituting group that is combined with Siliciumatom is more than 2 by aromatic hydrocarbyl and carbonatoms forms, main chain be branched structure and be supported with the silicone powder, organopolysiloxane-Copolycarbonate etc. of the polydiorganosiloxane polymkeric substance or do not have with functional group in the organo-functional group contained with the silicone compounds of aromatic series base, the surface of SiO 2 powder.Among these, preferred silicone varnish.

As silicone varnish, such as, can enumerate primarily of 2 functional-type unit [R0 ₂siO] and 3 functional-type unit [R0SiO _1.5] form and sometimes contain 1 functional-type unit [R0 ₃siO _0.5] and/or 4 functional-type unit [SiO ₂] the lower solution shape silicone resin of molecular weight.Herein, R0 to be carbonatoms be 1 ~ 12 alkyl or replacement have more than one substituent carbonatoms to be the alkyl of 1 ~ 12.Alternatively base, can enumerate epoxy group(ing), amino, hydroxyl and vinyl etc.By changing the kind of R0, the consistency with matrix resin can be improved.

As silicone varnish, solvent-free silicone varnish, silicone varnish etc. containing solvent can be enumerated.In present embodiment, preferably not solvent-laden silicone varnish.Silicone varnish can be manufactured by the hydrolysis of the alkylalkoxy silanes such as such as alkyltrialkoxysilaneand, dialkyl dialkoxy silicane, trialkyl alkoxy silane, tetraalkoxysilane.By adjusting the mol ratio, hydrolysis rate etc. of these raw materials, structure (degree of crosslinking) and the molecular weight of molecule can be controlled.In addition, according to manufacturing condition, likely residual organoalkoxysilane, but remain in the composition, the hydrolytic resistance of polycarbonate resin can reduce sometimes, so preferably residual organoalkoxysilane is a small amount of or noresidue.

The viscosity of silicone varnish is preferably below 300 centistokes, is more preferably below 250 centistokes, more preferably below 200 centistokes.The viscosity of silicone varnish is excessive, then flame retardant resistance is sometimes not enough.

Relative 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, be then difficult to obtain enough flame retardant resistances, and combined amount is too much, then thermotolerance easily reduces.

In present embodiment, in order to realize higher flame retardant resistance, preferably share anti-dripping and using tetrafluoroethylene.Anti-dripping easily is disperseed in the polymer with tetrafluoroethylene, and is easily bonded to each other by polymkeric substance and makes fibrous material.Such as Teflon (registered trademark) 6J, Teflon (registered trademark) 30J (fluorine chemistry Co., Ltd. of Mitsui Du Pont), POLYFLONF201L (large aurification Industrial Co., Ltd) etc. can be enumerated as the anti-commercially available tetrafluoroethylene dripped.

Relative to 100 weight part polycarbonate resins, anti-dripping is preferably 0.01 weight part ~ 2.0 weight part by the combined amount of tetrafluoroethylene.Anti-dripping uses the combined amount of tetrafluoroethylene very few, then prevent melting dripping effect when burning not enough, if combined amount is too much, then appearance of molded articles is easily deteriorated.

In addition, do not damaging the scope of effect of the present invention, the various additives showing the amount of its effect can added in poly carbonate resin composition of the present invention.As additive, such as stablizer, UV light absorber, releasing agent, tinting material, static inhibitor can be enumerated.In addition, in order to obtain other various uses, desired performance, the thermoplastic resins such as all right benzene mixed vinylite, polyester based resin; Thermoplastic elastomer; The inorganic fillers etc. such as glass fibre, glass flake, granulated glass sphere, carbon fiber, wollastonite, Calucium Silicate powder, aluminium borate whisker.

Blending means, the mixing of the polycarbonate resin use present embodiment and above-mentioned additive etc. are not particularly limited period, such as, as mixing period, can add in polymerization process or when polyreaction stops, can also add under the state of medium polycarbonate melt such as the mixing process of polycarbonate etc.In addition, carry out mixing with forcing machine etc. after can also mixing with the polycarbonate of the solid state such as particle or powder.

[6] < UV light absorber >

In addition, in present embodiment, the poly carbonate resin composition being mixed with UV light absorber in the polycarbonate resin of the present invention's use can be prepared in.The combined amount of UV light absorber can be selected according to the kind of UV light absorber.In present embodiment, relative to 100 weight part polycarbonates, UV light absorber is 0.005 weight part ~ 5 weight part.

Herein, as UV light absorber, as long as have the compound of ultraviolet absorption ability, be just not particularly limited.In present embodiment, preferably there is at wavelength 200nm ~ 240nm the compound of absorption.In addition, preferably, the specific absorbance ε of the light of wavelength 200nm ~ 240nm is greater than to 10000mL/ (gcm), is preferably the compound of more than 15,000mL/ (gcm).

Represent that the absorbancy as the ultraviolet absorption ability of UV light absorber can measure according to JISK0115 " photometric analysis of extinction general rule ".In addition, specific absorbance ε is difficult to mole indicated concentration, so present embodiment is denoted as mL/ (gcm).In addition be as the criterion with above-mentioned JISK0115.

The mensuration > of < molar absorptivity

In present embodiment, measure molar absorptivity by following method.

Based on JISK0115 " photometric analysis of extinction general rule ", in vial, dissolve about 10mg UV light absorber in 10ml acetonitrile.Therefrom take out 0.1ml and put into another vial, add 9.9ml acetonitrile further and dissolved.This solution is loaded the quartz colorimetric utensil of optical length 10mm, use ultraviolet-visible pectrophotometer (Japanese light splitting society manufactures, V-570), mode determination Abs, sensitivity is set in Medium, to measure wavelength 190 ~ 800nm, in the measuring space absorbance A of bandwidth 2nm.Molar absorptivity ε is obtained divided by the volumetric molar concentration c of solution and the amassing of optical length L of cuvette by the absorbance A being used in each wavelength.In addition, the volumetric molar concentration c of solvent is by obtaining divided by the molecular weight of UV light absorber by the concentration of solution.For the molar absorptivity ε of the UV light absorber obtained, the molar absorptivity (ε preferably at wavelength 210nm place in the present invention ₂₁₀) and from wavelength 250nm to the maximum value (ε of molar absorptivity the scope of wavelength 350nm _250-350) ratio (ε ₂₁₀/ ε _250-350) be less than 1.75, be more preferably less than 1.73, be particularly preferably and be less than 1.72.

In present embodiment, as the compound with ultraviolet absorption ability, organic compound, mineral compound can be enumerated.Wherein, organic compound easily guarantees the affinity of itself and polycarbonate resin, and easily dispersed, so be preferred.

The molecular weight of the 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 less than 600, be preferably less than 450, be more preferably less than 400.Molecular weight is too small, then the long-term chien shih used time exists the possibility causing UV resistant performance to reduce.Molecular weight is excessive, then the long-term chien shih used time exists the possibility of the transparency reduction of resin combination.

As preferred UV light absorber, 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. can be enumerated.Wherein, preferably triazine based compound, malonic ester based compound, oxanilide based compound is used.These compounds can be used alone and also can two or more share.

As the example more specifically of benzotriazole based compound, 2-(2 '-hydroxyl-3 '-methyl-5 '-hexyl phenyl) benzotriazole can be enumerated, 2-(2 '-hydroxyl-3 '-the tertiary butyl-5 '-hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-methyl-5 '-tertiary octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tertiary dodecylphenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-methyl-5 '-tertiary dodecylphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, methyl-3-(3-(2H-benzotriazole-2-base)-5-tert-butyl-hydroxy phenyl) propionic ester etc.

As triazine based compound, 2-[4-[(2-hydroxyl-3-dodecyl oxygen base propyl group) oxygen base]-2-hydroxy phenyl]-4 can be enumerated, 6-bis-(2,4-3,5-dimethylphenyl)-1,3,5-triazine, 2,4-bis-(2,4-3,5-dimethylphenyl)-6-(the different octyloxyphenyl of 2-hydroxyl-4-)-s-triazine, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-[(hexyl) oxygen base]-phenol (manufacture of vapour Ba-Jia Ji society, Tinuvin1577FF) etc.

As dihydroxy benaophenonel based compound, can 2 be enumerated, 2 '-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2-hydroxyl-4-octyloxybenzophenone etc.

As cyanoacrylate based compound, ethyl-2-cyano group-3,3-diphenylacrylate ester, 2 '-Octocrylen etc. can be enumerated.

As malonic ester based compound, 2-(1-aryl alkylene) malonic ester class etc. can be enumerated.Wherein, preferred propanedioic acid [(4-p-methoxy-phenyl)-methylene radical]-dimethyl esters (manufacture of Clariant society, HostavinPR-25), 2-(to methoxybenzylidene) dimethyl malonate.

As oxanilide based compound, 2-ethyl-2 can be enumerated '-oxyethyl group-oxanilide (manufacture of Clariant society, SanduvorVSU) etc.

Among these, preferred 2-(2 '-hydroxyl-3 '-the tertiary butyl-5 '-hexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-[4-[(2-hydroxyl-3-dodecyl propoxy-) oxygen base]-2-hydroxy phenyl]-4,6-bis-(2,4-3,5-dimethylphenyl)-1,3,5-triazine, 2,2 ', 4,4 '-tetrahydroxybenzophenone.

Blending means, the mixing of the polycarbonate resin use present embodiment and above-mentioned additive etc. are not particularly limited period.Such as, as mixing period, can add in polymerization process or when polyreaction stops, can also add under the state of medium polycarbonate melt such as the mixing process of polycarbonate etc.In addition, after can also mixing with the polycarbonate of the solid state such as particle or powder, carry out mixing with forcing machine etc.

[7] < thermoplastic resin >

In addition, in present embodiment, the poly carbonate resin composition being mixed with thermoplastic resin in the polycarbonate resin of the present invention's use can be manufactured on.Have no particular limits the combined amount of polycarbonate resin and thermoplastic resin, the scope in present embodiment is polycarbonate resin 10 weight part ~ 90 weight part and thermoplastic resin 90 weight part ~ 10 weight part.

Herein, as thermoplastic resin, such as, can enumerate the aromatic polyester resins such as polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, polycyclohexylene's diformazan alcohol ester; The saturated polyester system resins such as aliphatic polyester based resin such as poly(lactic acid), polybutylene succinate, polycyclic hexane dicarboxylic acid cyclohexanedimethanoester ester; The bis-phenol system polycarbonate resin obtained by the various bisphenols such as dihydroxyphenyl propane, bisphenol Z; By 3 (4), 8 (9)-two (hydroxymethyl) three polycarbonate-based resin of ester ring type of obtaining of the ester ring type glycol such as ring [5.2.1.02,6] decane; The polycarbonate-based resins such as the aliphatic polycarbonate system resin obtained by heterocycle glycol such as 3,9-bis-(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetra-oxaspiro [5,5] undecanes; 6, the fatty polyamide system resins such as 66,46,12; The polyamide series resin such as semiaromatic polyamide composition system resin such as 6T, 6I, 9T; The phenylethylene resin series such as polystyrene resin, high-impact polystyrene system resin, vinyl cyanide/phenylethylene resin series (AS), acrylonitrile/butadiene/styrene system resin (ABS), hydrogenation ABS resin (AES), crystallinity syndiotactic polystyrene resin; The acrylic resins such as PMMA, MBS; The polyethylene copolymer system resins such as low density, Midst density, high density polyethylene(HDPE), ethylene/methacrylic acid ester copolymer (EMA), ethylene/vinyl acetate (EVA), ethylene/methacrylic acid glycidyl ester copolymer (E/GMA); (gathering) the ethylene series resins such as polypropylene-based resin, 4-methyl pentene-1-resin, cyclic olefin polymer (COP), cyclic olefine copolymer (COC); Thermoplastic resin or these the mixtures such as polyacetal resin, polyamide-imide resin, polyethersulfone resin, polyimide resin, polyphenylene oxide resin, polyphenylene sulfide, polyphenylene sulfone resins, 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 two or more use, can according to the suitable choice for use of characteristic such as thermotolerance, reagent resistance, formability used needed for order.In addition, graft modification or end modified rear use can also be carried out with unsaturated compounds such as maleic anhydrides.

Blending means, the mixing of the polycarbonate resin use present embodiment and above-mentioned additive etc. are not particularly limited period.Such as, as mixing period, can add in polymerization process or when polyreaction stops, can also add under the state of the mixing medium polycarbonate melt of polycarbonate etc.In addition, after can also mixing with the polycarbonate of the solid state such as particle or powder, carry out mixing with forcing machine etc.

Embodiment

Below, by embodiment, the present invention will be described in more detail.But the present invention is not limited to following shown embodiment.

Hereinafter, the physicals of polycarbonate resin and poly carbonate resin composition, the evaluation of characteristic is carried out by following method.

(1) reduced viscosity

Use Ubbelohde viscometer (central physics and chemistry DT-504 type automatic viscometer), use the 1:1 mixed solvent of phenol and sym.-tetrachloroethane as solvent, measure temperature 30.0 DEG C ± 0.1 DEG C.Concentration fine setting is 1.00g/dl.

In 120 DEG C of stirred samples, dissolved with 30 minutes, for measuring after cooling.

By solvent by time t ₀, solution by time 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 higher, and molecular weight is larger.

(2) form and aspect measure

Use colour examining colour-difference-metre (" ZE-2000 " that Japanese electricity Se society manufactures), utilize illuminant-C penetrant method to measure 3 valuess of look, calculate the index of yellowness index (YI) value as yellowish discoloration by following formula.

Yellowness index YI=100 × (1.28X-1.06Z)/Y

(3) hydrolytic resistance

For through with the mixing particle obtained of twin screw extruder, carry out pressure cooking test test; At 110 DEG C (1.5 × 10 ⁵pa) 24 hours are left standstill.After test, sample is at 100 DEG C, 1.3 × 10 ³dry 5 hours of Pa, after removing moisture, measures the respective reduced viscosity of sample before and after test, calculates reduced viscosity conservation rate according to the following formula.

Reduced viscosity conservation rate (%)=(after test the front reduced viscosity of reduced viscosity/test) × 100

(4) injection molding evaluation (conventional shaping Δ YI, bad order product rate, the demoulding bad, metal pattern dirt settling)

For through with the mixing particle obtained of twin screw extruder, use injection moulding machine (Sumitomo Heavy Industries, Ltd manufactures MINIMAT8/7A), 100 molding shot are implemented at 240 DEG C, after obtaining the flat-plate molded product of 30mm × 30mm × 2mmt, for form and aspect, measure above-mentioned YI (being denoted as " the mixing product YI of additive ").

Conventional shaping Δ YI calculates as follows.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., the shaping flat-plate molded product obtained measures aftermentioned,, calculate according to the following formula for benchmark with the YI so obtained (being denoted as " not adding additive product YI ").

The mixing product YI-of conventional shaping Δ YI ≡ additive does not add additive product YI

Herein, 3 kinds of polycarbonate resins separately do not add additive product YI aspect, PC Resin A with the YI of embodiment 13 for benchmark, PC resin B with the YI of embodiment 16 for benchmark, PC resin D with the YI of comparative example 10 for benchmark, except PC resin C uses PC resin C-1, other carrying out similarly to Example 13 measure, and use the YI obtained separately.

Bad order product rate (%) calculates as follows: calculate the ratio of the bad order such as gray bar, blackstreak product quantity relative to the quantity of whole products formed by following formula.

Bad order product rate ≡ bad order product quantity/all products formed quantity

Bad and the metal pattern dirt settling about the demoulding, for through with the mixing particle obtained of twin screw extruder, be the flat board of 60mm × 60mm × 3mmt by having carried out 4 hours preparation dry granules JSW J75EII type injection moulding machines at the condition compacted under of barrel temperature 230 DEG C, shaping cycle 45 seconds, metal pattern temperature 60 C at 80 DEG C, each forming materials 100 times injection, with or without the dirt settling amount of the fixation side metal pattern after the bad generation of the demoulding and shaping 100 times during visual observation is shaping.

(5) (shaping delay Δ YI) is evaluated in shaping delay

For through with the mixing particle obtained of twin screw extruder, use injection moulding machine (Sumitomo Heavy Industries, Ltd manufactures MINIMAT8/7A), barrel temperature 240 DEG C, carry out the delay that maintains the original state under existing of the products formed (conventional products formed) of 7 molding shot and resin (240 DEG C) in forming machine by ordinary method and after 10 minutes, implement the products formed (delay products formed) of 7 molding shot, after obtaining 30mm × 30mm × 2mmt flat-plate molded product, for the form and aspect of each products formed, measure above-mentioned YI, after obtaining each mean value before and after being detained, shaping delay Δ YI is calculated according to following formula.

Shaping delay Δ YI=is detained the conventional products formed YI of products formed YI-

(6) terminal group structural analysis

Utilize NMR spectrometer (Bruker society manufactures AVANCEDRX400), use the deuterochloroform being added with TMS as mensuration solvent, measure ¹h-NMR spectrum.

The terminal group (being denoted as " phenyl end ") shown in above-mentioned structural formula (2) is belonged at the peak that the chemical shift 7.3ppm ~ 7.5ppm with TMS for benchmark detects, similarly for other whole ends, respectively by each area ratio at the peak belonged to, after calculating each end number of every 100 repeating units in polymkeric substance, calculate phenyl end ratio according to following formula.

Phenyl end ratio (%)=(terminal group formula (1) exists number/whole end and there is number) × 100

(7) extruded film evaluation

By mixing at the polycarbonate resin sample twin screw extruder of 80 DEG C of vacuum-dryings after 5 hours, the single axle extruding machine that the particle front end obtained has T-mould is extruded at 240 DEG C, then the casting roll chilling of 95 DEG C is used, obtain the stretching sheet of thickness about 100 μm, evaluate in the following order.

Bright spot foreign matter

Two polaroids are arranged to quadrature (cross Nicols), shield through light, between two polaroids, place the film sample made.Polaroid uses glass protecting sheet.Carry out rayed from one-sided, add up every 1cm from offside opticmicroscope (50 times) ²the quantity of the bright spot of more than diameter 0.01mm in scope.

◎: bright spot quantity is 0 ~ 30

Zero: 31 ~ 50

△: 51 ~ 80

×: 81 ~ 100

××: more than 101

Roller contaminative (sheet formability)

Use single screw extrusion machine and sheet mould, carry out the shaping of the sheet of thickness about 100 μm, visual observation now volatile component, to the degree of adhesion of roller minute surface, is evaluated with following standard.

◎: the attachment of volatile component is few

Zero: the attachment of volatile component is common

△: the attachment of volatile component is many

×: the attachment of volatile component is very

(8) residual phenol amount

After resin particle is dissolved in trichloromethane, adds methyl alcohol further and carry out redeposition process.After its supernatant liquor centrifugation, with metre filter, then implement phenol with HPLC quantitative, calculate residual quantity.

(HPLC quantitative conditions)

Device: Agilent Technologies society (strain) agilent1100

Analytical column: Northeast chemistry (strain) MightysilRP-18

Elutriant: 0.2% aqueous acetic acid/methanol gradient

Detect wavelength: 280nm

Post groove temperature: 40 DEG C

(9) photoelastic coefficient

The device being combined with double refraction detection device and the oscillating mode determination of viscoelasticity device (RheologyCo manufactures DVE-3) be made up of He-Ne laser apparatus, polarized light device, compensating plate, analyzer, photodetector is used to carry out measuring (specifically see Japanese rheology meeting will Vol.19, p93-97 (1991)).

Same with when carrying out roller contamination evaluating, use single screw extrusion machine and sheet mould, form the sheet of thickness about 100 μm, the sample of wide 5mm, length 20mm is cut out from sheet, be fixed in determination of viscoelasticity device, in the room temperature of 25 DEG C, with the frequency measurement storage modulus E ' of 96Hz.Simultaneously, make the laser of injection successively by polarized light device, sample, compensating plate, analyzer, pick up with photodetector (photodiode), pass through lock-in amplifier, for the waveform of angular frequency or 2 ω, obtain its amplitude and the phase differential relative to strain, and obtain strain optical coefficient O '.Now, the direction of polarized light device and analyzer is orthogonal, and is adjusted to separately and becomes π/4 angle relative to the prolonging direction of sample.

Use storage modulus E ' and strain optical coefficient O ', obtain photoelastic coefficient C by following formula.

C=O’/E’

(10) residual carbon acid diesters amount and there is the content (levels of residual monomers) of dihydroxy compound of bond structure of structural formula (1)

After 1.0g resin particle is dissolved in 10ml trichloromethane, adds 20ml methyl alcohol further, carry out redeposition process.For filtrate, use nitrogen carry out concentrated solid after, again dissolve with 1ml acetonitrile.With GC (gas chromatograph) carry out diphenyl carbonate quantitatively and have structural formula (1) bond structure dihydroxy compound quantitative after, calculate residual quantity.

(GC/FID quantitative conditions)

Device: Co., Ltd. of Agilent Technologies society manufactures HP6890

Analytical column: GL science Co., Ltd. manufactures TC-1

Oven temperature: 100 DEG C × 1min. → 10 DEG C/min. → 240 DEG C → 15 DEG C/min. → 320 DEG C × 5min.

Detector: flame ionization ditector

Detector temperature: 325 DEG C

Vector gas: He1ml/min.

Sample injection rate: 1 μ l

In addition, for below 10ppm, because quantitative accuracy reduces, so be denoted as 10ppm.

The distillation > of < Isosorbide

Herein, the distillating method for the Isosorbide of the manufacture of polycarbonate resin A, the B containing heterocycle is as follows.

After Isosorbide is put into distil container, start decompression at leisure, then heat, dissolve interior temperature about 100 DEG C.Thereafter, start to slip out interior temperature 160 DEG C.Pressure is now 133Pa ~ 266Pa.After obtaining fore-running, implement distillation at interior temperature 160 DEG C ~ 170 DEG C, tower top temperature 150 DEG C ~ 157 DEG C, 133Pa.Distillation is filled with argon gas, returns normal pressure after stopping.By the distillation product cooling crush under argon gas stream obtained, obtain the Isosorbide through distilation.This Isosorbide is together encapsulated in aluminium lamination with AGELESS (gas chemistry society of Mitsubishi manufactures) under nitrogen flowing to be amassed in bag, and Room-temperature seal is preserved.

(embodiment 1 ~ embodiment 7)

(manufacture containing the polycarbonate resin A-1 of heterocycle)

Relative 54,220 weight parts, through the Isosorbide of distillation, drop into 31,260 weight part Tricyclodecane Dimethanol (hereinafter referred to as " TCDDM "), 117,957 weight part diphenyl carbonates and 2.2 × 10 to reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

Next, with 40 minutes by pressure from atmospheric depressurized to 13.3kPa, and made heating tank temperature be elevated to 190 DEG C with 40 minutes, the phenol of generation be retracted to outside reaction vessel simultaneously.

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction, is exported the polycarbonate resin supplying molten state to the twin screw extruder with 3 venting ports and water injection equipment continuously by polymerization machine.

Each additive is added continuously by the composition shown in table 1 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the polycarbonate resin A-1 (being denoted as " PC Resin A-1 ") containing heterocycle of Isosorbide/TCDDM=70/30 (mol% ratio).

The polycarbonate resin A-1 containing heterocycle is given in Fig. 1 (A) and Fig. 1 (B) ¹h-NMR spectrogram.Fig. 1 (B) is the enlarged view of a part (near 6.2 ~ 7.8ppm) of Fig. 1 (A).

(manufacture containing the polycarbonate resin B-1 of heterocycle)

Relative 73,070 weight part Isosorbide, drops into 109,140 weight part diphenyl carbonates and 2.0 × 10 to reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

Each additive is added continuously by the composition shown in table 1 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously, utilize tablets press to obtain the particle (being denoted as " PC resin B-1 ") of the polycarbonate resin B-1 containing heterocycle.

(manufacture containing the polycarbonate resin C-1 of heterocycle)

Relative 59,630 weight parts, through the Isosorbide (ISB) of distillation, drop into 25,218 weight parts 1 to reaction vessel, 4-cyclohexanedimethanol (hereinafter referred to as " CHDM "), 124,867 weight part diphenyl carbonates (DPC) and 2.4 × 10 ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

Each additive is added continuously by the composition shown in table 1 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the polycarbonate resin C-1 (being denoted as " PC resin C-1 ") containing heterocycle of Isosorbide (ISB)/CHDM=70/30 (mol% ratio).

(comparative example 1 ~ comparative example 6)

For comparative example 1,2, use the polycarbonate resin A-2 (being denoted as " PC Resin A-2 ") obtained as follows: when manufacturing the polycarbonate resin A-1 containing heterocycle, the diphenyl carbonate amount used 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 polycarbonate resin B-2 (being denoted as " PC resin B-2 ") obtained as follows: when manufacturing the polycarbonate resin B-1 containing heterocycle, the diphenyl carbonate amount used 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 polycarbonate resin C-2 (being denoted as " PC resin C-2 ") obtained as follows: when manufacturing the polycarbonate resin C-1 containing heterocycle, the diphenyl carbonate amount used 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, the monomer recorded in table 1, antioxidant, acidic cpd are as follows.

(monomer)

ISB: Isosorbide

TCDDM: Tricyclodecane Dimethanol

BPA: dihydroxyphenyl propane

CHDM:1,4-cyclohexanedimethanol

(antioxidant)

IRGANOX259:1,6-hexylene glycol-bis-{ 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester } (manufacture of Ciba society)

IRGANOX1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester (manufacture of Ciba society)

ADKSTABPEP-4C: two (nonyl phenyl) pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s manufacture)

ADKSTABPEP-8: distearyl-pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s manufacture)

ADKSTABPEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacture)

IRGAFOS168: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (Asahi Denka Co., Ltd.'s manufacture)

(acidic cpd)

Butyl p-toluenesulfonate: Tokyo changes into Co., Ltd. and manufactures

[table 1]

Result is as shown in Table 1 known, the value had from routine shaping Δ YI in injection molding is evaluated of Isosorbide, the structural unit of Tricyclodecane Dimethanol (having the dihydroxy compound of structural formula (1)) and the PC Resin A-1 of the scope of ratio more than 20% of phenyl end, PC resin B-1, PC resin C-1 (embodiment 1 ~ embodiment 7) and shaping delay Δ YI is little, be in appearance painted less, material that the transparency is excellent.

On the other hand, the ratio of phenyl end be less than 20% the PC Resin A-2 of scope, PC resin B-2, the shaping delay Δ YI of PC resin C-2 (comparative example 1 ~ comparative example 6) in injection molding is evaluated value large, painted many in these material appearance, compromise the transparency.

(embodiment 8 ~ embodiment 16)

Use containing the polycarbonate resin A-1 (PC Resin A-1) of heterocycle, containing the polycarbonate resin B-1 (PC resin B-1) of heterocycle, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by proportioning shown in table 2, various evaluation is carried out for the poly carbonate resin composition prepared.The results are shown in Table 2.In addition, the photoelastic coefficient of the sample used in embodiment 8 is 9 × 10 ^-12pa ^-1.

[table 2]

Result is as shown in Table 2 known, there is structural unit from Isosorbide, Tricyclodecane Dimethanol and phenyl end ratio (%) be more than 20% PC Resin A-1, not only conventional shaping Δ YI and shaping delay Δ YI is little for PC resin B-1, and particularly when the content of residual phenol is below 700ppm, bad order product rate (%) in injection molding evaluation is little, and the value of shaping delay Δ YI is also little, it is the material that the transparency is excellent.

In addition, compare with the situation (embodiment 13,16) of unmixed antioxidant, due to mixing antioxidant (embodiment 8 ~ 12,14), shaping delay Δ YI significantly reduces.

(embodiment 17,18)

Embodiment 17, uses the polycarbonate resin A-3 (being denoted as " PC Resin A-3 ") containing heterocycle obtained as follows: change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, operate similarly to Example 1 in addition in 18.

Use containing the polycarbonate resin A-3 (PC Resin A-3) of heterocycle, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in table 3, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 3.

(comparative example 7 ~ comparative example 11)

The polycarbonate resin A-4 (being denoted as " PC Resin A-4 ") containing heterocycle obtained as follows is used: when manufacturing the polycarbonate resin A-1 containing heterocycle in comparative example 7, the diphenyl carbonate amount used is 115,688 weight parts, and, change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, operate equally in addition.

(not containing the manufacture of the polycarbonate resin D-1 of heterocycle)

Comparative example 8,10 uses the following polycarbonate resin D-1 not containing heterocycle manufactured.

Relative 91,200 parts by weight of bisphenol A, drop into 89,024 weight part diphenyl carbonate and 4.0 × 10 to reaction vessel ^-2weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 250 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction, is exported the polycarbonate resin supplying molten state to the twin screw extruder with 3 venting ports and water injection equipment continuously by polymerization machine.

Each additive is added continuously by the composition shown in table 3 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously, obtain not containing the particle (being denoted as " PC resin D-1 ") of the polycarbonate resin D-1 of heterocycle with tablets press.

Comparative example 9,11 uses the polycarbonate resin D-2 (being denoted as " PC resin D-2 ") obtained as follows: change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, operate in addition with same with comparative example 8.

In addition, in comparative example 7 ~ 11, change over the composition shown in table 3, obtain polycarbonate resin with identical operation in addition.

In the same manner as embodiment, use antioxidant, acidic cpd prepare poly carbonate resin composition according to the proportioning shown in table 3, carry out various evaluation to the poly carbonate resin composition prepared.The results are shown in Table 3.In addition, the photoelastic coefficient of the sample used in comparative example 11 is 80 × 10 ^-12pa ^-1.

[table 3]

Result is as shown in Table 3 known, even if polycarbonate resin of the present invention has the structural unit of peculiar chemical structure, but when phenyl end ratio (%) is less than 20% (comparative example 7), the value of the shaping delay Δ YI of this material is large, compromises the transparency time shaping.

In addition, it is known when embodiment compares each other, remain the polycarbonate resin A (embodiment 17 of content more than 700ppm of phenol, 18) the bad order product rate (%) in injection molding is evaluated is higher, and the value of the shaping delay Δ YI of this material is also larger, time shaping, the transparency receives infringement.

On the other hand, when having the polycarbonate resin D from the structural unit of dihydroxyphenyl propane (comparative example 8 ~ comparative example 11), do not using the condition (comparative example 8 of antioxidant, 9) under, even if residual phenol amount is controlled at below 700ppm, can not improve shaping delay Δ YI, be deteriorated on the contrary, and the improvement degree of bad order rate is also little.Therefore, roller adhesion amount is not also greatly improved.In addition, even use the condition (comparative example 10,11) of antioxidant, the improvement degree of conventional shaping Δ Y, shaping delay Δ YI, bad order rate is all little, and roller adhesion amount does not also significantly improve.

On the other hand, the impact of the residual phenol that polycarbonate resin of the present invention is subject to is large, by residual phenol amount is controlled to below 700ppm, conventional shaping Δ Y, shaping delay Δ YI, bad order rate, roller adhesion amount can be improved, especially largely improve bad order rate and roller adhesion amount.

(embodiment 19 ~ embodiment 29)

(manufacture containing the polycarbonate resin A-5 of heterocycle)

Relative 54,220 weight parts, through the Isosorbide of distillation, drop into 31,260 weight part TCDDM, 117,957 weight part diphenyl carbonates and 2.2 × 10 to reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.Next, with 40 minutes by pressure from atmospheric depressurized to 13.3kPa, and made heating tank temperature be elevated to 190 DEG C with 40 minutes, the phenol of generation be retracted to outside reaction vessel simultaneously.

Then, after whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, the relief outlet of molten resin from lower vessel portion is discharged, then while it is supplied continuously to spectacle paddle polymerization machine (Hitachi Co., Ltd's manufacture), while be detained 1 hour at 240 DEG C, while making polymerization carry out further with this setting, the phenol of generation is extracted out outside container.Then, supply exporting the polycarbonate melt resin of discharging by spectacle paddle polymerization machine continuously to the twin screw extruder with 3 venting ports and water injection equipment.Each additive is added continuously by the composition shown in table 1 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the copolymerized panlite A-5 (being denoted as " PC Resin A-5 ") of Isosorbide/TCDDM=70/30 (mol% ratio).

(the polycarbonate resin B-3 containing heterocycle)

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, the relief outlet of molten resin from lower vessel portion is discharged, then while it is supplied continuously to spectacle paddle polymerization machine (Hitachi Co., Ltd's manufacture), while be detained 1 hour at 240 DEG C, while making polymerization carry out further with this setting, the phenol of generation is extracted out outside container.

Next, supply exporting the polycarbonate melt resin of discharging by spectacle paddle polymerization machine continuously to the twin screw extruder with 3 venting ports and water injection equipment.Each additive is added continuously by the composition shown in table 4 with twin screw extruder; utilize each exhaust oral area by after the low molecular weight substance water filling devolatilizations such as phenol simultaneously; carry out granulation with tablets press, obtain the copolymerized panlite B-3 (being denoted as " PC resin B-3 ") of Isosorbide/TCDDM=70/30 (mol% ratio).

In addition, embodiment 29 use obtain as follows obtain PC Resin A-4: when manufacturing containing the polycarbonate resin A-1 of heterocycle, the diphenyl carbonate amount used is 115,688 weight parts (DPC decrement), and change in twin screw extruder and only carry out vacuum volatilization and not water filling, similarly carry 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 table 4, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 4.

[table 4]

Result is as shown in Table 4 known, there is structural unit from Isosorbide, Tricyclodecane Dimethanol and phenyl end ratio (%) is more than 20% when, not only conventional shaping Δ YI and shaping delay Δ YI is little, and the content of residual carbon acid diesters is that the PC Resin A-1 of 0.1ppm ~ below 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 evaluated are little, and the value of shaping delay Δ YI is also little, it is the material that the transparency is excellent.

In addition, compare with the situation (embodiment 26,28) of unmixed antioxidant, due to mixing antioxidant (embodiment 19 ~ 25,27,29), shaping delay Δ YI significantly reduces.

(embodiment 30 ~ embodiment 33)

Use in embodiment 30,31 and manufacture the PC Resin A-3 that not water filling obtains containing only carrying out vacuum volatilization during the polycarbonate resin A-1 of heterocycle in twin screw extruder.

The polycarbonate resin A-6 (being denoted as " PC Resin A-6 ") containing heterocycle obtained as follows is used: when manufacturing the polycarbonate resin A-1 containing heterocycle in embodiment 32, the diphenyl carbonate amount used is 120,225 weight parts, and in twin screw extruder, only carry out vacuum volatilization and do not carry out water filling.

The polycarbonate resin B-4 (being denoted as " PC resin B-4 ") obtained as follows is used: when manufacturing the polycarbonate resin B-1 containing heterocycle, in twin screw extruder, only carrying out vacuum volatilization and do not carry out water filling in embodiment 33.

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 table 5, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 5.

(comparative example 12 ~ comparative example 16)

Polycarbonate resin D-1 is used in comparative example 12,15,16.

The polycarbonate resin D-2 (being denoted as " PC resin D-2 ") obtained as follows is used: when manufacturing polycarbonate resin D-1, in twin screw extruder, only carrying out vacuum volatilization and do not carry out water filling in comparative example 13,14.Use PC resin D-1, PC resin D-2, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in table 5, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 5.

[table 5]

Result is as shown in Table 5 known, composition (comparative example 12 ~ 16) contains the polycarbonate resin of the structural unit not containing the dihydroxy compound from the bond structure with structural formula (1), even if phenyl end ratio is more than 20%, the photoelastic coefficient of composition (comparative example 12 ~ 16) is also large, poor quality.

In addition, polycarbonate resin A (embodiment 30 ~ 33) is even if having the structural unit from Isosorbide, Tricyclodecane Dimethanol, the content of residual carbon acid diesters is also greater than 60ppm, embodiment compares known each other, the bad order product rate (%) of polycarbonate resin A (embodiment 30 ~ 33) in injection molding is evaluated is large, and shaping delay Δ YI value is large, and the transparency of this material is poor.

In addition, have from the PC resin D-1 of the structural unit of dihydroxyphenyl propane and the balanced differences between the bad order product rate (%) of PC resin D-2 (comparative example 12 ~ 16) and shaping delay Δ YI.

(embodiment 34 ~ embodiment 39)

Use containing polycarbonate resin A-1 (PC Resin A-1), the polycarbonate resin A-5 (PC Resin A-5) containing heterocycle of heterocycle, the polycarbonate resin B-1 (PC resin B-1) containing heterocycle, containing the polycarbonate resin B-3 (PC resin B-3) of heterocycle, above-mentioned antioxidant, acidic cpd, prepare poly carbonate resin composition by the proportioning shown in table 6, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 6.

(comparative example 17 ~ comparative example 20)

PC Resin A-4 is used in comparative example 17, comparative example 18; Comparative example 19, comparative example 20 use polycarbonate resin B-5 (being denoted as " PC resin B-5 "), polycarbonate resin B-5 obtains as follows: in the manufacture of the polycarbonate resin B-1 containing heterocycle, use 104,860 weight part diphenyl carbonates, and change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, carry out the operation identical with the manufacture of the polycarbonate resin B-1 containing heterocycle in addition, obtain described PC resin B-5, the content of its Isosorbide is 60ppm.

Use the above-mentioned polycarbonate resin A-1 (PC Resin A-1) containing heterocycle, 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 table 6, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 6.

[table 6]

Result is as shown in Table 6 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, Tricyclodecane Dimethanol (having the dihydroxy compound of structural formula (1)), and phenyl end ratio is more than 20%, the content (levels of residual monomers) of Isosorbide is below 60ppm, they injection molding evaluate in bad order product rate (%) low, and the value of shaping delay Δ YI is little, these materials in appearance painted few, the transparency is excellent.In addition, during extruded film is evaluated, the dirt settling amount on roller, number of defects are also few, stably can carry out film manufacture.

On the other hand, PC Resin A-4, the Isosorbide of PC resin B-5 (comparative example 17 ~ comparative example 20) or the content (levels of residual monomers) of Tricyclodecane Dimethanol are greater than 60ppm, bad order product rate (%) in injection molding is evaluated is large, and shaping delay Δ YI value is large, these materials in appearance painted many, compromise the transparency.In addition, in extruded film is evaluated, also can be observed the tendency that the dirt settling amount on roller, number of defects are all slightly many, during film manufactures, stability is slightly poor.

(embodiment 40 ~ embodiment 46)

Use contains polycarbonate resin A-7 (being denoted as " PC Resin A-7 "), above-mentioned antioxidant, the following releasing agent of heterocycle, prepare poly carbonate resin composition by the proportioning shown in table 7, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 7.Described PC Resin A-7 obtains as follows: the heating tank temperature manufactured containing the 2nd stage when polycarbonate resin A-1 (PC Resin A-1) of heterocycle, PC Resin A-2, PC Resin A-3, above-mentioned polycarbonate resin A-1 (PC Resin A-1) containing heterocycle is set as 280 DEG C, in addition, carry out in the same manner as the manufacture of PC Resin A-1, obtain PC Resin A-7.

(releasing agent)

NAA-180: stearic acid (NOF Corp's manufacture)

Gold medal powder (ゴー Le デ Application Block ラ Application De パウダー): cera alba (three wooden chemistry Industrial Co., Ltd manufacture)

Solid paraffin 155: solid paraffin (Japanese Jing La Co., Ltd. manufactures)

[table 7]

Result is as shown in Table 7 known, poly carbonate resin composition (embodiment 40 ~ embodiment 46) employs the polycarbonate resin of the scope of ratio more than 20% of phenyl end, and in its injection molding evaluation and Δ YI, at least any one is excellent.

In addition, obtained by the polycondensation of Isosorbide (ISB), Tricyclodecane Dimethanol (TCDDM) and diphenyl carbonate (DPC) and the terminal group (double bond end) shown in above-mentioned structural formula (2) is less than 7% when, Δ YI is little, and the content of residual monomer is when being below 60ppm, Δ YI is less, is painted few elite clone.Particularly when containing below 60ppm residual carbon acid diesters, in addition to the advantages described above, also have no matter whether contain the elite clone that releasing agent is all metal pattern hardly staining metals.

< is mixed with the poly carbonate resin composition > of inorganic filler

The preparation > of < polycarbonate resin

(the polycarbonate resin A-8 containing heterocycle)

Relative 54,220 weight parts are through the Isosorbide (ISB) of distillation, 31,260 weight part Tricyclodecane Dimethanol (hereinafter referred to as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 × 10 are dropped into reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

In twin screw extruder; each additive is added continuously by the composition shown in table 8; simultaneously by each exhaust oral area by lower molecular weight thing water filling devolatilizations such as phenol; then carry out granulation by tablets press, obtain the polycarbonate resin A-8 (being denoted as " PC Resin A-8 ") containing heterocycle of Isosorbide (ISB)/TCDDM=70/30 (mol% ratio).

The physical property evaluation > of < poly carbonate resin composition

(injection molding)

The particle of the polycarbonate resin with the mixing preparation of twin screw extruder is predrying 4 hours at 80 DEG C, next, this particle and various additive are put in injection moulding machine (JSW J75EII type), carry out injection molding in the condition of barrel temperature 230 DEG C, shaping cycle 45 seconds, metal pattern temperature 60 C, make various test film.

(modulus in flexure)

For the test film using injection moulding machine to prepare, the bend test method specified according to ISO178 carries out three point bending test.

(metal pattern dirt settling)

For each poly carbonate resin composition, under above-mentioned injection molding condition, respectively carry out the shaping of the flat board of injection 100 length 60mm × wide 60mm × thickness 3mm, with or without the dirt settling amount of the bad generation of the demoulding and shaping rear fixation side metal pattern during visual observation is shaping.

(shaping delay Δ YI)

For each poly carbonate resin composition, in above-mentioned injection molding condition, shaping cycle is changed into 300 seconds, respectively carry out the shaping of the flat board of injection 10 length 60mm × wide 60mm × thickness 3mm in addition with identical condition, prepare test film.

Then, for each test film of preparation, utilize light splitting colour-difference meter (Japanese electricity Se Industrial Co., Ltd manufactures SE-2000), measure yellowness index (YI) value (300 second cycle products formed YI) with illuminant-C reflection method.

By this 300 second cycle products formed YI and yellowness index (YI) value (45 second cycle products formed YI) of carrying out injection molding test film with 45 seconds shaping cycles, calculate shaping delay Δ YI by following formula.

Shaping delay Δ YI=(300 second cycle products formed YI)-(45 second cycle products formed YI)

(embodiment 47 ~ 49)

The polycarbonate resin A-9 (being denoted as " PC Resin A-9 ") containing heterocycle is used in embodiment 49, it obtains as follows: in the manufacture of above-mentioned PC Resin A-8, change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, carry out same operation in addition, obtain described PC Resin A-9.

Use polycarbonate resin A-8 (PC Resin A-8), PC Resin A-9, following antioxidant, the following inorganic filler containing heterocycle, prepare poly carbonate resin composition by the proportioning shown in table 8, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 8.

(comparative example 21,22)

The polycarbonate resin A-10 (being denoted as " PC Resin A-10 ") containing heterocycle is used in comparative example 22, it obtains as follows: in the manufacture of PC Resin A-8, diphenyl carbonate amount is changed into 115,688 weight parts, carry out same operation in addition.

Use above-mentioned polycarbonate resin A-8 (PC Resin A-8), following antioxidant, following inorganic filler containing heterocycle, prepare poly carbonate resin composition by the proportioning shown in table 8, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 8.

(antioxidant)

(1) IRGANOX1010: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester (manufacture of Ciba society)

(2) ADKSTABPEP-36: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites) (Asahi Denka Co., Ltd.'s manufacture)

(3) IRGAFOS168: three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (Asahi Denka Co., Ltd.'s manufacture)

(inorganic filler)

(1) glass fibre: glass strand ECS03T-571 (Nippon Electric Glass Co., Ltd's manufacture) (2) carbon fiber: PyrofilChoppedFiberTR06U (Mitsubishi Rayon Co., Ltd's manufacture)

[table 8]

Result is as shown in Table 8 known, poly carbonate resin composition is obtained by Isosorbide (ISB), polycondensation between Tricyclodecane Dimethanol (TCDDM) and diphenyl carbonate (DPC), and the scope of ratio more than 20% of the phenyl end shown in above-mentioned structural formula (2), and when described poly carbonate resin composition contains 1 weight part ~ 100 parts by weight of inorganic weighting agent (embodiment 47 ~ 49), said composition has high modulus in flexure, and at least one party of shaping delay Δ YI and metal pattern dirt settling is excellent.Known when particularly comparing between embodiment, when the residual carbon acid diesters contained is below 60ppm, this material is especially excellent, and its metal pattern dirt settling is especially few, and modulus in flexure is high.

< is mixed with the poly carbonate resin composition > of fire retardant

The preparation > of < polycarbonate resin

(the polycarbonate resin A-11 containing heterocycle)

In twin screw extruder; each additive is added continuously by the composition shown in table 9; simultaneously at each exhaust oral area by lower molecular weight thing water filling devolatilizations such as phenol; then carry out granulation by tablets press, obtain the polycarbonate resin A-11 (being denoted as " PC Resin A-11 ") containing heterocycle of Isosorbide (ISB)/TCDDM=70/30 (mol% ratio).

The physical property evaluation > of < poly carbonate resin composition

(injection molding)

(incendivity)

For through with the mixing particle obtained of twin screw extruder, by 80 DEG C of particle JSW J75EII type injection moulding machine conditions at barrel temperature 230 DEG C, shaping cycle 45 seconds, metal pattern temperature 60 C after predrying 4 hours, based on UL94 standard, carry out the shaping of the combustion test sheet of 1.5mmt.The testing vertical flammability in UL94 standard is carried out with the test film obtained.

(embodiment 50 ~ 52)

In embodiment 52, use the polycarbonate resin A-12 (being denoted as " PC Resin A-12 ") containing heterocycle, it obtains as follows: in the manufacture of above-mentioned PC Resin A-11, change in twin screw extruder and only carry out vacuum volatilization and do not carry out water filling, carry out same operation in addition.

Use polycarbonate resin A-11 (PC Resin A-11), PC Resin A-12, following antioxidant, the following fire retardant containing heterocycle, prepare poly carbonate resin composition by the proportioning shown in table 9, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 9.

(comparative example 23,24)

In comparative example 24, use the polycarbonate resin A-13 (being denoted as " PC Resin A-13 ") containing heterocycle, it obtains as follows: in the manufacture of PC Resin A-11, and the temperature of the heating tank in the 2nd stage is changed to 280 DEG C.

Use above-mentioned polycarbonate resin A-11 (PC Resin A-11), PC Resin A-13, following antioxidant, following fire retardant containing heterocycle, prepare poly carbonate resin composition by the proportioning shown in table 9, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 9.

(antioxidant)

(fire retardant)

(1) SPS-100: phosphazene compound (Otsuka Chemical Co., Ltd manufactures)

(2) PX-200: aromatic condensation phosphoric acid ester (Daihachi Chemical Industry Co., Ltd.'s manufacture)

[table 9]

Result is as shown in Table 9 known, poly carbonate resin composition is obtained by Isosorbide (ISB), polycondensation between Tricyclodecane Dimethanol (TCDDM) and diphenyl carbonate (DPC), and the ratio of the phenyl end shown in above-mentioned structural formula (2) is more than 20%, when the fire retardant contained is 0.01 weight part ~ 30 weight part (embodiment 50 ~ 52), the shaping delay Δ YI of this polycarbonate compositions is little, painted few, and flame retardant resistance is also excellent.In addition, embodiment be compared to each other known, the residual carbon acid diesters contained is the poly carbonate resin composition (embodiment 50,51) of below 60ppm is more excellent material, and metal pattern dirt settling does not also increase.

< is mixed with the poly carbonate resin composition > of UV light absorber

The preparation > of < polycarbonate resin

(Production Example 1: the polycarbonate resin R-1 containing heterocycle)

Relative 54,220 weight parts are through the Isosorbide (ISB) of distillation, 31,260 weight part Tricyclodecane Dimethanol (hereinafter referred to as " TCDDM "), 117,957 weight part diphenyl carbonates (DPC) and 2.2 × 10 are dropped into reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.Next, with 40 minutes by pressure from atmospheric depressurized to 13.3kPa, and made heating tank temperature be elevated to 190 DEG C with 40 minutes, the phenol of generation be retracted to outside reaction vessel simultaneously.

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction, is exported the polycarbonate resin R-1 (being denoted as below " PC resin R-1 ") obtaining molten state by polymerization machine.

(Production Example 2: the polycarbonate resin R-2 containing heterocycle)

For the operation in the 2nd stage of Production Example 1, heating tank temperature is changed to 280 DEG C from 240 DEG C, in addition, carry out in the same manner as Production Example 1, obtain polycarbonate resin R-2 (being denoted as below " PC resin R-2 ").

(Production Example 3: the polycarbonate resin R-3 containing heterocycle)

Change the DPC of Production Example 1 amount into 115,688 weight parts, replace 117,957 weight parts, and heating tank temperature is changed into 280 DEG C from 240 DEG C as the operation in the 2nd stage in the same manner as Production Example 2, to carry out equally with Production Example 1 in addition, obtain polycarbonate resin R-3 (being denoted as below " PC resin R-3 ").

(Production Example 4: the polycarbonate resin R-4 containing heterocycle)

Relative 73,070 weight part Isosorbide (ISB), drops into 109,140 weight part diphenyl carbonates (DPC) and 2.0 × 10 to reaction vessel ^-1weight part, as the cesium carbonate of catalyzer, in a nitrogen atmosphere, as the operation in the 1st stage of reaction, by heating tank heating temperatures to 150 DEG C, makes material dissolution (about 15 minutes) as required while stirring.

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion, stopped reaction, is exported the polycarbonate resin R-4 (being denoted as below " PC resin R-4 ") obtaining molten state by polymerization machine.

(Production Example 5: the polycarbonate resin R-5 containing heterocycle)

As the operation in the 2nd stage of Production Example 4, heating tank temperature is changed to 280 DEG C from 240 DEG C, in addition, to carry out equally with Production Example 1, obtain polycarbonate resin R-5 (being denoted as below " PC resin R-5 ").

(Production Example 6: the polycarbonate resin R-6 containing heterocycle)

Change the DPC of Production Example 4 amount into 107,102 weight parts replace 109,140 weight parts, same with Production Example 2, as the operation in the 2nd stage, heating tank temperature is changed to 280 DEG C from 240 DEG C, in addition, to carry out equally with Production Example 1, obtain polycarbonate resin R-6 (being denoted as below " PC resin R-6 ").

The physical property evaluation > of < poly carbonate resin composition

(injection molding)

(Investigation on Photodegradation)

By light splitting colour-difference meter (Japanese electricity Se Industrial Co., Ltd manufactures SE-2000), measure yellowness index (YI) value (initial stage YI) with each test film of illuminant-C reflection method to preparation.

Then, resistance to wait (MetalingWeatherMeterM6T that SUGA trier Co., Ltd. manufactures) of metal is used, at radiation illumination 1.5kW/m ², temperature 63 DEG C, humidity implement 20 hours radiation treatment to each test film 50% time in groove, measure thereafter yellowness index (YI) value (YI after test).

Δ YI=(YI after test)-(initial stage YI)

(delay stability)

Glass tubing to band arm adds 30g polycarbonate resin, airtight after carrying out displacement with nitrogen, soaks 8 hours in the oil bath of 250 DEG C.Thereafter, the reduced viscosity measuring polycarbonate resin (soaks rear reduced viscosity (η _red) ').Then, with reduced viscosity (η after immersion _red) ' divided by the reduced viscosity (η of polycarbonate resin before soaking _red), obtain this ratio (unit: %).

(embodiment 53 ~ embodiment 65)

Use containing polycarbonate resin R-1 (PC resin R-1), the polycarbonate resin R-2 (PC resin R-2) containing heterocycle of heterocycle, the polycarbonate resin R-3 (PC resin R-3) containing heterocycle, the polycarbonate resin R-4 (PC resin R-4) containing heterocycle, following antioxidant, following acidic cpd, following UV light absorber, prepare poly carbonate resin composition by the proportioning shown in table 10, various evaluation is carried out to the poly carbonate resin composition prepared.

Each resin and mixture are supplied to the twin screw extruder with 3 venting ports and water injection equipment, utilizes each exhaust oral area by after the lower molecular weight thing water filling devolatilizations such as phenol, carry out granulation by tablets press.The results are shown in Table 10.

(comparative example 25 ~ comparative example 28)

Use containing polycarbonate resin R-2 (PC resin R-2), the polycarbonate resin R-3 (PC resin R-3) containing heterocycle of heterocycle, the polycarbonate resin R-6 (PC resin R-6) containing heterocycle, following acidic cpd, following UV light absorber, prepare poly carbonate resin composition by proportioning shown in table 11, various evaluation is carried out to the poly carbonate resin composition prepared.The results are shown in Table 11.

(antioxidant)

(acidic cpd)

PTSB: butyl p-toluenesulfonate (Tokyo changes into Co., Ltd. and manufactures)

(UV light absorber)

(1) UV-1:2-(4,6-phenylbenzene-1,3,5-triazines-2-base)-5-((hexyl) oxygen base)-phenol (Ciba society manufactures, TINUVIN1577FF: molecular weight 425)

(2) UV-2:N-(2-ethoxyl phenenyl)-N '-(4-ethylphenyl)-oxalamide (manufacture of society of Clariant Japan, HostavinVSU)

(3) UV-3:4-methoxybenzylidene dimethyl malonate (manufacture of society of Clariant Japan, HostavinPR-25)

(4) UV-4:2-(2 '-hydroxyl-5 '-tertiary octyl phenyl) benzotriazole (Ciba society manufactures, TINUVIN329: molecular weight 323)

(5) UV-5: salol (apicorporation society manufactures, salol: molecular weight 214)

(6) UV-6:2-cyano group-3,3-diphenyl-ethyl acrylate (society of BASF Japan manufactures, Uvinul3035: molecular weight 277)

In addition, the UV light absorber used is at the molar absorptivity (ε at wavelength 210nm place ₂₁₀) with 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

[table 10]

[table 11]

From result shown in table 10, table 11, poly carbonate resin composition uses the polycarbonate obtained by the polycondensation of Isosorbide (ISB), Tricyclodecane Dimethanol (TCDDM) and diphenyl carbonate (DPC), and when this polycarbonate has above-mentioned terminal group (phenyl end) (embodiment 53 ~ 65) shown in structural formula (2), the Δ YI in Investigation on Photodegradation is little for this poly carbonate resin composition, painted few, be the material of excellent in light-resistance.

< is mixed with the poly carbonate resin composition > of thermoplastic resin

The preparation > of < polycarbonate resin

(Production Example 7: the polycarbonate resin R-7 containing heterocycle)

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion; stopped reaction; exported by polymerization machine; the polycarbonate resin of relative 100 weight part molten states; 0.0006 weight part butyl p-toluenesulfonate is supplied as acidic cpd to the twin screw extruder with 3 venting ports and water injection equipment; after each exhaust oral area is by lower molecular weight thing water filling devolatilizations such as phenol, obtains the polycarbonate resin R-7 (being denoted as below " PC resin R-7 ") containing heterocycle, utilize tablets press to carry out granulation.

The reduced viscosity of the particle obtained is 0.571dl/g, and the ratio of double bond end and whole end is 5.6%, the ratio of phenyl end is 64%.

(Production Example 8: the polycarbonate resin R-8 containing heterocycle)

As the operation in the 2nd stage of Production Example 7, heating tank temperature is changed to 280 DEG C by 240 DEG C, in addition, to carry out equally with Production Example 1, obtain polycarbonate resin R-8 (being denoted as below " PC resin R-8 ").Reduced viscosity is 0.554dl/g, the ratio of double bond end and whole end is 5.5%, the ratio of phenyl end is 63%.

(Production Example 9: the polycarbonate resin R-9 containing heterocycle)

Change the DPC of Production Example 7 amount into 115,688 weight parts replace 117,957 weight parts, same with Production Example 8, as the operation in the 2nd stage, heating tank temperature is changed to 280 DEG C from 240 DEG C, and do not add pTSB as acidic cpd, in addition, to carry out equally with Production Example 1, obtain polycarbonate resin R-9 (being denoted as below " PC resin R-9 ").Reduced viscosity is 0.561dl/g, the ratio of double bond end and whole end is 4.9%, the ratio of phenyl end is 10%.

(Production Example 10: the polycarbonate resin R-10 containing heterocycle)

After whole reaction vessel is kept 15 minutes at 190 DEG C, as the operation in the 2nd stage, heating tank temperature was made to be elevated to 240 DEG C with 30 minutes.After starting to heat up 10 minutes, made the pressure in reaction vessel be below 0.200kPa with 30 minutes, the phenol of generation is distillated.After reaching predetermined stirring moment of torsion; stopped reaction; exported by polymerization machine; the polycarbonate resin of relative 100 weight part molten states; 0.0006 weight part pTSB is supplied 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 the lower molecular weight things such as phenol, obtain the polycarbonate resin R-10 (being denoted as below " PC resin R-10 ") containing heterocycle, utilize tablets press to carry out granulation.Reduced viscosity is 0.562dl/g, the ratio of double bond end and whole end is 6.3%, the ratio of phenyl end is 60%.

(Production Example 11: the polycarbonate resin R-11 containing heterocycle)

As the operation in the 2nd stage of Production Example 10, heating tank temperature is changed to 280 DEG C by 240 DEG C, in addition, carry out in the same manner as Production Example 10, obtain polycarbonate resin R-11 (being denoted as below " PC resin R-11 ").Reduced viscosity is 0.548dl/g, the ratio of double bond end and whole end is 6.7%, the ratio of phenyl end is 58%.

(Production Example 12: the polycarbonate resin R-12 containing heterocycle)

Change the DPC of Production Example 10 amount into 107,102 weight parts replace 109,140 weight parts, same with Production Example 9, as the operation in the 2nd stage, heating tank temperature is changed to 280 DEG C from 240 DEG C, and do not add pTSB as acidic substance, in addition, to carry out equally with Production Example 10, obtain polycarbonate resin R-12 (being denoted as below " PC resin R-12 ").Reduced viscosity is 0.554dl/g, the ratio of double bond end and whole end is 5.5%, the ratio of phenyl end is 11%.

The thermoplastic resin used is as follows.

Polybutylene terephthalate resin (PBT) (manufacture of Mitsubishi Engineering-Plastics society, trade(brand)name NOVADURAN5010)

Amorphism pet resin (PETG) (manufacture of society of eastman chemical Japan, trade(brand)name EASTARPETG6763)

Bisphenol-a polycarbonate (PC) (manufacture of Mitsubishi Engineering-Plastics society, trade(brand)name NOVAREX7022J)

High density polyethylene(HDPE) (HDPE) (manufacture of Japanese polyethylene society, trade(brand)name NOVATECHDHF410)

(antioxidant)

The antioxidant used is as follows.

A-1: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester (manufacture of Ciba society, IRGANOX1010)

A-2: two (2, the 6-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites (manufacture of ADEKA society, ADKSTABPEP-36)

The physical property evaluation > of < poly carbonate resin composition

(injection molding)

(tone (YI) of sheet)

The particle injection moulding machine (manufacture of society of JSW, form: J75EII) each embodiment, comparative example obtained obtains the sheet of 60mm × 4mmt under barrel temperature 230 DEG C, metal pattern temperature 90 DEG C of conditions.The sheet light splitting colour-difference meter obtained (Japanese electricity Se Industrial Co., Ltd manufactures ZE-2000) is measured the index of yellowness index (YI) value as yellowish discoloration using illuminant-C reflection method.

(delay thermostability)

Glass tubing to band arm adds 30g resin, airtight after carrying out displacement with nitrogen, soaks 8 hours in the oil bath of 250 DEG C.By the reduced viscosity after immersion divided by the reduced viscosity before immersion.

(embodiment 66 ~ embodiment 72)

With proportioning shown in table 12, polycarbonate resin, antioxidant, the twin screw compounder (TECHNOVEL society manufacture, KZW-15-30MG) of thermoplastic resin with de-gassing vessel are extruded under the condition of barrel temperature 230 DEG C, propeller speed 200rpm, discharge-amount 1kg/h, obtains particle.According to above-mentioned evaluation method, measure the tone of sheet and be detained thermostability.The results are shown in Table 12.

(comparative example 29 ~ comparative example 32)

With the proportioning shown in table 13, carry out mixing in the same manner as embodiment 66, obtain particle.Evaluation result is in table 13.

[table 12]

[table 13]

From result shown in table 12, table 13, the polycarbonate resin that poly carbonate resin composition uses is obtained by the polycondensation of Isosorbide (ISB), Tricyclodecane Dimethanol (TCDDM) and diphenyl carbonate (DPC), and relative to whole end number, when the above-mentioned phenyl end shown in structural formula (2) is more than 20% (embodiment 66 ~ 72), the tone aspect of sheet, yellowish discoloration is little, and from employing the polycarbonate compositions of thermoplastic resin of the same race each other relatively, it is detained the also excellent material of stability.

Above in detail and describe the present invention with reference to specific embodiment, but for a person skilled in the art, obviously can carry out various change or amendment not departing from the spirit and scope of the present invention.The application is the Japanese patent application (Japanese Patent Application 2008-305648) based on submitting on November 28th, 2008, the Japanese patent application (Japanese Patent Application 2008-305651) that on November 28th, 2008 submits to, the Japanese patent application (Japanese Patent Application 2008-305665) that on November 28th, 2008 submits to, the Japanese patent application (Japanese Patent Application 2008-305687) that on November 28th, 2008 submits to, the Japanese patent application (Japanese Patent Application 2009-144171) that on June 17th, 2009 submits to, the Japanese patent application (Japanese Patent Application 2009-144775) that on June 17th, 2009 submits to, the Japanese patent application (Japanese Patent Application 2009-144776) that on June 17th, 2009 submits to, the Japanese patent application (Japanese Patent Application 2009-144779) that on June 17th, 2009 submits to, the application of the Japanese patent application (Japanese Patent Application 2009-144780) that on June 17th, 2009 submits to, its content is introduced this specification sheets by this form sentencing reference.

Utilizability in industry

According to the present invention, thermotolerance, the polycarbonate resin of transparency excellence and the poly carbonate resin composition containing this polycarbonate resin can be obtained.

Claims

1. a polycarbonate resin, it is at least containing the structural unit from dihydroxy compound, and this dihydroxy compound has the bond structure of following structural formula (1), and the feature of described polycarbonate resin is:

Containing below 700ppm phenol, this phenol has or does not have the alkyl that carbonatoms is less than 5,

Wherein, not bonded hydrogen atoms on the Sauerstoffatom in structural formula (1);

The content of the carbonic diester shown in following general formula (3) is 0.1ppm ~ 60ppm,

In general formula (3), A ¹, A ²be with substituting group or without substituent carbonatoms be 1 ~ 18 1 valency fatty group or with substituting group or without substituent 1 valency aromatic series base, A ¹and A ²identical or different; And

2. polycarbonate resin as claimed in claim 1, it is characterized in that, the remaining content with the dihydroxy compound of the bond structure of described structural formula (1) is below 60ppm.

3. polycarbonate resin as claimed in claim 1, it is characterized in that, the dihydroxy compound with the bond structure of described structural formula (1) has heterocyclic radical.

4. polycarbonate resin as claimed in claim 3, it is characterized in that, the dihydroxy compound with the bond structure of described structural formula (1) is the compound with the heterocyclic radical shown in following general formula (4);

5. polycarbonate resin as claimed in claim 1, it is characterized in that, the terminal group shown in following structural formula (2) there is ratio (A/B) scope more than 20% of number (A) relative to whole end number (B);

6. polycarbonate resin as claimed in claim 1, it is characterized in that, second-order transition temperature is more than 90 DEG C.

7. polycarbonate resin as claimed in claim 1, it is characterized in that, described polycarbonate resin is also containing the structural unit from least one compound be selected from the group that is made up of aliphatics dihydroxy compound, ester ring type dihydroxy compound, oxyalkylene group glycol, bis-phenol, the glycol with cyclic acetal structure.

8. a poly carbonate resin composition, is characterized in that, described composition contains the lipid acid of polycarbonate resin described in 100 any one of weight part claim 1 ~ 7 and 0.0001 weight part ~ 2 weight part.

9. poly carbonate resin composition as claimed in claim 8, is characterized in that, described composition contains the natural system wax of polycarbonate resin described in 100 any one of weight part claim 1 ~ 7 and 0.0001 weight part ~ 2 weight part.

10. poly carbonate resin composition as claimed in claim 8, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part claim 1 ~ 7 and 0.0001 weight part ~ 2 weight part and is selected from least one compound in olefines wax, silicone oil.

11. poly carbonate resin compositions as claimed in claim 8, is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part claim 1 ~ 7 and 0.00001 weight part ~ 0.1 weight part acidic cpd.

12. poly carbonate resin compositions as claimed in claim 8, is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part claim 1 ~ 7 and 0.001 weight part ~ 1 weight part phosphorus series compound.

13. poly carbonate resin compositions as claimed in claim 8, it is characterized in that, described composition contains polycarbonate resin, 0.00001 weight part ~ 0.1 weight part at least one acidic cpd and 0.001 weight part ~ 1 weight part at least one phosphorus series compound described in 100 any one of weight part claim 1 ~ 7.

14. poly carbonate resin compositions as claimed in claim 8, it is characterized in that, described composition contains polycarbonate resin described in 100 any one of weight part claim 1 ~ 7, aromatic monohydroxy compound that 0.001 weight part ~ 1 weight part is the alkyl substituent of more than 5 with more than 1 carbonatoms.

15. poly carbonate resin compositions as claimed in claim 8, is characterized in that, described composition contains poly carbonate resin composition described in 100 any one of weight part claim 1 ~ 7 and 0.000001 weight part ~ 1 weight part bluing agent.

16. 1 kinds of bloomings, is characterized in that, it contains the polycarbonate resin described in any one of claim 1 ~ 7.

17. 1 kinds of polycarbonate resin moldings, is characterized in that, it carries out shaping obtaining by by the polycarbonate resin described in any one of claim 1 ~ 7 or the poly carbonate resin composition described in any one of claim 8 ~ 15.

18. polycarbonate resin moldings as claimed in claim 17, it is characterized in that, described polycarbonate resin moldings obtains by injection moulding is shaping.

19. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and the 1 weight part ~ 100 parts by weight of inorganic filler of 100 weight parts,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and described polycarbonate resin contains below 700ppm has or do not have the phenol that carbonatoms is the alkyl of less than 5;

Wherein, not bonded hydrogen atoms on the Sauerstoffatom in structural formula (1).

20. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and the 1 weight part ~ 100 parts by weight of inorganic filler of 100 weight parts,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, 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 following general formula (3) is 0.1ppm ~ 60ppm;

In general formula (3), A ¹, A ²be with substituting group or without substituent carbonatoms be 1 ~ 18 1 valency fatty group or with substituting group or without substituent 1 valency aromatic series base, A ¹and A ²identical or different.

21. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and the 1 weight part ~ 100 parts by weight of inorganic filler of 100 weight parts,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), and, in described polycarbonate resin, the content with the dihydroxy compound of the bond structure of following structural formula (1) is below 60ppm;

22. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and 0.01 weight part ~ 30 parts by weight of flame retardant of 100 weight parts,

Described polycarbonate resin is at least containing the structural unit from dihydroxy compound, this dihydroxy compound has the bond structure of following structural formula (1), further, described polycarbonate resin contains below 700ppm and has or do not have the phenol that carbonatoms is the alkyl of less than 5;

23. poly carbonate resin compositions as claimed in claim 22, is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

24. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and 0.01 weight part ~ 30 parts by weight of flame retardant of 100 weight parts,

25. poly carbonate resin compositions as claimed in claim 24, is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

26. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and 0.01 weight part ~ 30 parts by weight of flame retardant of 100 weight parts,

27. poly carbonate resin compositions as claimed in claim 26, is characterized in that, fire retardant is selected from least one in the group that is made up of P contained compound flame retardant, halogen contained compound flame retardant.

28. 1 kinds of poly carbonate resin compositions, it contains polycarbonate resin according to claim 1 and the 0.005 weight part ~ 5 weight part UV light absorber of 100 weight parts,

29. poly carbonate resin compositions as claimed in claim 28, is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

30. poly carbonate resin compositions as described in claim 28 or 29, is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

31. 1 kinds of poly carbonate resin compositions, it contains polycarbonate resin according to claim 1 and the 0.005 weight part ~ 5 weight part UV light absorber of 100 weight parts,

32. poly carbonate resin compositions as claimed in claim 31, is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

33. poly carbonate resin compositions as described in claim 31 or 32, is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

34. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin according to claim 1 and the 0.005 weight part ~ 5 weight part UV light absorber of 100 weight parts,

35. poly carbonate resin compositions as claimed in claim 34, is characterized in that, the molar absorptivity of described UV light absorber at wavelength 210nm place is less than 1.75 with the ratio of the maximum value from wavelength 250nm to the molar absorptivity of wavelength 350nm.

36. poly carbonate resin compositions as described in claim 34 or 35, is characterized in that, described UV light absorber is selected from least one in the group that is made up of triazine based compound, oxanilide based compound, malonic ester based compound.

37. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin (a) according to claim 1 and 90 weight part ~ 10 weight parts thermoplastic resin (b) of 10 weight part ~ 90 weight parts,

38. poly carbonate resin compositions as claimed in claim 37, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

39. 1 kinds of poly carbonate resin compositions, it contains polycarbonate resin (a) according to claim 1 and 90 weight part ~ 10 weight parts thermoplastic resin (b) of 10 weight part ~ 90 weight parts,

40. poly carbonate resin compositions as claimed in claim 39, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

41. 1 kinds of poly carbonate resin compositions, is characterized in that, it contains polycarbonate resin (a) according to claim 1 and 90 weight part ~ 10 weight parts thermoplastic resin (b) of 10 weight part ~ 90 weight parts,

42. poly carbonate resin compositions as claimed in claim 41, it is characterized in that, thermoplastic resin (b) is selected from least one in phenylethylene resin series, saturated polyester resin, bis-phenol system polycarbonate resin, polyolefin-based resins and acrylic resin.

43. 1 kinds of polycarbonate resin moldings, is characterized in that, it carries out shaping obtaining to the poly carbonate resin composition described in any one of claim 19 ~ 42.

44. polycarbonate resin moldings as claimed in claim 43, it is characterized in that, polycarbonate resin moldings carries out shaping obtaining by injection moulding.