CN101501101B - Polycarbonate copolymer, process for producing the same, molded body, optical material, and electrophotographic photoreceptor - Google Patents

Abstract

The present invention provides a polycarbonate copolymer which comprises 0.1 to 50 mol% of a monomer unit represented by the following formula and a monomer unit represented by the following formula (2), wherein the content of biphenols having a structure represented by the following formula (3) is 90 mass ppm or less. (in the formula, R¹、R²Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom. ) (2) (in the formula, R³、R⁴Independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom, and X represents-O-, -S-, -SO-, -SO₂-, -CO-, 9-fluorenylidene group. ) (3) (in the formula, R¹、R²Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen atom. )

Description

Copolycarbonate, its manufacture method, molding, optical material and Electrophtography photosensor

Technical field

The molding, optical material and the Electrophtography photosensor that the present invention relates to Copolycarbonate, its manufacture method, by this multipolymer, are formed.

background technology

In the past, by 2, the polycarbonate resin (following also referred to as " PC resin ") that two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane) of 2-is manufactured, because the transparency is high, has outstanding mechanical properties, so for various uses such as optical material or electronic materials., along with the expansion of purposes, for the performance that requires of PC resin, become strictly, urgently expect a kind of PC resin with better performance.For example, the PC resin of using as Electrophtography photosensor, not only require mechanical properties, though also to the transparency, can tolerate charged-except the stable static characteristic repeatedly of electric circulation or also there is good solubility etc. with respect to non-halogen series solvent higher requirement is arranged.

Therefore, disclose a kind of obtain Copolycarbonate (below, also be called " copolymer p C ") method, in the method, as the phenol structure unit, the raw material that use is mixed with dihydroxyphenyl propane and specific xenol carries out polycondensation, obtains can not damaging the transparency and the Copolycarbonate (for example, patent documentation 1) of excellent heat resistance.Again, the also known technology (for example, patent documentation 2) that this multipolymer is applicable to Electrophtography photosensor.

Again, the also known technology (for example patent documentation 3) that obtains the Copolycarbonate that YI is about 1.3-1.4 according to melt co-polycondensation, and make the not enough 150ppb of dissolved oxygen content in the bis-phenol sodium solution and obtain the technology (for example, patent documentation 4) of the polycarbonate of low yellow chromaticity (YI) when interfacial polycondensation.

Again, known for example, by using the fluorenes series bisphenols to obtain the method (, patent documentation 5) of the Copolycarbonate that tone is good under the non-existent condition of oxygen actually.

Patent documentation 1: No. 1965051 communique of Japanese Patent

Patent documentation 2: No. 2531852 communique of Japanese Patent

Patent documentation 3: Japanese patent laid-open 5-117382 communique

Patent documentation 4: the special table of Japanese Patent 2002-533544 communique

Patent documentation 5: Japanese Patent Laid-Open 2005-82677 communique

summary of the invention

The problem that invention will solve

Yet, have following problem in the technology of record in above-mentioned patent documentation 1,2, owing to thering is the xenol skeleton, so with bisphenol A-type PC resin-phase ratio, after even being shaped after polymerization, Copolycarbonate itself is painted.Become a problem in the such a painted optical material transparent in attention.And such a painted multipolymer also often affects static characteristic.Especially, as Electrophtography photosensor, use the problem that while having Reusability, rest potential rises.

Again, as described in patent documentation 3, there is the problem of removing the impurity difficulty in the Copolycarbonate that melt co-polycondensation obtains.Again, patent documentation 4 is disclosed is to use separately the polycarbonate of dihydroxyphenyl propane as the biphenyl phenols, about carrying out such special of copolycondensation, is not disclose a bit.According to from dihydroxyphenyl propane, carrying out kind different of the comonomer of copolycondensation, painted characteristic is also fully different, so the disclosed technology of patent documentation 4 is applied on the cohesively managed of above-mentioned Copolycarbonate, is difficult.

Even in the technology of patent documentation 5, while under the non-existent condition of oxygen, manufacturing Copolycarbonate, need to make the oxygen concn of gas phase and liquid phase below 0.5 quality ppm, because needs equipment is corresponding, so method that neither be easy.

Therefore, the object of the present invention is to provide not only after polymerization but also at shaping after stain also few, static characteristic also good Copolycarbonate, the molding formed by this multipolymer, optical material and Electrophtography photosensor.

Solve the means of problem

Copolycarbonate of the present invention contains the monomeric unit that 0.1～50 % by mole of monomeric unit that following formula (1) means and following formula (2) mean and forms, it is characterized in that thering is the content of biphenyl phenols of the structure that following formula (3) means below 90 quality ppm.

(in formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12.)

(in formula, R ³, R ⁴the aryl or the halogen atom that mean independently respectively hydrogen atom, carbonatoms 1～6 aliphatic alkyl, carbonatoms 6～12, mean-O-of X ,-S-,-SO-,-SO ₂-,-CO-, 9,9-fluorenylidene, following formula (2a), (2b), (2c) and any bonding radical (2d) meaned.)

(in formula, R ⁵, R ⁶mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6 or the aryl of carbonatoms 6～12.Again, R ⁵, R ⁶bonding and form the ring alkylidene group of carbonatoms 4～12 mutually.)

(in formula, R is the alkyl of hydrogen atom or carbonatoms 1～3.Again, in R, have at least one to be the alkyl of carbonatoms 1～3, it is desirable to three is the alkyl of carbonatoms 1～3.)

(in formula, bonding position can be adjacent,, right any one.)

(in formula, R ⁷～R ¹²mean independently respectively the alkyl of hydrogen, carbonatoms 1～4 or the bonding radical formed by singly-bound or alkylidene group.Wherein, R ⁷～R ¹²in two be bonding radical, remaining is the alkyl of hydrogen or carbonatoms 1～4.)

(in formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12.)

According to such copolymerization PC of the present invention, because the content of the biphenyl phenols (initial substance of the monomeric unit of above-mentioned formula (1)) that above-mentioned formula (3) means is below 90 quality ppm, so copolymerization PC is not only painted few in the early stage, and painted also few when melt-shaping.And, the content of biphenyl phenols below 90 quality ppm, when copolymerization PC of the present invention is made to the molding that Electrophtography photosensor uses, the rising of rest potential in the time of can suppressing the Reusability Electrophtography photosensor.

In the present invention, the content of the biphenyl phenols that above-mentioned formula (3) means is the unreacted residues amount in copolymerization PC after polycondensation, more preferably, below 60 quality ppm, more preferably, below 30 quality ppm, it would be desirable below 10 quality ppm.

Copolycarbonate of the present invention contains the monomeric unit that 0.1～50 % by mole of monomeric unit that above-mentioned formula (1) means and above-mentioned formula (2) mean and forms, it is characterized in that, in a part, the content of the biphenol compound of 3 phenol hydroxyls of existence is below 200 quality ppb.

According to such copolymerization PC of the present invention, because in a part, the content of the biphenol compound (following also be called " trihydroxy-biphenyl class ") of 3 phenol hydroxyls of existence is below 200 quality ppb, so copolymerization PC is not only painted few in the early stage, and painted also few when melt-shaping.And, the content of trihydroxy-biphenyl class below 200 quality ppb, when copolymerization PC of the present invention is made to the molding that Electrophtography photosensor uses, the rising of rest potential in the time of can suppressing the Reusability Electrophtography photosensor.

In the present invention, the content of the trihydroxy-biphenyl class in copolymerization PC, below 150 quality ppb, more preferably, below 100 quality ppb, it would be desirable below 50 quality ppb.

Copolycarbonate of the present invention, in 2 phase series solvents, polyreaction under the existence of alternate moving catalyst and obtaining, described 2 phase series solvents are by the Copolycarbonate finally obtained more than solubilized 5 quality %, in fact solvent not mixed with water, with the aqueous solution that is dissolved with alkali metal hydroxide or alkaline-earth metal oxyhydroxide, form, it is characterized in that, Copolycarbonate contains the monomeric unit that 0.1～50 % by mole of monomeric unit that above-mentioned formula (1) means and above-mentioned formula (2) mean and forms, the YI of this carbonate copolymer (according to JIS K7105, measuring flaky powder) is below 3.

According to copolymerization PC of the present invention, the monomeric unit meaned due to above-mentioned formula (1) is 0.1～50 % by mole, the YI of this carbonate copolymer (according to JIS K 7105, measuring flaky powder), below 3, also payes attention to water white optical material so be suitable for use in except thermotolerance.Again, because the YI of flaky powder below 3, also means that the amount of the impurity that static characteristic is worsened is few simultaneously, so the raw material of the molding used as Electrophtography photosensor is also useful.

Just, 0.1 % by mole of the monomeric unit less than that (1) means, as copolymerization PC, stable on heating raising is concluded, again in the outermost purposes for Electrophtography photosensor, the wear resistance deficiency, weather resistance is inadequate.On the other hand, the monomeric unit that above-mentioned (1) means surpasses 50 % by mole, the easy crystallization of xenol skeleton and transparency deterioration.Again, generate such crystallization in the sensitive layer of Electrophtography photosensor, static characteristic worsens.The desirable scope of the monomeric unit shown in above-mentioned formula (1) is 1～40 % by mole, more preferably 5～30 % by mole.

Again, the monomer that the monomer that Copolycarbonate of the present invention is meaned by above-mentioned formula (3) and following formula (4) mean forms by polycondensation, it is characterized in that, content in the monomer that exists the biphenol compound (following also be called " trihydroxy-biphenyl class ") of 3 phenol hydroxyls to mean in above-mentioned formula (3) in a part (below, also be called " xenol monomer ") is below 300 quality ppm.

(in formula, R ³, R ⁴the aryl or the halogen atom that mean independently respectively hydrogen atom, carbonatoms 1～6 aliphatic alkyl, carbonatoms 6～12, mean-O-of X ,-S-,-SO-,-SO ₂-,-CO-, 9,9-fluorenylidene, above-mentioned formula (2a), (2b), (2c) and any bonding radical (2d) meaned.)

According to such copolymerization PC of the present invention, because in the xenol monomer, the content of contained impurity trihydroxy-biphenyl class is below 300 quality ppm, so copolymerization PC sheet itself does not almost have painted.Therefore, be suitable for the optical material also paid attention to except the thermotolerance water white transparency.Again, the residual quantity of the trihydroxy-biphenyl class that static characteristic is worsened is also few, so the raw material of the molding used as Electrophtography photosensor is also useful.The content of the trihydroxy-biphenyl class in the xenol monomer it is desirable to below 150 quality ppm, more preferably, below 20 quality ppm, it would be desirable below 10 quality ppm.

In Copolycarbonate of the present invention, it is desirable to YI (according to J1S K 7105, measuring flaky powder) below 3.

Here, after polymerization, copolymerization PC obtains as flaky powder, and the YI value in copolymerization PC of the present invention can be used and measure the value obtained like this.Again, copolymerization PC obtains with the shape outside sheet, and preparation YI as described below measures the sample of use.

Methylene dichloride with respect to 1L, dissolve copolymerization PC with the ratio of 30～70g and obtain a solution, on one side this solution is dripped in 2L methyl alcohol with the speed that forms sheet, stir fully on one side, after full dose is dripped, then increase 2L methyl alcohol, for the adhesion of melting does not more occur, take out solids, abundant dried is measured and use sample as YI.In addition, the concentration by copolymerization PC in dichloromethane solution is adjusted to above-mentioned concentration range, to obtain being applicable to carrying out the sheet of the shape of YI mensuration.

According to the present invention, the YI of copolymerization PC is below 3, owing to being that painted origin material is few, for example, and when the molding that will consist of this copolymerization PC is applied on Electrophtography photosensor, the rising of the rest potential while suppressing Reusability.Again, because painted origin material is few, so in forming process thereafter, can not carry out yet further painted, so also useful as the raw material of paying attention to transparent optical material.As the YI of copolymerization PC, it is desirable to below 2.3, more preferably below 1.8, more preferably below 1.2.

Molding of the present invention it is desirable to that above-mentioned Copolycarbonate is carried out to melt-shaping and forms.

According to such molding of the present invention, due to copolymerization PC melt-shaping is formed, so the molding with various shapes can easily be provided.

Especially, at the YI that uses sheet, in the copolymerization PC 3 below carries out molding that melt-shaping forms, painted also few due to the molding after melt-shaping, so also be suitable as optical material use.

Molding of the present invention it is desirable to that above-mentioned Copolycarbonate is carried out to wet forming and forms.

According to such molding of the present invention, owing to being wet forming, so molding through the time variable color (in time passage and variable color) suppressed, outcome quality worsens few.

Especially, the content of biphenyl phenols below 90ppm or the content of trihydroxy-biphenyl class below 200ppb, the deterioration caused by light, heat, oxidizing substance, moisture etc. is suppressed, thus molding through the time variable color suppressed, outcome quality worsens few.Again, as Electrophtography photosensor, use because during Reusability rest potential rise suppressed especially, so very useful.

Again, the YI of the sheet of copolymerization PC is below 3, while making molding equally through the time variable color suppressed, the rising of rest potential during Reusability while using as Electrophtography photosensor is especially suppressed.We think that this is because the YI of the sheet by making copolymerization PC, below 3, makes copolymerization PC change to yellow material relatively less under the effect of light, heat, oxidizing substance, moisture etc.

Optical material of the present invention is characterized in that containing above-mentioned Copolycarbonate or the molding consisted of it.

According to such optical material of the present invention, owing to containing above-mentioned Copolycarbonate, be melt into body or the wet forming body forms, so almost do not have paintedly, the transparency is also good, good as optical material.

Electrophtography photosensor of the present invention is characterized in that containing above-mentioned Copolycarbonate or the molding consisted of it.

Here, Electrophtography photosensor is that the Electrophtography photosensor of sensitive layer for example is set on conductive board, can be by above-mentioned copolymerization PC suitably as adhesive resin, top coat resin or binding resin etc.

According to such Electrophtography photosensor of the present invention, because used using above-mentioned copolymerization PC as so-called adhesive resin etc., so static characteristic is good, especially the ascensional range of rest potential during Reusability is little, thereby extremely useful.

The manufacture method of Copolycarbonate of the present invention, the monomer that the monomer that uses above-mentioned formula (3) to mean and above-mentioned formula (4) mean carries out polycondensation, it is characterized in that, 1 mole of the monomer meaned with respect to above-mentioned formula (3), add antioxidant in reaction system to the ratio of 0.0001～1 molar equivalent.

According to such manufacture method, because while using the monomer of regulation to manufacture copolymerization PC, 1 mole of the monomer meaned with respect to above-mentioned formula (3), antioxidant is added in reaction system with the ratio of 0.0001～0.1 molar equivalent, so can suppress side reaction, can suppress the initial coloration of resulting copolymerization PC.The YI that for example, easily will obtain according to JIS K 7105 test pieces is controlled at below 3.Namely, in the present invention, be characterised in that, even there is actually the copolymerization PC that under the condition of oxygen, also can obtain having good characteristic.

In manufacture method of the present invention, it is desirable to above-mentioned antioxidant is hydrosulphite.

According to the manufacture method of such invention, because use hydrosulphite as antioxidant, so the side reaction in the time of can further suppressing polycondensation can more effectively suppress the initial coloration of resulting copolymerization PC.

In manufacture method of the present invention, the temperature while it is desirable to make polyreaction is below 20 ℃.

According to such manufacture method of the present invention, because the temperature while making polyreaction is below 20 ℃, so easily suppress the initial coloration of resulting copolymerization PC.

In manufacture method of the present invention, it is desirable in oxygen partial pressure is to carry out polycondensation under the atmosphere below 5065Pa.

According to such manufacture method of the present invention, because be to carry out polycondensation under the atmosphere below 5065Pa in oxygen partial pressure, so easily suppress the initial coloration of resulting copolymerization PC.More preferably this oxygen partial pressure is below 1013Pa.

The feature of Copolycarbonate of the present invention is manufactured by the manufacture method of above-mentioned any.

Such a Copolycarbonate of the present invention is because the method by above-mentioned is manufactured, so the initial coloration of resulting copolymerization PC is considerably less.Therefore, be suitable for requiring transparent optical material field.Again, the impurity contained due to copolymerization PC is also few, and static characteristic is good, for example, and can be suitably for the Electrophtography photosensor field.

Embodiment

Below, explain embodiment for Copolycarbonate of the present invention (copolymerization PC) and manufacture method thereof.Also the embodiment that contains the Electrophtography photosensor that uses this copolymerization PC to make the molding of adhesive resin and form is described.

The<the 1 embodiment >

Below, the 1st embodiment of the present invention is described in detail.

[formation of copolymerization PC]

The copolymerization PC of present embodiment contains the monomeric unit that 0.1～50 % by mole of monomeric unit that following formula (1) means and following formula (2) mean and forms, and has the content of biphenyl phenols of the structure that following formula (3) means below 90 quality ppm.

(in formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12.)

(in formula, R ³, R ⁴the aryl or the halogen atom that mean independently respectively hydrogen atom, carbonatoms 1～6 aliphatic alkyl, carbonatoms 6～12, mean-O-of X ,-S-,-SO-,-SO ₂-,-CO-, 9,9-fluorenylidene, above-mentioned formula (2a), (2b), (2c) and any bonding radical (2d) meaned.)

(in formula, R ⁵, R ⁶mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6 or the aryl of carbonatoms 6～12.Again, R ⁵, R ⁶bonding and form the ring alkylidene group of carbonatoms 4～12 mutually.)

(in formula, R is the alkyl of hydrogen atom or carbonatoms 1～3.Again, in R at least one, to it is desirable to three be the alkyl of carbonatoms 1～3.)

(in formula, bonding position can be adjacent,, right any one.)

(in formula, R ⁷～R ¹²mean independently respectively the alkyl of hydrogen, carbonatoms 1～4 or the bonding radical formed by singly-bound or alkylidene group.Wherein, R ⁷～R ¹²in two be bonding radical, remaining is the alkyl of hydrogen or carbonatoms 1～4.)

(in formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12.)

In addition, meet R ¹, R ², R ³, R ⁴substituting group can be a plurality of and a phenyl ring bonding, the substituting group of bonding can be the same or different.

0.1 % by mole of the ratio deficiency of the monomeric unit that above-mentioned formula (1) means, can not get the modified effect that the xenol skeleton brings, and thermotolerance is inadequate, or the painting work liquid flooding white (gelation) during wet forming.While using as the molding (adhesive resin) of Electrophtography photosensor, be difficult to prevent the crystallization of charge transport layer or be difficult to reach the raising in anti-brush life-span again.On the other hand, the ratio of this monomeric unit surpasses 50 % by mole, because crystallization easily occurs a part of copolymerization PC (xenol skeleton), transparency deterioration, so be not suitable for sticking with glue the agent resin as Electrophtography photosensor.For example, see through light quantity and descend, the sensitivity of Electrophtography photosensor descends.Again, (ヘ イ ズ) is large for mist, produces image diffusion and undesirable.

The desirable scope of the monomeric unit shown in above-mentioned formula (1) is 1～40 % by mole, more preferably 5～30 % by mole.

In such present embodiment, because the content of the biphenyl phenols shown in the above-mentioned formula (3) in copolymerization PC (initial substance of the monomeric unit of above-mentioned formula (1)) is below 90 quality ppm, so not only so-called reduced in initial coloration, and continuous smelting melts painted while being shaped and also tails off.Again, the content of biphenyl phenols below 90 quality ppm, when copolymerization PC is made to the molding that Electrophtography photosensor uses, the rising of the rest potential in the time of can suppressing the Reusability Electrophtography photosensor.

The content of this biphenyl phenols is the unreacted residues amount in polycondensation, more preferably, below 60 quality ppm, more preferably, below 30 quality ppm, it would be desirable below 10 quality ppm.

Again, the copolymerization PC of present embodiment it is desirable to, the reducing viscosity [η of the solution of the concentration 0.5g/dl that solvent is methylene dichloride in 20 ℃ _sp/ C] scope in 0.2～5.0dl/g.Reducing viscosity [η _sp/ C] not enough 0.2dl/g, the physical strength of copolymerization PC is low.Especially, when this copolymerization PC is made to Electrophtography photosensor for example with the adhesive resin of molding, the surface hardness of adhesive layer is inadequate, photoreceptor abrasion and anti-brush lifetime is unfavorable in practicality.On the other hand, reducing viscosity [η _sp/ C] surpass 5.0dl/g, the soltion viscosity of copolymerization PC rises, and while utilizing solution to be coated with engineering method, it is difficult that the photoreceptor manufacture becomes.

In addition, the copolymerization PC of present embodiment, in the scope that does not hinder purpose of the present invention, can have other monomeric unit except above-mentioned, again, also can suitably add the polycarbonate composition or the additive that mix other and use.

[manufacture method of copolymerization PC]

The copolymerization PC of this example, by using the monomer shown in above-mentioned formula (3) and the mix monomer of the monomer shown in following formula (4) to carry out polycondensation, can easily obtain the powder of sheet.

(in formula, R ³, R ⁴the aryl or the halogen atom that mean independently respectively hydrogen atom, carbonatoms 1～6 aliphatic alkyl, carbonatoms 6～12, mean-O-of X ,-S-,-SO-,-SO ₂-,-CO-, 9,9-fluorenylidene, above-mentioned formula (2a), (2b), (2c) and any bonding radical (2d) meaned.)

As the monomer (biphenyl phenols) shown in above-mentioned formula (3), have for example 4,4 '-xenol, 3,3 '-dimethyl-4,4 '-xenol, 3,3 ', 5-trimethylammonium-4,4 '-xenol, 3-propyl group-4,4 '-xenol, 3,3 ', 5,5 '-tetramethyl--4,4 '-xenol, 3,3 '-phenylbenzene-4,4 '-xenol, 3,3 '-dibutyl-4,4 '-xenol etc.Especially, 4,4 '-xenol sees ideal from giving painted few copolymerization PC this point.Again, the occasion that the copolymerization PC used as Electrophtography photosensor is applied, weather resistance also improves.These can use separately a kind, also can two or more also use.

As the monomer shown in above-mentioned formula (4), two (3-methyl-4-hydroxy phenyl) ethane of 1,1-is arranged for example, two (3-phenyl-4-hydroxy phenyl) fluorenes of 9,9-, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) ethane of 1,1-, two (4-hydroxy phenyl) ethane of 1,2-, two (4-hydroxy phenyl) propane of 2,2-, two (3-methyl-4-hydroxy phenyl) butane of 2,2-, two (4-hydroxy phenyl) butane of 2,2-, two (4-hydroxy phenyl) octanes of 2,2-, two (4-hydroxy phenyl) heptane of 4,4-, two (the 4-hydroxy phenyls)-1 of 1,1-, the 1-ditan, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1,1-, two (4-the hydroxy phenyl)-1-phenylmethanes of 1,1-, two (4-hydroxy phenyl) ether, sulfuration two (4-hydroxy phenyl), two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) pentamethylene of 1,1-, two (3-methyl-4-hydroxy phenyl) pentamethylene of 1,1-, 1,1-bis(4-hydroxyphenyl) cyclohexane, two (3-methyl-4-hydroxy phenyl) propane of 2,2-, two (3-phenyl-4-hydroxy phenyl) propane of 2,2-, two (4-hydroxy phenyl) diamantane of 2,2-, two (3-methyl-4-hydroxy phenyl) diamantane of 2,2-, two (4-hydroxy phenyl) diamantane of 1,3-, two (3-methyl-4-hydroxy phenyl) diamantane of 1,3-, 2-(3-methyl-4-hydroxy phenyl)-2-(4-hydroxy phenyl)-1-diphenylphosphino ethane, sulfuration two (3-methyl-4-hydroxy phenyl), two (3-methyl-4-hydroxy phenyl) sulfone, two (3-methyl-4-hydroxy phenyl) methane, two (3-methyl-4-hydroxy phenyl) hexanaphthenes of 1,1-, 2,7-naphthalene glycol, 2,6-naphthalene glycol, Isosorbide-5-Nitrae-naphthalene glycol, 1,5-naphthalene glycol, two (2-methyl-4-hydroxy phenyl) propane of 2,2-, two (2-butyl-4-hydroxy-5-methyl base phenyl) butane of 1,1-, two (2-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) ethane of 1,1-, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propane of 1,1-, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) butane of 1,1-, two (2-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) Trimethylmethanes of 1,1-, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) heptane of 1,1-, two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-1-phenylmethanes of 1,1-, two (2-tert-pentyl-4-hydroxy-5-methyl base phenyl) butane of 1,1-, two (3-chloro-4-hydroxyl phenyl) methane, two (the bromo-4-hydroxy phenyl of 3,5-bis-) methane, two (the 3-chloro-4-hydroxyl phenyl) propane of 2,2-, two (the fluoro-4-hydroxy phenyl of the 3-) propane of 2,2-, two (the bromo-4-hydroxy phenyl of the 3-) propane of 2,2-, two (the fluoro-4-hydroxy phenyl of 3, the 5-bis-) propane of 2,2-, two (the chloro-4-hydroxy phenyl of 3, the 5-bis-) propane of 2,2-, two (the bromo-4-hydroxy phenyl of 3, the 5-bis-) propane of 2,2-, two (the bromo-4-hydroxyl of the 3--5-chloro-phenyl-) propane of 2,2-, two (the chloro-4-hydroxy phenyl of 3, the 5-bis-) butane of 2,2-, two (the bromo-4-hydroxy phenyl of 3, the 5-bis-) butane of 2,2-, 1-phenyl-1, two (the fluoro-4-hydroxy phenyl of the 3-) ethane of 1-, two (the fluoro-4-hydroxy phenyl of 3-) ether, 3,3 '-bis-is fluoro-4,4 '-dihydroxybiphenyl, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthenes of 1,1-, two (4-hydroxy phenyl) HFC-236fa of 2,2-, two (3-phenyl-4-hydroxy phenyl) hexanaphthenes of 1,1-, two (3-phenyl-4-hydroxy phenyl) sulfone, 4,4 '-(3,3,5-trimethylammonium cyclohexylene) biphenol, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] biphenol, 4,4 '-[1,3-phenylene two (1-methyl ethylidene)] biphenol, two (4-hydroxy phenyl) fluorenes of 9,9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, end phenol polydimethylsiloxane, α, ω-bis-(3-(4-hydroxy 3-methoxybenzene base) propyl group)-dimethylsilane oxygen base-polydimethylsiloxane, and α-trimethylsiloxy-ω-bis-{ 3-(2-hydroxy phenyl) propyl-dimethyl siloxy-}-methyl-silicane oxygen base-2-dimetylsilyl ethyl-polydimethylsiloxanes etc.These biphenol compounds can be used separately a kind, also can mix two or more use.Again, also can use the above phenol of ternary, make it to there is branched structure.

In these biphenol compounds, it is desirable to two (4-hydroxy phenyl) ethane of 1,1-, two (4-hydroxy phenyl) butane of 2,2-, two (4-hydroxy phenyl) propane of 2,2-, two (the 4-hydroxy phenyls)-1 of 1,1-, the 1-ditan, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1,1-, two (4-hydroxy phenyl) sulfone, 1,1-bis(4-hydroxyphenyl) cyclohexane, two (3-methyl-4-hydroxy phenyl) propane of 2,2-, two (3-methyl-4-hydroxy phenyl) hexanaphthenes of 1,1-, two (3-methyl-4-hydroxy phenyl) pentamethylene of 1,1-, two (3-phenyl-4-hydroxy phenyl) propane of 2,2-, 4,4 '-(3,3,5-trimethylammonium cyclohexylene) biphenol, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] biphenol, 4,4 '-[1,3-phenylene two (1-methyl ethylidene)] biphenol, two (4-hydroxy phenyl) fluorenes of 9,9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, end phenol polydimethylsiloxane, α-trimethylsiloxy-ω-bis-{ 3-(2-hydroxy phenyl) propyl-dimethyl siloxy-}-methyl-silicane oxygen base-2-dimetylsilyl ethyl-polydimethylsiloxane, and α, ω-bis-(3-(4-hydroxy 3-methoxybenzene base) propyl group)-dimethylsilane oxygen base-polydimethylsiloxane.

More preferably 1, two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) butane, 2 of 2-, two (4-hydroxy phenyl) propane, 1 of 2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane, 2, two (3-methyl-4-hydroxy phenyl) propane, 1 of 2-, two (3-methyl-4-hydroxy phenyl) hexanaphthenes, 1 of 1-, two (3-methyl-4-hydroxy phenyl) pentamethylene, 2 of 1-, two (3-phenyl-4-hydroxy phenyl) propane, 4 of 2-, 4 '-(3,3,5-trimethylammonium cyclohexylene) biphenol, 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-.

Copolymerization PC using such biphenol compound as the monomer manufacture is applied to Electrophtography photosensor, in matting etc., even with other members frictions, also be difficult for abrasion, weather resistance improves and desirable as a result.

The copolymerization PC of present embodiment, by using the monomer shown in above-mentioned formula (3) and the monomer shown in above-mentioned formula (4) to carry out the polycondensation of interfacial polycondensation etc., can easily obtain.

For example, by using, take the haloformate class, carbonate products etc. of various two halogen phosphinylidynes that carbonyl chloride is representative or chloro-formic ester compound etc., carry out interfacial polycondensation under the existence of sour linking agent, can form aptly carbonic acid ester bond.Perhaps, also can adopt transesterification reaction.These reactions are carried out under the existence of terminator and/or branching agent as required endways.

As the above-mentioned end terminator, can use the carboxylic acid of monobasic and the phenol of its derivative or monobasic.For example, can suitably use p-tert-butylphenol, p-phenyl phenol, to cumyl phenol, to the perfluor nonylphenol, to (perfluor nonyl phenyl) phenol, to (perfluor xylyl phenyl) phenol, to tertiary perfluoro butyl phenol, 1-(para hydroxybenzene methyl) perfluoro decane, to [2-(1H, 1H-perfluor laccerane oxygen base)-1, 1, 1, 3, 3, 3-hexafluoro propyl group] phenol, 3, two (the perfluoro hexyl oxygen carbonyl) phenol of 5-, to Para Hydroxy Benzoic Acid perfluor dodecyl ester, to (1H, 1H-perfluor octyloxy) phenol, 2H, 2H, the 9H-perfluoro-pelargonic acid, 1, 1, 1, 3, 3, 3-tetrafluoro-2-propyl alcohol, or the alcohol that means of following formula etc.

H(CF ₂) _nCH ₂OH

(n is 1～12 integer)

H(CF ₂) _mCH ₂OH

(m is 1～12 integer)

The adding proportion of these end terminators is 0.05～30 % by mole as the copolymerization ratio of components, more preferably 0.1～10 % by mole, this ratio surpasses 30 % by mole, sometimes causes physical strength to descend, less than 0.05 % by mole, sometimes cause plasticity to descend.

As the object lesson of branching agent, Phloroglucinol is arranged for example again, pyrogallol, 4,6-dimethyl-2,4,6-tri-(4-hydroxy phenyl)-2-heptene, 2,6-dimethyl-2,4,6-tri-(4-hydroxy phenyl)-3-heptene, 2,4-dimethyl-2,4,6-tri-(4-hydroxy phenyl) heptane, 1,3,5-tri-(2-hydroxy phenyl) benzene, 1,3,5-tri-(4-hydroxy phenyl) benzene, 1,1,1-tri-(4-hydroxy phenyl) ethane, three (4-hydroxy phenyl) phenylmethane, 2,2-two [two (4-hydroxy phenyl) cyclohexyl of 4,4-] propane, 2,4-two [two (4-the hydroxy phenyl)-2-propyl group of 2-] phenol, two (2-hydroxy-5-methyl base the phenmethyl)-4-methylphenols of 2,6-, 2-(4-hydroxy phenyl)-2-(2,4-dihydroxy phenyl) propane, four (4-hydroxy phenyl) methane, four [4-(4-hydroxy phenyl sec.-propyl) phenoxy group] methane, 2,4-dihydroxyl M-nitro benzoic acid, trimesic acid, the acid of cyanogen urea, two (3-methyl-4-hydroxy phenyl)-2-oxo-2 of 3,3-, 3-dihydro indoles, two (4-hydroxyaryl) Oxoindoles of 3,3-, 5-chloro isatin, 5,7-, bis-chlorisatides, 5-bromoisatin etc.

The addition of these branching agents, it is desirable to below 5 % by mole below 30 % by mole with the copolymerization ratio of components, and it surpasses 30 % by mole, sometimes causes plasticity to descend.

While carrying out interfacial polycondensation, as sour linking agent, can use the organic bases of alkaline carbonate, pyridine etc. of the alkali metal hydroxide, sodium carbonate, salt of wormwood etc. of alkaline-earth metal oxyhydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide etc., lithium hydroxide, cesium hydroxide etc. or their mixture.The usage ratio of this acid linking agent also can consider the reaction stoichiometric ratio (equivalent) carry out suitable adjustment.Specifically, every 1 mole of the hydroxyl of raw material binary phenol, use 1 equivalent or than its excess quantity, it is desirable to the sour linking agent of 1～10 equivalent, get final product.

As the solvent here used, suitable aromatic hydrocarbons, methylene dichloride, chloroform, 1 that toluene, dimethylbenzene etc. are arranged for example, 1-ethylene dichloride, 1,2-ethylene dichloride, 1，1，1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1, the halon of 1,2,2-tetrachloroethane, pentaline, chlorobenzene etc., methyl phenyl ketone etc.These solvents, can be used separately a kind, also can two or more be used in combination.And, can use 2 kinds of insoluble solvents mutually to carry out interfacial polycondensation.

Again, as above-mentioned catalyzer, suitable have Trimethylamine 99, triethylamine, Tributylamine, N, quaternary alkylphosphonium salts such as the quaternary ammonium salt of the tertiary amine of N-dimethylcyclohexylamine, pyridine, xylidine etc., Three methyl Benzene ammonium methyl muriate, triethylbenzene ammonium methyl muriate, tributyl phenmethyl ammonium muriate, tricaprylmethylammonium muriate, TBuA muriate, TBuA bromide etc., 4-butyl-phosphonium muriate, 4-butyl-phosphonium bromide etc.

As required, can in this reaction system, add the antioxidant of a small amount of S-WAT or hydrosulphite etc. again.

The concrete available various modes of the manufacturing process of this copolymerization PC are implemented, for example, can adopt following method, make binary phenol (the biphenol class of the biphenyl phenols of above-mentioned formula (3) and/or above-mentioned formula (4)) and carbonyl chloride reaction, manufacture polycarbonate oligomer, then under the existence of the mixed solution of the alkali aqueous solution of above-mentioned solvent and sour linking agent, make this Copolycarbonate and above-mentioned binary phenol reactant.Can adopt the method that above-mentioned binary phenol and carbonyl chloride are reacted in the mixed solution of above-mentioned solvent and alkali aqueous solution again.Usually, the former method of manufacturing in advance polycarbonate oligomer is efficient, so desirable.

For manufacturing polycarbonate oligomer, at first, dissolve binary phenol in alkali aqueous solution, the alkali aqueous solution of preparation binary phenol.Then, import carbonyl chloride in the mixed solution of the organic solvent of this alkali aqueous solution and methylene dichloride etc. and make it reaction, the polycarbonate oligomer of synthetic binary phenol.Then, reaction soln is separated into to water and organic phase, obtains the organic phase that contains polycarbonate oligomer.Now, the alkali concn of alkali aqueous solution it is desirable to the scope of 0.1～5 regulation, and again, the volumetric ratio of organic phase and water is 10: 1～1: 10, it is desirable to 5: 1～scope of 1: 5.

Temperature of reaction is generally 0～70 ℃ under cooling, it is desirable to 5～65 ℃, 15 minutes～4 hours reaction times, it is desirable to 30 minutes～and about 3 hours.The molecular-weight average of the polycarbonate oligomer obtained like this is below 6000, and the polymerization degree, usually below 20, it is desirable to the material of 2～10 polymers.

In the organic phase that contains the polycarbonate oligomer obtained like this, add above-mentioned binary phenol to make it reaction.Temperature of reaction is 0～150 ℃, it is desirable to 5～40 ℃, more preferably 5～30 ℃, and particularly desirably 5～20 ℃.Especially, by making temperature of reaction below 30 ℃, especially below 20 ℃, can suppress the copolymerization PC of generation painted (rising of YI).

Reaction pressure can be any one in decompression, normal pressure, pressurization, usually can under the self-pressure degree of normal pressure or reaction system, suitably carry out.Reaction times reflected temperature left and right, but normally 0.5 minute～10 hours, it is desirable to 1 minute～about 2 hours.

When this reaction is carried out, wish binary phenol is made to organic solvent solution and/or alkali aqueous solution interpolation.The order of its interpolation has no particular limits.In addition, catalyzer, end terminator and branching agent etc. can be in above-mentioned manufacturing processs, as required, when manufacturing polycarbonate oligomer, polymer thereafter quantize reaction the time any one reaction in or all add use in both.

As the method for residual concentration below 90 quality ppm that makes biphenyl phenols (unreacted monomer) contained in generated copolymerization PC, can apply various methods again.For example, (1) reaction equivalent optimizing while making polymerization is arranged for example, reduce the method for monomer residual content, (2) in the matting after polymerization, make the cleaning condition optimizing in alkali aqueous solution, remove the method for residual unreacted monomer, (3) optimum solvation unreacted monomer in the crystallization operation, and the method with solvent treatment copolymerization PC that can crystallization, (4) (move to the alkali matting in the way of manufacturing process, the moment before the crystallization operation), confirm residual unreacted monomer amount, according to the unreacted monomer amount, carry out monomer and remove operation (in the alkali matting, in the crystallization operation) method etc.

In matting after above-mentioned (2) polymerization, can be as described below.

In the present embodiment, after copolymerization PC sheet, because unreacted monomer or low molecular weight impurities enter polymer solids inside, so, even the liquid of water etc. is cleaned, also only remove the thing that is attached to the sheet surface.On the other hand, in the cleaning of polymers soln, can reduce impurity as residual monomer of the solvable composition of alkali etc. by counterextraction.

In the cleaning of polymers soln, at first by being washed, the highly concentrated solution during dilution polymerization, easily fractionate aqueous solutions and polymers soln.Then, by being cleaned with aqueous sodium hydroxide solution, utilize the residual xenol of alkali to be removed by the tank counterextraction.In the present invention, cleaning meets the degree of constitutive requirements of the present invention to the impurity in final polymkeric substance.For example, 1～3 left and right in embodiments of the invention described later.

The suitable concentration range of aqueous sodium hydroxide solution is 0.01～1N, and biphenyl phenols residual in this scope is removed effectively.Not enough 0.01N, I'm afraid that the extraction efficiency of residual biphenyl phenols descends, and residual quantity increases.And surpass 1N, probably polymkeric substance can decompose.

After cleaning with aqueous sodium hydroxide solution, alkaline components is residual, and the goods polymkeric substance probably can be hydrolyzed, so use the HCl aqueous cleaning.

The suitable concentration scope of the HCl aqueous solution for example, as long as the concentration (, 0.001～0.1N) be neutralized at alkali gets final product.In the cleaning with the HCl aqueous solution, clean the degree that does not affect polymer unwinds to residual alkali composition.For example, 1～3 left and right in embodiments of the invention described later.

After being cleaned with the HCl aqueous solution, for deionizing impurity, finally washed.

The copolymerization PC obtained like this is that the repeating unit meaned by the repeating unit of above-mentioned (1) expression and above-mentioned formula (2) is that form, the multipolymer of content below 90 quality ppm of the biphenyl phenols of structure that have above-mentioned (3) expression.

In addition, can be, in not hindering the scope that reaches purpose of the present invention, contain the polycarbonate unit with the structural unit outside above-mentioned formula (1) and above-mentioned formula (2) in this copolymerization PC or contain there is polyester, the unit of urethane, polyethers, polysiloxane structure.

Again, usually contain micro-impurity in biphenyl phenols in the binary phenol used as monomer, wherein, by the content management by trihydroxy-biphenyl class (having the biphenol compound of 3 phenol hydroxyls in a part), below 300 quality ppm, easily the YI of copolymerization PC is controlled at below 3.As a result, the spheroid or the molding that by this copolymerization PC (flaky powder), are shaped almost do not have painted.When the content of trihydroxy-biphenyl base class surpasses 300 quality ppm, can reduce impurity by the cleaning condition optimizing that makes polymkeric substance.

Again, the content of the trihydroxy-biphenyl class that static characteristic is worsened is few, and this raw material to the molding that uses as Electrophtography photosensor is also useful.The content of the trihydroxy-biphenyl class in the biphenyl phenols it is desirable to below 150 quality ppm, more preferably, below 20 quality ppm, it would be desirable below 10 quality ppm.

Again, the YI of copolymerization PC is controlled at below 3, make the 3-tertiary butyl-4,4 in the biphenyl phenols '-content of dihydroxybiphenyl it is desirable to below 300 quality ppm below 370 quality ppm, more preferably also effective below 30 quality ppm.

The content that reduces such impurity has following method, during synthetic biphenyl phenols, from the raw material high precision, removes the method for the binary phenol of catechol etc., the method for with alcohols (methyl alcohol, ethanol, Virahol etc.) or ketone (acetone, ethyl methyl ketone etc.), resulting biphenyl phenols being carried out the method for recrystallize or utilizing post to be separated etc.Especially, resulting biphenyl phenols is carried out to the method for recrystallize due to the high purity product that can obtain on technical scale, thus desirable.

In addition, make the reducing viscosity [η of resulting copolymerization PC _sp/ C] (value relevant to viscosity-average molecular weight) in above-mentioned scope, can by such as selecting above-mentioned reaction conditions, the whole bag of tricks such as usage quantity of regulating branching agent or molecular weight regulator carry out.Again, also can according to circumstances to resulting copolymerization PC, implement suitable physical treatment (mixing, separation etc.) and/or chemical treatment (polymer reaction, crosslinking Treatment, decomposed processing etc.), obtain the reducing viscosity [η of regulation _sp/ C] copolymerization PC.Again, can implement the various aftertreatments of known separation and purification method etc. to resulting resultant of reaction (thick resultant), the material of desired purity (refining degree) is reclaimed as copolymerization PC.

[structure of Electrophtography photosensor]

Can contain the molding that use obtains using the copolymerization PC of above-mentioned present embodiment as adhesive resin and form Electrophtography photosensor.

The Electrophtography photosensor of present embodiment is as long as utilized the above-mentioned adhesive resin of copolymerization PC in sensitive layer, known various forms of Electrophtography photosensor certainly needless to say, other any type of also can, but it is desirable to sensitive layer is made and had the electrophotographic photoreceptor that at least 1 layer charge produces the electrophotographic photoreceptor of layer and at least 1 layer charge transfer layer or has charge generation material and charge transport material at one deck.

Copolymerization PC can be for any part of sensitive layer; but in order to give full play to effect of the present invention; hope adhesive resin as the electric charge moving matter in charge transport layer is used, or uses as the adhesive resin of single sensitive layer, or uses as sealer.While thering is the Electrophtography photosensor of multi-layered type of 2 layer charge transfer layer, it is desirable to for its arbitrary charge transport layer.

In the Electrophtography photosensor of present embodiment, the copolymerization PC of above-mentioned present embodiment can be used separately a kind, also can two or more be used in combination.Can, as requested in the scope that does not hinder purpose of the present invention, can contain the adhesive resin composition of other polycarbonate etc. again.The additive that can contain again, antioxidant etc.

The Electrophtography photosensor of present embodiment is the Electrophtography photosensor that has sensitive layer on conductive board.Sensitive layer has the situation of charge generation layer and charge transport layer, can, in charge generation layer upper strata piezoelectricity lotus transfer layer, also can press on the charge transport layer upper strata charge generation layer.Can in one deck, contain charge generation material and charge transport material again, simultaneously.As required, can on upper layer, form the protective membrane of electroconductibility or insulativity again.Also can form the middle layer etc. of the tack coat that the cohesiveness that improves each interlayer uses or the trapping layer that plays the prevention electric charge etc. again.

The conductive board material used as the Electrophtography photosensor of present embodiment, can use the various materials such as known, can use aluminium particularly, nickel, chromium, palladium, titanium, molybdenum, indium, gold, platinum, silver, copper, zinc, brass, stainless steel, plumbous oxide, stannic oxide, Indium sesquioxide, tin-doped indium oxide) or the plate formed by graphite 1TO (indium tin oxide:, rotary drum, thin slice and pass through evaporation, the splash method, the glass through conductive processing that coating etc. is applied, cloth, the film of paper or plastics, thin slice and by seamless-band (シ mono-system レ ス ベ Le ト) and the metal rotary drum etc. that carries out the burning processing by anodizing etc.

Above-mentioned charge generation layer is the layer that at least has charge generating material, by form the layer of charge generating material on the substrate as its substrate by vacuum evaporation, splash method etc., perhaps form on the substrate as its substrate and stick with glue the layer that the resin-bonded charge generating material of agent forms, with this, can obtain this charge generation layer.As using adhesive resin to form the method for charge generation layer, can use the whole bag of tricks of known method etc., but suitable method is is usually for example dispersed or dissolved charge generating material to be obtained being coated with work liquid by suitable solvent together with adhesive resin, this painting work liquid is coated on the substrate of the substrate of stipulating, carry out drying, obtain as the wet forming body.

Can use known various material as the charge generating material in above-mentioned charge generation layer.As concrete compound, selenium alloy, the AS of the selenium simple substance, selenium-tellurium etc. of amorphousness selenium, three prismatic crystal selenium etc. arranged for example ₂se ₃deng selenium compound or containing the selenium composition, zinc oxide, the inorganic materials formed by the periodic table of elements the 12nd family and the 16th family's element of CdS-Se etc., the oxide based semi-conductor of titanium oxide etc., the silicon based material of amorphous silicon etc., τ type metal-free phthalocyanine, the metal-free phthalocyanine of χ type metal-free phthalocyanine etc., the α type copper phthalocyanine, beta-type copper phthalocyanine, the γ type copper phthalocyanine, the ε type copper phthalocyanine, the X-type copper phthalocyanine, A type titanyl phthalocyanine, the Type B titanyl phthalocyanine, C type titanyl phthalocyanine, D type titanyl phthalocyanine, E type titanyl phthalocyanine, F type titanyl phthalocyanine, G type titanyl phthalocyanine, H type titanyl phthalocyanine, K type titanyl phthalocyanine, the L-type titanyl phthalocyanine, M type titanyl phthalocyanine, the N-type titanyl phthalocyanine, Y type titanyl phthalocyanine, the oxo titanyl phthalocyanine, the titanyl phthalocyanine of the diffraction peak that the demonstration that Bragg angle 2 θ in X-ray diffractogram are 27.3 ± 0.2 degree is strong, the metal phthalocyanine of potassium phthalocyanine etc., anthocyanin dye, anthracene pigment, disazo pigment, pyrene pigment, many ring quinone pigmentss, quinacridone pigment, indigo pigment, perylene dye, pyrylium dye, Si Kualin (ス Network ェ ア リ ウ system) pigment, anthrone buttress anthrone pigment, benzoglyoxaline pigment, azo pigment, thioindigo color, quinoline pigment, pigment lake, oxazine pigment, two oxazine pigment, triphenyl methane pigment, azulene (azulenuium) dyestuff, triarylmethane dye, the xanthine dyestuff, thiazine dyes, the thiophene pyrylium dye, polyvinyl carbazole, bisbenzimidazole pigment etc.These compounds can be independent a kind or mix two or more and use as the charge generation material.In these charge generation materials, the suitable material that concrete record in Japanese patent laid-open 11-172003 communique is arranged for example.

Above-mentioned charge transport layer can stick with glue the layer that the resin-bonded charge transport material of agent forms and obtains by forming on the substrate as substrate.

As above-mentioned charge generation layer or the adhesive resin of charge transport layer, have no particular limits, can use various known.Particularly, polystyrene is arranged for example, polyvinyl chloride, polyvinyl acetate (PVA), vinyl chloride-vinyl acetate copolymer, the polyethylene acetal, Synolac, acrylic resin, polyacrylonitrile, polycarbonate, polymeric amide, butyral resin, polyester, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, polyorganosiloxane resin, polysiloxane-ol acid resin, phenol-formaldehyde Trees fat, vinylbenzene-ol acid resin, melantine, polyether resin, the benzoguanamine resin, Epocryl, polyurethane acrylate resin, the poly-N-vinyl carbazole, polyvinyl butyral acetal, polyvinyl formal, polysulfones, casein, Keratin sulfate, polyvinyl alcohol, ethyl cellulose, Nitrocellulose, carboxy methyl cellulose, vinylidene chloride based polymer latex, acrylonitrile butadiene copolymer, Vinyl toluene-styrol copolymer, soybean oil modified alkyd, the nitration polystyrene, polyvinyltoluene, polyisoprene, polythiocarbonates, polyene propyl ester (Port リ ア リ レ mono-ト), poly-haloalkene propyl ester, polyallyl ether, polyethylene acrylate, polyester acrylate etc.

These can independent a kind of use, or also can two or more mix and use.In addition, the above-mentioned copolymerization PC of the suitable use of adhesive resin in charge generation layer or charge transport layer.

Formation method as the electric charge transportation level, can use known variety of way, but suitable method is is usually dispersed or dissolved and is obtained being coated with work liquid by suitable solvent together with the copolymerization PC of charge transport material and present embodiment, using this painting work liquid be coated on regulation on the substrate of substrate, carry out drying, obtain as the wet forming body.It is 20～80～80: 20 that the charge transport material formed for charge transport layer and the blending ratio of copolymerization PC it is desirable to mass ratio, more preferably 30: 70～70: 30.

In this charge transport layer, the copolymerization PC of present embodiment can independent a kind of use, also can two or more mix and use.In the scope that does not hinder purpose of the present invention, also can and use the copolymerization PC of other adhesive resin and present embodiment again.

The thickness of the charge transport layer formed like this is generally 5～100 μ m left and right, it is desirable to 10～30 μ m.This thickness less than 5 μ m, the initial stage current potential probably can reduce, and surpasses 100 μ m, probably can cause the reduction of electrofax characteristic.

As can with the charge transport material used together with the copolymerization PC of present embodiment, can use known various compound.As such compound, suitable use carbazole compound, benzazolyl compounds, imidazolium compounds, oxazole compounds, pyrazole compound, oxadiazole compound, pyrazoline compounds, thiadiazole compound, aniline compound, hydrazone compound, aromatic amines compound, fatty amine compound,

compound, the Fluorenone compound, adiene cpd, naphtoquinone compounds, quinone bismethane compound, thiazolium compounds, triazole compounds, the imidazolone compound, imidazolidine compound, two imidazolidine compounds, the azolactone compound, benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine compounds, compound phenazine, poly--N-vinyl carbazole, the polyethylene pyrene, the polyethylene anthracene, the polyethylene acridine, poly--9-vinyl phenyl anthracene, pyrene-formaldehyde resin, the ethyl carbazole resin, perhaps at main chain or side chain, there is polymkeric substance of these structures etc.These compounds can independent a kind of use, also can two or more be used in combination.

In these charge transport materials, the especially suitable compound that Japanese patent laid-open 11-172003 communique particular instantiation is arranged for example.

In addition, in the Electrophtography photosensor of present embodiment, at least one deck of charge generation layer or charge transport layer is used the copolymerization PC of present embodiment as adhesive resin.

In the Electrophtography photosensor of present embodiment, normally used precoated layer can be set between above-mentioned conductive board and sensitive layer.As this precoated layer, can use that titanium oxide, aluminum oxide, zirconium white, metatitanic acid, zirconic acid, lanthanumization are plumbous, titanium is black, the composition of the particulate of silicon-dioxide, lead titanate, barium titanate, stannic oxide, Indium sesquioxide, silicon oxide etc., polyamide resin, phenolic resin, casein, melantine, benzoguanamine resin, urethane resin, epoxy resin, Mierocrystalline cellulose, Nitrocellulose, polyvinyl alcohol, polyvinyl butyral resin etc.Again, as the resin for this precoated layer, can use above-mentioned adhesive resin, also can use the copolymerization PC of present embodiment.These particulates or resin can independent or various mixing uses.The occasion of being used as these mixture, and with inanimate matter particulate and resin, owing to forming tunicle that smoothness is good thereby suitable.

The thickness of this precoated layer is 0.01～10 μ m, it is desirable to 0.1～7 μ m.This thickness less than 0.01 μ m, it is difficult forming equably precoated layer, again, surpasses 10 μ m, electrofax characteristic sometimes reduces.Normally used known trapping layer can be set between above-mentioned conductive base and sensitive layer again.As this trapping layer, can use the resin that belongs to one species with above-mentioned adhesive resin.Can use the polycarbonate resin of present embodiment again.The thickness of this trapping layer is 0.01～20 μ m, it is desirable to 0.1～10 μ m.This thickness less than 0.01 μ m, it is difficult forming equably trapping layer, again, surpasses 20 μ m, electrofax characteristic sometimes reduces.

Again, the Electrophtography photosensor of present embodiment can be on sensitive layer the lamination protective layer.This protective layer can be used the resin that belongs to one species with above-mentioned adhesive resin.Particularly desirably use the polycarbonate of present embodiment again.The thickness of this protective layer is 0.01～20 μ m, it is desirable to 0.1～10 μ m.And this protective layer can contain the conductive material of above-mentioned charge generation material, charge transport material, additive, metal or its oxide compound, nitride, salt, alloy, carbon black, organic conductive compound etc.

And, in order to improve the performance of this Electrophtography photosensor, can in above-mentioned charge generation layer and charge transport layer, add tackiness agent, softening agent, curing catalysts, mobility and give agent, pore control agent, spectral sensitivity sensitizing agent (sensitizing dye).For the purpose of the reduction of the reduction that prevents increase for the rest potential of Reusability, hot-line electrical potential, sensitivity, can add the additive of various chemical substances, antioxidant, tensio-active agent, anti-curl agent, flow agent etc. again.

As above-mentioned tackiness agent, polysiloxane resin for example, polyamide resin, urethane resin, vibrin, epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene, the polyisoprene resin, melantine, the benzoguanamine resin, polychlorostyrene fourth resin, polyacrylonitrile resin, ethyl cellulose resin, Nitro cellulose resin, urea resin, phenolic resin, phenoxy resin, polyvinyl butyral resin, vinyl-formal resin, the vinyl acetate resin, vinyl acetate/chloroethylene copolymer resin, polyestercarbonate resin etc.In addition, also can use heat and/or light-cured resin.Whichsoever, so long as resin electrical insulating property, can form tunicle under common state, in the scope of not damaging effect of the present invention, just has no particular limits.

As the object lesson of above-mentioned softening agent, biphenyl, chlorodiphenyl, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Diethylene Glycol phthalic ester, triphenylphosphate, diisobutyl adipate, dimethyl sebacate, Uniflex DBS, butyl laurate, phthalic acid (methyl esters) ethyl glycollate, phthalic acid dimethyl second diester, methylnaphthalene, benzo benzophenone, polypropylene, polystyrene, hydrofluoric ether etc. are arranged for example.

Object lesson as above-mentioned curing catalysts, methanesulfonic, Witco 1298 Soft Acid, dinonylnaphthalene disulfonic acid etc. are arranged for example, as mobility, give agent, モ ダ Off ロ mono-, ア Network ロ Na one Le 4F etc. are arranged for example, as the pore control agent, bitter almond oil camphor, dimethyl phthalate are arranged for example.It is desirable to, these softening agent, curing catalysts, flow give agent, the pore control agent is used below 5 quality % with respect to above-mentioned charge transport substance.

Again, while as the spectral sensitivity sensitizing agent, using sensitizing dye, the oxazine dyestuff of indigo plant, meldola blue etc., anthocyanin dye, merocyanine dyes, styryl color, pyranium salt dyestuff, sulfo-pyranium salt dyestuff etc. in the thiazine dyes of the suitable acridine dye that triphenyl methane based dye such as methyl violet, Viola crystallina, nitric acid indigo plant, victoria blue etc., tetraiodofluorescein, rhodamine B, rhodamine 3R, acridine orange, Off ラ ペ オ シ Application etc. are arranged, methylenum coeruleum, methylene green etc., Kapp.

The purpose of the fatigue during for raising sensitivity, minimizing rest potential, reduction Reusability etc., can add the electronics property held material in sensitive layer.As its object lesson, it is desirable to succinyl oxide, MALEIC ANHYDRIDE, the dibromo MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride, 3-nitrophthalic acid acid anhydride, 4-nitrophthalic acid acid anhydride, PMA, the mellic acid acid anhydride, tetracyanoethylene, four cyano benzoquinone bismethane (tetracyanoquinodimethane), o-dinitrobenzene, Meta-dinitrobenzene, 1，3，5-trinitrobenzene, the p-nitrophenyl nitrile, picryl chloride, quinone chlorimide, tetrachloroquinone, tetrabromoquinone, benzoquinones, 2,3-dichloro quinone, the dichloro dicyano is stretched benzoquinones, naphthoquinones, the connection para benzoquinone, the cycloheptadiene triketone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, the 4-nitro benzophenone, 4,4 '-the dinitrobenzene benzophenone, 4-nitrobenzal propane dinitrile, alpha-cyano-β-(to cyano-phenyl) ethyl propenoate, 9-anthryl methyl-prop dintrile, 1-cyano group-(p-nitrophenyl)-2-(rubigan) ethene, 2,7-dinitrobenzene Fluorenone, 2,4,7-trinitro-fluorenone, 2,4,5,7-tetranitro Fluorenone, 9-fluorenylidene-(dicyano methylene propane dinitrile), poly-nitro-9-fluorenylidene-(dicyano methylene propane dinitrile), picric acid, adjacent nitro M-nitro benzoic acid, to the nitro M-nitro benzoic acid, 3,5-dinitrobenzene M-nitro benzoic acid, pentafluoro benzoic acid, 5-NITROSALICYLIC ACID, 3,5-dinitrosalicylic acid, phthalic acid, the compound that the electron affinity of mellic acid etc. is large.These compounds can be added to the arbitrary layer of charge generation layer, charge transport layer, and its blending ratio, during as 100 mass parts, being 0.01～200 mass parts using charge generation material or charge transport amount of substance, it is desirable to 0.1～50 mass parts.

Again, for improved surface, can use tetrafluoroethylene resin, chlorine trifluoride ethenoid resin, tetrafluoroethylene hexafluoro acrylic resin, fluoroethylene resin, pvdf resin, bifluoride polyvinylidene chloride resin and their multipolymer, fluorine is graftomer.The blending ratio of these surface-modifying agents is 0.1～60 quality % with respect to above-mentioned adhesive resin, it is desirable to 5～40 quality %.This mixing ratio is less than 0.1 quality %, and the surface modification of surface durability, surface energy reduction etc. is insufficient, more than 60 quality %, sometimes causes the electrofax characteristic to descend.

As the antioxidant that adds charge generation layer, charge transport layer to, it is desirable to sterically hindered phenol and be antioxidant, aromatic amine and be antioxidant, bulky amine and be antioxidant, sulfide-based antioxidant, organic phosphoric acid and be the material that free radical complementarity, free radical chain are forbidden effect and/or peroxide breakdown effect that has of antioxidant etc.The blending ratio of these antioxidants is 0.01～10 quality % with respect to above-mentioned charge transport material, it is desirable to 0.1～2 quality %.

As the object lesson of such antioxidant, the compound of the chemical formula ([changing 94]～[changing 101]) of the suitable specification sheets record that Japanese patent laid-open 11-172003 communique is arranged.

These antioxidants can be used separately a kind, also can two or more mix use, and these,, except being added in above-mentioned sensitive layer, can also be added in sealer, precoated layer or trapping layer.

By adding such antioxidant, can supplement free radical, prevent the deterioration of charge generation layer or charge transport layer.

The object lesson of the above-mentioned solvent used when forming above-mentioned charge generation layer, charge transport layer, there can be exemplified the ether, dimethyl formamide, methyl-sulphoxide, diethylformamide of the halohydrocarbon, tetrahydrofuran (THF), diox etc. of the ester, tetracol phenixin, carbon tetrabromide, chloroform, methylene dichloride, tetrachloroethane etc. of the alcohol, vinyl acetic monomer, ethyl cellosolve etc. of the ketone, methyl alcohol, ethanol, Virahol etc. of aromatic series series solvent such as benzene,toluene,xylene, chlorobenzene etc., acetone, ethyl methyl ketone, pimelinketone etc. etc.These solvents can be used separately a kind, or can use two or more as mixed solvent.

The sensitive layer of mono-layer electronic photographic photoreceptor is by being used above-mentioned charge generation material, charge transport material, additive, and the adhesive resin (copolymerization PC) of application present embodiment, can easily form.It is desirable to add above-mentioned all (ホ mono-Le) transporting material and/or electron transport materials as the charge transport material again.As the electron transport material, it is desirable to apply the illustrative material of Japanese Patent Laid-Open 2005-139339 communique.

The coating of each layer can be used the various apparatus for coating of known grade, can use particularly such as applicator, spraying machine, bar varnishing machine, section coater, glue spreader, dipping coater, scraper etc. to carry out.

The thickness of the sensitive layer in Electrophtography photosensor is 5～100 μ m, it is desirable to 8～50 μ m, less than 5 μ m, and the easy step-down of initial stage current potential, surpass 100 μ m, and electrofax characteristic sometimes descends.The charge generation material that the manufacture of Electrophtography photosensor is used: the ratio of adhesive resin, take mass ratio as 1: 99～30: 70, it is desirable to 3: 97～15: 85.Again, charge transport material: it is 10: 90～80: 20 that the ratio of adhesive resin be take the words of mass ratio, it is desirable to 30: 70～70: 30.

The Electrophtography photosensor of the present embodiment obtained like this is due to the copolymerization PC that uses present embodiment, so be coated with work liquid can not whiten (gelation) while making sensitive layer.Again, the molding (adhesive resin) that photoreceptor forms due to the copolymerization PC had by present embodiment, so have, weather resistance is good, the little so good static characteristic of ascensional range of rest potential during Reusability simultaneously, maintain for a long time good electrofax characteristic, be suitable for duplicating machine (monochrome, polychrome, full color; Simulation, numeral), printer (laser, LED, liquid crystal shutter), facsimile recorder, platemaking machine and the various electrofax field of machine etc. with these a plurality of functions.

In addition, when using the Electrophtography photosensor of present embodiment, the charged corona discharge that can use (corona tube (corotron), has grid electrode (scorotron), contact electrification (charged roller, band brush) etc.Exposure can adopt any of the inner Exposure mode of halogen lamp, luminescent lamp, laser (semi-conductor, He-Ne), LED, photoreceptor.Development can be used dry process development mode or the wet developing mode of cascade (cascade) development, binary magnetic brush development, a composition insulation toner development, a composition conduction toner development etc.For duplicating Xxerography or the pressure duplicating method that can use corona duplicating, roller duplicating, belt duplicating etc., the duplicating method of adhering.Can use heat roller fixation, radiation flash fusing, open photographic fixing, pressure photographic fixing etc. for photographic fixing.Again, for the clean electric member that can use brush clearer, magnetoelectricity brush clearer, static brush clearer, magnetic roller clearer, blade cleaner and omission clearer etc. that removes.As the resin of toner (ト Na one) use, can apply the polymkeric substance of phenylethylene resin series, Styrene And Chloroalkyl Acrylates based copolymerized resin, polyester, epoxy resin, cyclic hydrocarbon etc. again.The shape of toner can be spherical, can be also unsetting, also can use and be controlled to definite shape (ellipsoid of revolution shape, potato-like etc.).Toner can be crush type, be suspended polymerized toner, any in emulsion polymerization toner, chemical granulation toner or ester elongation toner.

The<the 2 embodiment >

Below, the 2nd embodiment of the present invention is described in detail.

In the present embodiment, omit the explanation repeated with above-mentioned the 1st embodiment again.

[structure of copolymerization PC]

The copolymerization PC of present embodiment contains the monomeric unit that 0.1～50 % by mole of monomeric unit that above-mentioned formula (1) means and above-mentioned formula (2) mean and the Copolycarbonate formed, and in a part, exists the content of biphenol compound of 3 phenol hydroxyls below 200 quality ppb.

In such present embodiment, because the content of the trihydroxy-biphenyl base class in copolymerization PC is below 200 quality ppb, can be when melt-shaping copolymerization PC, painted few, improve significantly the tone of molding, be suitable for optical material.Again, the content of this trihydroxy-biphenyl base class below 200 quality ppb, when copolymerization PC is made to the molding that Electrophtography photosensor uses, the rising of the rest potential in the time of can suppressing the Reusability Electrophtography photosensor.

More preferably the content of this trihydroxy-biphenyl base class, below 150 quality ppb, more preferably, below 100 quality ppb, it would be desirable below 50 quality ppb.

[manufacture method of copolymerization PC]

The copolymerization PC of present embodiment is the same with above-mentioned the 1st embodiment, and the monomer by using above-mentioned formula (3) and the monomer of above-mentioned formula (4) carry out the polycondensation of interfacial polycondensation etc., can easily obtain.

Here, in the present embodiment, residual concentration as trihydroxy-biphenyl base class (trisphenol) contained in the copolymerization PC by generating is controlled at the following method of 200 quality ppb, (1) reaction equivalent optimizing while making polymerization is arranged for example, reduce the method for monomer residual content, (2) in the matting after polymerization, make the cleaning condition optimizing in alkali aqueous solution, remove the method for residual unreacted monomer, (3) optimum solvation unreacted monomer in the crystallization operation, but and by the method for the solvent treatment copolymerization PC of crystallization, (4) (arrive the alkali matting in the way of manufacturing process, the moment before crystallization work operation), confirm residual unreacted monomer amount, according to the unreacted monomer amount, carry out monomer and remove operation (in the alkali matting, in the crystallization operation) method etc.

In the present embodiment, after copolymerization PC sheet, because unreacted monomer or low molecular weight impurities enter polymer solids inside, so, even the liquid of water etc. is cleaned, also only remove the thing that is attached to the sheet surface.On the other hand, in the cleaning of polymers soln, can reduce impurity as residual monomer of the solvable composition of alkali etc. by counterextraction.

In addition, in the matting after above-mentioned (2) polymerization, can say equally with above-mentioned the 1st embodiment, omission is described.

The copolymerization PC obtained like this is that the repeating unit meaned by the repeating unit of above-mentioned formula (1) expression and above-mentioned formula (2) forms, the multipolymer of content (residual content) below 200 quality ppb of trihydroxy-biphenyl base class.

Again, can be, in not hindering the scope that reaches purpose of the present invention, in this copolymerization PC, contain: there is the polycarbonate unit of the structural unit outside above-mentioned formula (1) and above-mentioned formula (2) or there is the unit of polyester, urethane, polyethers, polysiloxane structure.

Again, in the biphenyl phenols in the binary phenol used as monomer, usually contain micro-impurity, wherein, by the content of trihydroxy-biphenyl base class is managed below 300 quality ppm, it is easy that the YI of copolymerization PC is controlled at below 3.As a result, the spheroid or the molding that by this copolymerization PC (flaky powder), are shaped almost do not have painted.When the content of trihydroxy-biphenyl base class surpasses 300 quality ppm, can reduce impurity by the cleaning condition optimizing that makes polymkeric substance.

Again, the content of the trihydroxy-biphenyl class that static characteristic is worsened is few, and this raw material to the molding as for Electrophtography photosensor is also useful.The content of the trihydroxy-biphenyl base class in the biphenyl phenols it is desirable to below 150 quality ppm, more preferably, below 20 quality ppm, it would be desirable below 10 quality ppm.

Again, the YI of copolymerization PC is controlled at below 3, make the 3-tertiary butyl-4,4 in the biphenyl phenols '-content of dihydroxybiphenyl it is desirable to below 300 quality ppm below 370 quality ppm, more preferably also effective below 30 quality ppm.

[structure of Electrophtography photosensor]

At the Electrophtography photosensor of present embodiment, except the copolymerization PC using above-mentioned, the adhesive resin in sensitive layer utilizes, other structure is the same with above-mentioned the 1st embodiment.

The<the 3 embodiment >

Below, the 3rd embodiment of the present invention is described in detail.

In the present embodiment, omit the explanation repeated with the above-mentioned the 1st and the 2nd embodiment again.

[formation of copolymerization PC]

The copolymerization PC of present embodiment contains the monomeric unit that 0.1～50 % by mole of monomeric unit that following formula (1) means and following formula (2) mean and the Copolycarbonate formed, and the YI of this Copolycarbonate (according to JlS K 7105, measuring flaky powders) is below 3.

The YI of the copolymerization PC of such present embodiment is below 3, so can be described as water white.As the manufacturing process of copolymerization PC, can be the wet forming that is dissolved in the type be coated with in the suitable organic solvent of usually knowing again.Again, during wet forming molding through the time variable color (in time passage and variable color) suppressed, outcome quality worsens few.Especially, the YI of copolymerization PC is below 3, and its effect is remarkable.We think that this is relatively less because make copolymerization PC change to yellow material under the effect of light, heat, oxidizing substance, moisture etc.

Again, as the YI of the flaky powder of shaping raw material, below 3, this also means to static characteristic and brings the impurity of bad impact few, while being applied to Electrophtography photosensor, and the rising of the rest potential while suppressing Reusability.

Here, 0.1 % by mole of the ratio deficiency of the monomeric unit that above-mentioned formula (1) means, be coated with work liquid flooding white (gelation), or prevent from the crystallization of charge transport layer or reach improving the anti-brush life-span and becoming difficult.On the other hand, the ratio of this monomeric unit surpasses 50 % by mole, because crystallization easily occurs a part of copolymerization PC (xenol skeleton), transparency deterioration, so be not suitable for sticking with glue the agent resin as Electrophtography photosensor.The desirable scope of the monomeric unit shown in above-mentioned formula (1) is 1～40 % by mole, more preferably 5～30 % by mole.

[manufacture method of copolymerization PC]

The copolymerization PC of present embodiment is the same with above-mentioned the 1st embodiment, and the monomer by using above-mentioned formula (3) and the monomer of above-mentioned formula (4) carry out the polycondensation of interfacial polycondensation etc., can easily obtain.

The copolymerization PC obtained in present embodiment is the multipolymer by the repeating unit formation of the repeating unit of above-mentioned formula (1) expression and above-mentioned formula (2) expression.

Again, can be, in not hindering the scope that reaches purpose of the present invention, in this copolymerization PC, contain: there is the polycarbonate unit of the structural unit outside above-mentioned formula (1) and above-mentioned formula (2) or there is the unit of polyester, urethane, polyethers, polysiloxane structure.

Again, for the xenol in the binary phenol used as monomer, content by the impurity trihydroxy-biphenyl class by contained in its composition (having the biphenol compound of 3 phenol hydroxyls in a part) is managed below 300 quality ppm, easily the YI of copolymerization PC is controlled at below 3.As a result, the spheroid or the molding that by this copolymerization PC (flaky powder), are shaped almost do not have painted.

Again, the content of the trihydroxy-biphenyl class that static characteristic is worsened is few, and this raw material to the molding as for Electrophtography photosensor is also useful.The content of the trihydroxy-biphenyl class in the xenol monomer it is desirable to below 150 quality ppm, more preferably, below 20 quality ppm, it would be desirable below 10 quality ppm.

Again, the YI of copolymerization PC is controlled at below 3, make the 3-tertiary butyl-4,4 in the biphenyl phenols '-content of dihydroxybiphenyl it is desirable to below 300 quality ppm below 370 quality ppm, more preferably also effective below 30 quality ppm.

[structure of Electrophtography photosensor]

The Electrophtography photosensor of present embodiment is except the copolymerization PC using above-mentioned the utilization of adhesive resin in sensitive layer, and other structure is the same with the above-mentioned the 1st and the 2nd embodiment.

The<the 4 embodiment >

Below, the 4th embodiment of the present invention is described in detail.

In the present embodiment, omit the explanation repeated with above-mentioned the 1st to the 3rd embodiment again.

[formation of copolymerization PC]

The formation of the copolymerization PC of this example is the same with above-mentioned the 1st embodiment, and omission is described.

[manufacture method of copolymerization PC]

The concrete available various modes of the manufacturing process of copolymerization PC in present embodiment are implemented, for example, can adopt following method, make binary phenol (the biphenol class of the biphenyl phenols of above-mentioned formula (3) and/or above-mentioned formula (4)) and carbonyl chloride reaction, manufacture polycarbonate oligomer, then under the existence of the mixed solution of the alkali aqueous solution of above-mentioned solvent and sour linking agent, make this polycarbonate oligomer and above-mentioned binary phenol reactant.Can adopt the method that above-mentioned binary phenol and carbonyl chloride are reacted in the mixed solution of above-mentioned solvent and alkali aqueous solution again.Usually, the former method of manufacturing in advance polycarbonate oligomer is efficient, so desirable.

For manufacturing polycarbonate oligomer, at first, at alkali aqueous solution, dissolve binary phenol, the alkali aqueous solution of preparation binary phenol.Then, import carbonyl chloride in the mixed solution of the organic solvent of this alkali aqueous solution and methylene dichloride etc. and make it reaction, the polycarbonate oligomer of synthetic binary phenol.Then, reaction soln is separated into to water and organic phase, obtains the organic phase that contains polycarbonate oligomer.Now, the alkali concn of alkali aqueous solution it is desirable to the scope of 0.1～5 regulation, and again, the volumetric ratio of organic phase and water is 10: 1～1: 10, it is desirable to 5: 1～scope of 1: 5.

Temperature of reaction is generally 0～70 ℃ under cooling, it is desirable to 5～65 ℃, 15 minutes～4 hours reaction times, it is desirable to 30 minutes～and about 3 hours.The molecular-weight average of the polycarbonate oligomer obtained like this is below 2000, and the polymerization degree, usually below 20, it is desirable at 2～10 polymers.

In the organic phase that contains polycarbonate oligomer obtained like this, add above-mentioned binary phenol to be reacted.Temperature of reaction it is desirable to 0～20 ℃, especially it is desirable to 5～15 ℃.Especially by temperature of reaction being controlled at below 20 ℃, can suppress the copolymerization PC of generation painted (rising of YI).

Reaction pressure can be any in decompression, normal pressure, pressurization, usually can under the self-pressure degree of normal pressure or reaction system, suitably carry out.Reaction times by temperature of reaction left and right, be generally 0.5 minute～10 hours, it is desirable to 1 minute～about 2 hours.

Again, polycondensation it is desirable to carry out under the inert gas atmosphere of nitrogen or argon gas etc.By oxygen partial pressure being controlled at below 5065Pa (0.05 air pressure), can suppress resulting copolymerization PC painted (rising of YI).More preferably this oxygen partial pressure is below 1013Pa (0.01 air pressure).

In the present embodiment, 1 mole of the biphenyl phenols meaned with respect to above-mentioned formula (3), add antioxidant in reaction system to the ratio of 0.0001～1 molar equivalent.Here, the meaning of molar equivalent is while having the structural unit of a plurality of performance antioxygen functions in a part, and the structural unit of bringing into play each function is respectively 1 mole.For example, in a part, 1 mole of 2 functional group's type antioxidant of the type of 2 steric hindrance phenol of bonding is 2 molar equivalents.As the addition of antioxidant, more preferably 0.0002～0.5 molar equivalent, more preferably 0.001～0.1 molar equivalent, it would be desirable 0.002～0.05 molar equivalent.

As such antioxidant, the antioxidant with reductibility is arranged, such as S-WAT or hydrosulphite etc., especially it is desirable to hydrosulphite (sodium bisulfite, Potassium hydrogen sulfite).By adding hydrosulphite, can suppress resulting copolymerization PC painted (rising of YI).Again, can prevent the oxidation of monomer, or reduce oxidized monomer and recover reactive, contribute to the efficient activity of polymerization.

While carrying out this reaction, wish that binary phenol is added as organic solvent solution and/or alkali aqueous solution.For its order of addition, have no particular limits.In addition, catalyzer, end terminator and branching agent etc. can be in above-mentioned manufacturing processs, as required, when manufacturing polycarbonate oligomer, polymer thereafter quantize reaction the time any one reaction in or all add use in both.

[structure of Electrophtography photosensor]

The structure of the Electrophtography photosensor of this example is the same with above-mentioned the 1st embodiment, and omission is described.

Embodiment

Below, by embodiment and comparative example, in further detail the 1st to the 4th embodiment of the present invention is described, but the present invention is not limited to these embodiment, in the scope that does not break away from thought of the present invention, can carry out various distortion and application.

Particularly, use biphenol compound monomer and the diphenol compound monomer of regulation, carry out polycondensation, manufacture copolymerization PC, and use this copolymerization PC to manufacture Electrophtography photosensor, carry out afterwards various evaluations.

The embodiment of the<the 1 embodiment >

[embodiment 1-1]

(manufacture of copolymerization PC)

By 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-are dissolved in the aqueous sodium hydroxide solution 550ml of 6 quality % concentration, to dissolve resulting solution and methylene dichloride 250ml mixes, be blown into carbonyl chloride gas while stirring in the cooling lower ratio toward dividing with 950ml/ in liquid, blow 15 minutes.Then, this reaction solution of standing separation, the polymerization degree of organic layer is 2～4, obtains the dichloromethane solution that molecular end has the oligopolymer of chloroformic acid ester group.Add methylene dichloride in resulting oligomer solution, making full dose is 450ml.

Then, by 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 349 quality ppm) 24g is dissolved in the aqueous sodium hydroxide solution 150ml of 8 quality % concentration, toward wherein adding molecular weight regulator p-tert-butylphenol 3.0g (the xenol aqueous solution).In the present embodiment, 4,4 '-dihydroxybiphenyl uses unpurified commercially available product.Again, 4,4 '-foreign matter content in dihydroxybiphenyl uses liquid chromatography to be measured.

In above-mentioned oligomer solution, add the xenol aqueous solution to be mixed, this mixed solution of high degree of agitation on one side, as catalyzer add the triethylamine aqueous solution 2ml of 7 quality % concentration on one side, keeping under the state of 28 ℃, limit continues to stir, and interfacial polycondensation reaction 1.5 hours is carried out on limit.After reaction finishes, with 1 liter of diluting reaction resultant of methylene dichloride, then with 1.5 premium on currency, clean 1 time, clean 1 time with 0.05 regulation aqueous sodium hydroxide solution, confirm now not exist an alkali metal salt of starting monomer in water layer.This is confirmed to be according to making water layer is below pH3, to have or not precipitate to carry out.Then, with 1 liter of 0.01 regulation hydrochloric acid, clean 1 time in order, 1 liter of cleaning of water 2 times, obtain polymers soln.

Then, prepare to be equipped with in addition the band baffle plate container of agitating vane, drop into inward 2 liters of methyl alcohol.The agitating vane methyl alcohol in stirred vessel fully for one side, one side splashes into 1 liter of above-mentioned polymers soln at leisure with the speed that forms particle, by redeposition, carry out the sheet processing.After splashing into end, one side keeps enough stirring velocitys, after one side stirs 10 minutes, then 2 liters of methyl alcohol of additional input, then continue to stir 5 minutes.Carry out filtration drying to resulting, as the copolymerization PC (PC-1-1) that estimates use.

(evaluation of copolymerization PC)

PC-1-1, under this state (flaky powder), is carried out to YI mensuration (according to JIS K 7150).

Then, PC-1-1 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.In addition, utilize ¹after H-NMR is analyzed the chemical structure of PC-1-1, be confirmed to be the copolymerization PC that following chemical formula (5) means.

Residual 4,4 to the inside of resulting PC-1-1 '-concentration of dihydroxybiphenyl (4,4 '-xenol) is determined as follows.

PC-1-1 (2.5g) is put into to the Erlenmeyer flask with stopper, dissolve with methylene dichloride 25ml.Then, (チ バ ス ペ シ ヤ リ テ ィ ケ ミ カ Le ズ manufactures イ Le ガ ノ Star Network ス 1010 to add antioxidant, 30mg) afterwards, magnetic stirring apparatus violent stirring solution for one side, one side is slowly added 100ml acetone, 100ml hexane successively, each about 1 minute, one side was separated out resinous principle.After attracting to filter precipitate, filtrate is moved to the concentrated container of using, at next top blast of state that keeps the water-bath of 45 ℃, enter oxide gas, one side makes solvent evaporates and concentrates.After resulting enriched material is dissolved in to tetrahydrofuran (THF) 10ml, utilize HPLC (Highperformance liquid chromatography high efficiency liquid chromatography) to measure 4 with the Absolute Calibration curve method, 4 '-(Agilent company manufactures 100 series for the amount of xenol, post (chromatogram): TOSOH company manufactures, ODS system, internal diameter 4.6mm, length 25cm).Here, the mixed stocker of distilled water (adding the formic acid of 0.1 capacity %) and acetonitrile is used in movement during mensuration mutually, (acetonitrile concentration: 30～100 capacity %-20 divide to use gradient method (グ ラ ジ ェ Application ト モ mono-De), flow: 1.0ml/ divides), by UV-detector (280nm), measured.

In addition, for add 4 of normality in resin, 4 '-system that xenol (sterling) obtains, obtain in addition the rate of recovery (%), carry out revisal, for " 4,4 of HPLC mensuration '-xenol concentration (quality ppm)/(rate of recovery (%)/100) ", obtain residual 4,4 in PC-1-1 '-xenol concentration (quality ppm).

Again, utilize the minor axis forcing machine of 50mm φ, 280 ℃ of cylinder temperature, under revolution speed of screw 100rpm, the sheet of PC-1-1 is melt extruded, carry out granulating.After under 120 ℃, this particle being carried out to the drying treatment of 5 hours, use the metal pattern (S55C minute surface #1000) of 20 * 50 * 3mm, carry out injection molding forming, make the test film (20 * 50 * 3mm) that physical property measurement is used.This test film (injection molding forming product) is carried out to the mensuration (all according to JIS K7105) of YI (according to JIS K 7105) and total light transmittance.These evaluation results are judged with following benchmark.

The YI:2 of injection molding forming product is following is A (very good), below 4, is B (good), and surpassing 4 is C (bad).

Total light transmittance: more than 89%, being B (good), is C (bad) less than 89%.

(manufacture of Electrophtography photosensor)

As the conductive base polyethylene terephthalate resin film of aluminum metal that used evaporation, lamination charge generation layer and electric charge transportation level successively on its surface, form layers die mould sensitive layer, manufacture Electrophtography photosensor.Particularly, form as follows charge generation layer and electric charge transportation level.

As the charge generation material, use oxo titanium phthalocyanines 0.5 mass parts, use butyral resin 0.5 mass parts as adhesive resin.These are joined in methylene chloride 19 mass parts, disperse with ball mill, by the bar varnishing machine, this dispersion liquid is coated on to above-mentioned conductive base film surface, carry out drying, thereby form the approximately charge generation layer of 0.5 μ m of thickness.

Then, as charge transport substance, the sheet 0.5g of compound (CTM-1) 0.5g shown in following formula (6) and PC-1-1 is dispersed in the tetrahydrofuran (THF) of 10ml, preparation is coated with work liquid.By applicator, this painting work liquid is coated on above-mentioned charge generation layer and carries out drying, form the approximately electric charge transportation level of 20 μ m of thickness.

(evaluation of Electrophtography photosensor)

To resulting Electrophtography photosensor, use electrostatic charging testing apparatus EPA-8100 (Kawaguchi's motor is made manufacturing) to estimate the electrofax characteristic.Particularly, with the corona discharge of carry out-6kV of static schema, measure initial stage surface potential (V _o), rest potential (the initial stage rest potential V of rayed (10Lux) after 5 seconds _r), partly absorb exposure (initial stage sensitivity, E _1/2).Again, at the commercially available printer (capital セ ラ manufactures FS-600) of transformation, can measure on the basis of surface potential of photoreceptor, above-mentioned photoreceptor is arranged on rotary drum, carries out the evaluation of charged characteristic.Particularly, under hot and humid (35 ℃ 85%RH), under the condition of obstructed toner and paper, are carried out 24 hours (rest potential (△ V that rise repeatedly of the charged characteristic before and after running repeatedly _r)) evaluation.

Above-mentioned projects are judged according to following metewand.

Initial stage surface potential (V _o) :-700V is following is B (good), surpasses this value for C (bad).

Initial stage rest potential (V _r) :-40V above (value of absolute value below 40V) is B (good), lower than this value (absolute value surpasses the value of 40V), is C (bad).

Initial stage sensitivity (E _1/2): 0.85Luxsec is following is B (good), surpasses this value for C (bad).

Repeat rest potential rising (Δ V _r): due to the ascensional range of the absolute value of the rest potential repeatedly caused, at 40V, take interior is B (good), and surpassing this value is C (bad).

[embodiment 1-2]

In the manufacture of the copolymerization PC of embodiment 1-1, add 4 in being dissolved in acetone in the polymers soln finished in washing, 4 '-dihydroxybiphenyl (manufacture by Honshu chemistry system, trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 49 quality ppm), calculate above-mentioned 4,4 '-amount of dihydroxybiphenyl, its amount is 90 quality ppm with respect to resin solid composition total amount, (obtain by experiment to the stripping quantity of solvent with to the ratio of the residual quantity of solid composition, determine addition).

Except above-mentioned, other manufacture copolymerization PC (PC-1-2) the samely with embodiment 1-1.Then, PC-1-2 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹h-NMR is confirmed to be the structure the same with PC-1-1 after the chemical structure of PC-1-2 is analyzed.

For PC-1-2 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[embodiment 1-3]

In the manufacture of the copolymerization PC of embodiment 1-1, except the number of times cleaned with aqueous sodium hydroxide solution by resultant of reaction changes to 3 times, other and embodiment 1-1 similarly manufacture copolymerization PC (PC-1-3).Then, PC-1-3 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹h-NMR is confirmed to be the structure structure same with PC-1-1 after the chemical structure of PC-1-3 is analyzed.

For PC-1-3 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[embodiment 1-4]

In the manufacture of the copolymerization PC of embodiment 1-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1,1-bis(4-hydroxyphenyl) cyclohexane 87g, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-1-4) the samely with embodiment 1-1.PC-1-4 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-1-4, be confirmed to be the copolymerization PC that following (7) mean.For PC-1-4 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[embodiment 1-5]

In the manufacture of the copolymerization PC of embodiment 1-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1, two (4-hydroxy phenyl) the ethane 69g of 1-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-1-5) the samely with embodiment 1-1.PC-1-5 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-1-5, be confirmed to be the copolymerization PC that following (8) mean.For PC-1-5 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[embodiment 1-6]

In the manufacture of the copolymerization PC of embodiment 1-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (4-hydroxy phenyl) the butane 79g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-1-6) the samely with embodiment 1-1.PC-1-6 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-1-6, be confirmed to be the copolymerization PC that following (9) mean.For PC-1-6 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[embodiment 1-7]

In the manufacture of the copolymerization PC of embodiment 1-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (3-methyl-4-hydroxy phenyl) the propane 83g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-1-7) the samely with embodiment 1-1.PC-1-7 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-1-7, be confirmed to be the copolymerization PC that following (10) mean.For PC-1-7 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[comparative example 1-1]

In the manufacture of the copolymerization PC of embodiment 1-1, the order that 1 liter, 1 liter of the purging method of the polymers soln with the methylene dichloride dilution after polycondensation is finished changes to 1.5 liters, water 2 time, 0.01 regulation hydrochloric acid 1 time, water are 2 times, other manufacture copolymerization PC (PC-1-8) the samely with embodiment 1-1.PC-1-8 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-1-8, confirm that its structure is identical with PC-1-1.

For PC-1-8 and by this copolymerization PC the same with embodiment 1-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 1-1.

[evaluation result]

Table 1 and table 2 mean the evaluation result of embodiment 1-1～1-7 and comparative example 1-1.

[table 1]

[table 2]

The embodiment of the<the 2 embodiment >

Then, by embodiment and comparative example, the 2nd embodiment of the present invention is described in detail.

[embodiment 2-1]

(manufacture of copolymerization PC)

By 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-are dissolved in the aqueous sodium hydroxide solution 550ml of 6 quality % concentration, to dissolve resulting solution and methylene dichloride 250ml mixes, be blown into carbonyl chloride gas while stirring in the cooling lower ratio toward dividing with 950ml/ in liquid, blow 15 minutes.Then, this reaction solution of standing separation, the polymerization degree of organic layer is 2～4, obtains the dichloromethane solution that molecular end has the oligopolymer of chloroformic acid ester group.Add methylene dichloride in resulting oligomer solution, making full dose is 450ml.

Then, by 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 49 quality ppm) 24g is dissolved in the aqueous sodium hydroxide solution 150ml of 8 quality % concentration, toward wherein adding molecular weight regulator p-tert-butylphenol 3.0g (the xenol aqueous solution).

In the present embodiment, 4,4 '-dihydroxybiphenyl uses unpurified commercially available product.Again, 4,4 '-foreign matter content in dihydroxybiphenyl uses liquid chromatography to be measured.

Add the xenol aqueous solution in above-mentioned oligomer solution, mixed, on one side this mixed solution of high degree of agitation, add the triethylamine aqueous solution 2ml of 7 quality % concentration on one side as catalyzer, under the state of 28 ℃ of maintenances, limit continues to stir, and interfacial polycondensation reaction 1.5 hours is carried out on limit.After reaction finishes, with 1 liter of diluting reaction resultant of methylene dichloride, then by the order of 1 liter, 1 liter of 1 liter, 1.5 premium on currency 1 time, 0.05 regulation aqueous sodium hydroxide solution 2 times, 0.01 regulation hydrochloric acid 1 time, water 2 times, cleaned, obtained polymers soln.

Then, prepare to be equipped with in addition the band baffle plate container of agitating vane, drop into inward 2 liters of methyl alcohol.The agitating vane methyl alcohol in stirred vessel fully for one side, one side splashes into 1 liter of above-mentioned polymers soln at leisure with the speed that forms particle, by redeposition, carry out the sheet processing.After splashing into end, one side keeps enough stirring velocitys, after one side stirs 10 minutes, then 2 liters of methyl alcohol of additional input, then continue to stir 5 minutes.Carry out filtration drying to resulting, as the copolymerization PC (PC-2-1) that estimates use.

(evaluation of copolymerization PC)

PC-2-1, under this state (flaky powder), is carried out to YI mensuration (according to JIS K7105).

Then, PC-2-1 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.In addition, utilize ¹after H-NMR is analyzed the chemical structure of PC-2-1, be confirmed to be the copolymerization PC that following chemical formula (5) means.

Residual 3,4,4 to the inside of resulting PC-2-1 '-concentration of trihydroxy-biphenyl is determined as follows.

PC-2-1 (5.0g) is put into to the Erlenmeyer flask with stopper, dissolve with methylene dichloride 50ml.Then, (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ manufactures イ Le ガ ノ ッ Network ス 1010 to add antioxidant, 60mg) afterwards, magnetic stirring apparatus violent stirring solution for one side, one side is slowly added 200ml acetone, 200ml hexane successively, each about 2 minutes, one side was separated out resinous principle.After attracting to filter precipitate, filtrate is moved to the concentrated container of using, enter oxide gas at next top blast of state that keeps the water-bath of 45 ℃ and simultaneously make solvent evaporates and concentrate.After resulting enriched material is dissolved in to tetrahydrofuran (THF) 5ml, utilize HPLC (High performanceliquid chromatography high efficiency liquid chromatography) to measure 3 with the Absolute Calibration curve method, 4,4 '-(Agilent company manufactures 100 series for the amount of trihydroxy-biphenyl, post (chromatogram): TOSOH company manufactures, ODS system, internal diameter 4.6mm, length 25cm).Here, the mixed stocker of distilled water (adding the formic acid of 0.1 capacity %) and acetonitrile is used in movement during mensuration mutually, use grangentmode (グ ラ Application ヅ ェ Application ト モ mono-De) (acetonitrile concentration: 32 capacity % (0～14 minute)～100 capacity % (20～40 minutes), flow: 1.0ml/ divides), by UV-detector (260nm), measured.

In addition, for in resin, add 3,4,4 of normality '-system that trihydroxy-biphenyl (sterling) obtains, obtain in addition the rate of recovery (%), carry out revisal, for " 3,4 of HPLC mensuration; 4 '-trihydroxy-biphenyl concentration (quality ppb)/(rate of recovery (%)/100) ", obtain residual 3,4,4 in PC-2-1 '-concentration (quality ppb) of trihydroxy-biphenyl.

Again, utilize the minor axis forcing machine of 50mm φ, 280 ℃ of cylinder temperature, under revolution speed of screw 100rpm, the sheet of PC-2-1 is melt extruded, carry out granulating.After under 120 ℃, this particle being carried out to the drying treatment of 5 hours, use the metal pattern (S55C minute surface #1000) of 20 * 50 * 3mm, carry out injection molding forming, make the test film (20 * 50 * 3mm) that physical property measurement is used.This test film (injection molding forming product) is carried out to the mensuration (all according to JIS K7105) of YI (according to JIS K 7105) and total light transmittance.These evaluation results are judged with following benchmark.

The YI:2 of injection molding forming product is following is A (very good), below 4, is B (good), and surpassing 4 is C (bad).

Total light transmittance: more than 89%, being B (good), is C (bad) less than 89%.

(manufacture of Electrophtography photosensor)

The embodiment 1-1 of the manufacture of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

(evaluation of Electrophtography photosensor)

The embodiment 1-1 of the evaluation of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

[embodiment 2-2]

In the manufacture of the copolymerization PC of embodiment 2-1, interpolation 3,4,4 in being dissolved in acetone in the polymers soln finished in washing '-trihydroxy-biphenyl, above-mentioned 3,4,4 '-trihydroxy-biphenyl is with respect to resin solid composition total amount, and its amount is 150 quality ppb.Particularly, measure to distribute the addition of complex points and obtain 3,4 in resin, 4 '-trihydroxy-biphenyl residual quantity, select 150 quality ppb, as the evaluation sample.

Except above-mentioned, other manufacture copolymerization PC (PC-2-2) the samely with embodiment 2-1.PC-2-2 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-2, confirm that its structure is identical with PC-2-1.

For PC-2-2 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[embodiment 2-3]

In the manufacture of the copolymerization PC of embodiment 2-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1,1-bis(4-hydroxyphenyl) cyclohexane 87g, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-2-3) the samely with embodiment 2-1.PC-2-3 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-3, be confirmed to be the copolymerization PC that following (7) mean.For PC-2-3 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[embodiment 2-4]

In the manufacture of the copolymerization PC of embodiment 2-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1, two (4-hydroxy phenyl) the ethane 69g of 1-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-2-4) the samely with embodiment 2-1.PC-2-4 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-4, be confirmed to be the copolymerization PC that following (8) mean.For PC-2-4 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[embodiment 2-5]

In the manufacture of the copolymerization PC of embodiment 2-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (4-hydroxy phenyl) the butane 79g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-2-5) the samely with embodiment 2-1.PC-2-5 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-5, be confirmed to be the copolymerization PC that following (9) mean.For PC-2-5 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[embodiment 2-6]

In the manufacture of the copolymerization PC of embodiment 2-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (3-methyl-4-hydroxy phenyl) the propane 83g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-2-6) the samely with embodiment 2-1.PC-2-6 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-6, be confirmed to be the copolymerization PC that following (10) mean.For PC-2-6 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[embodiment 2-7]

In the manufacture of the copolymerization PC of embodiment 2-1, except the number of times cleaned with aqueous sodium hydroxide solution by resultant of reaction changes to 3 times, other and embodiment 2-1 similarly manufacture copolymerization PC (PC-2-7).PC-2-7 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-7, confirm that its structure is identical with PC-2-1.

For PC-2-7 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[comparative example 2-1]

In the manufacture of the copolymerization PC of embodiment 2-1, the order that 1 liter, 1 liter of the purging method of the polymers soln with the methylene dichloride dilution after polycondensation is finished changes to 1.5 liters, water 2 time, 0.01 regulation hydrochloric acid 1 time, water are 2 times, other manufacture copolymerization PC (PC-2-8) the samely with embodiment 2-1.PC-2-8 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-2-8, confirm that its structure is identical with PC-2-1.

For PC-2-8 and by this copolymerization PC the same with embodiment 2-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 2-1.

[evaluation result] table 3 and table 4 mean the evaluation result of embodiment 2-1～2-7 and comparative example 2-1.

[table 3]

[table 4]

The embodiment of the<the 3 embodiment >

Then, by embodiment and comparative example, the 3rd embodiment of the present invention is described in detail.

[embodiment 3-1]

By 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-are dissolved in the aqueous sodium hydroxide solution 550ml of 6 quality % concentration, to dissolve resulting solution and methylene dichloride 250ml mixes, be blown into carbonyl chloride gas while stirring in the cooling lower ratio toward dividing with 950ml/ in liquid, blow 15 minutes.Then, this reaction solution of standing separation, the polymerization degree of organic layer is 2～4, obtains the dichloromethane solution that molecular end has the oligopolymer of chloroformic acid ester group.Add methylene dichloride in resulting oligomer solution, making full dose is 450ml.

Then, by 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 131 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 347 quality ppm) 24g is dissolved in the aqueous sodium hydroxide solution 150ml of 8 quality % concentration (the xenol aqueous solution).

Use in the present embodiment 4,4 '-dihydroxybiphenyl is by make the raw material phenol recrystallize be made with extra care with methyl alcohol, synthesize 4 by it, 4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 276 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 370 quality ppm), it is carried out to recrystallize with methyl alcohol and obtain.

Add molecular weight regulator p-tert-butylphenol 3.0g in above-mentioned oligomer solution after, add the above-mentioned xenol aqueous solution, mixed, one side this mixed solution of high degree of agitation, add the triethylamine aqueous solution 2ml of 7 quality % concentration on one side as catalyzer, under the state of 28 ℃ of maintenances, limit continues to stir, and interfacial polycondensation reaction 1.5 hours is carried out on limit.After reaction finishes, with 1 liter of diluting reaction resultant of methylene dichloride, then by the order of 1 liter, 1 liter, 1.5 premium on currency 2 times, 0.01 regulation hydrochloric acid 1 time, water 2 times, cleaned, obtained polymers soln.

Then, prepare to be equipped with in addition the band baffle plate container of agitating vane, drop into inward 2 liters of methyl alcohol.The agitating vane methyl alcohol in stirred vessel fully for one side, one side splashes into 1 liter of above-mentioned polymers soln at leisure with the speed that forms particle, by redeposition, carry out the sheet processing.After splashing into end, one side keeps enough stirring velocitys, after one side stirs 10 minutes, then 2 liters of methyl alcohol of additional input, then continue to stir 5 minutes.Carry out filtration drying to resulting, as the copolymerization PC (PC-3-1) that estimates use.

(evaluation of copolymerization PC)

PC-3-1, under this state (flaky powder), is carried out to YI mensuration (according to JIS K 7105).

Then, PC-3-1 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.In addition, utilize ¹after H-NMR is analyzed the chemical structure of PC-3-1, be confirmed to be the copolymerization PC that following chemical formula (5) means.

Again, take THF as solvent, the sheet of PC-3-1 is carried out to the wet type casting forming, obtain the film of thickness 0.1mm.This film is carried out to the mensuration (according to JIS K 7105) of total light transmittance.In total light penetration, more than 89%, being B (good), is C (bad) less than 89%.This is to see through light quantity while using as optical component due to the film less than 89% to be declined to become a problem.

(manufacture of Electrophtography photosensor)

The embodiment 1-1 of the manufacture of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

(evaluation of Electrophtography photosensor)

The embodiment 1-1 of the evaluation of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

[embodiment 3-2]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, after use is refining with the methyl alcohol recrystallize by raw material phenol synthetic obtain 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 276 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 370 quality ppm) outside 24g, other manufacture copolymerization PC (PC-3-2) the samely with embodiment 3-1.PC-3-2 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-2, confirm that its structure is identical with PC-3-1.

For PC-3-2 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-3]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, after use is refining by raw material phenol distillation synthetic obtain 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 15 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: outside the material 24g 206 quality ppm) obtained with the methyl alcohol recrystallize again, other manufacture copolymerization PC (PC-3-3) the samely with embodiment 3-1.PC-3-3 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-3, confirm that its structure is identical with PC-3-1.

For PC-3-3 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-4]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, after use is refining with distillation by raw material phenol synthetic obtain 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 10 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 266 quality ppm) outside 24g, other manufacture copolymerization PC (PC-3-4) the samely with embodiment 3-1.PC-3-4 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-4, confirm that its structure is identical with PC-3-1.

For PC-3-4 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-5]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, use is by 4 of Honshu chemistry manufacture, 4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 8 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: outside the material 24g 23 quality ppm) obtained with the acetone recrystallize, other manufacture copolymerization PC (PC-3-5) the samely with embodiment 3-1.PC-3-5 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-5, confirm that its formation is identical with PC-3-1.

For PC-3-5 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-6]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, with above-described embodiment, 3-2 is identical, use 4,4 '-dihydroxybiphenyl, by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1,1-bis(4-hydroxyphenyl) cyclohexane 87g, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-3-6) the samely with embodiment 3-1.PC-3-6 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-6, be confirmed to be the copolymerization PC that following (7) mean.For PC-3-6 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-7]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, use 4 identical with above-described embodiment 3-2,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2,2-are changed to two (4-hydroxy phenyl) the ethane 69g of 1,1-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-3-7) the samely with embodiment 3-1.PC-3-7 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-7, be confirmed to be the copolymerization PC that following (8) mean.For PC-3-7 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-8]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, use 4 identical with above-described embodiment 3-2,4 '-dihydroxybiphenyl, by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (4-hydroxy phenyl) the butane 79g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-3-8) the samely with embodiment 3-1.PC-3-8 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-8, be confirmed to be the copolymerization PC that following (9) mean.For PC-3-8 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[embodiment 3-9]

In the manufacture of the copolymerization PC of embodiment 3-1, except the biphenol compound of using as comonomer, use 4 identical with above-described embodiment 3-2,4 '-dihydroxybiphenyl, by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (3-methyl-4-hydroxy phenyl) the propane 83g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-3-9) the samely with embodiment 3-1.PC-3-9 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-9, be confirmed to be the copolymerization PC that following (10) mean.For PC-3-9 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[comparative example 3-1]

Except the biphenol compound of using as comonomer, use 4 of Honshu chemistry manufacture, 4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 49 quality ppm), outside 24g, other and embodiment 3-1 manufacture copolymerization PC (PC-3-10) in the same manner.PC-3-10 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-3-10, confirm that its structure is identical with PC-3-1.

For PC-3-10 and by this copolymerization PC the same with embodiment 3-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 3-1.

[evaluation result]

Table 5 and table 6 mean the evaluation result of embodiment 3-1～3-9 and comparative example 3-1.

[table 5]

[table 6]

The embodiment of the<the 4 embodiment >

Then, by embodiment and comparative example, the 4th embodiment of the present invention is described in detail.

[embodiment 4-1]

(manufacture of copolymerization PC)

By 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-are dissolved in the aqueous sodium hydroxide solution 550ml of 6 quality % concentration, to dissolve resulting solution and methylene dichloride 250ml mixes, be blown into carbonyl chloride gas while stirring in the cooling lower ratio toward dividing with 950ml/ in liquid, blow 15 minutes.Then, this reaction solution of standing separation, the polymerization degree of organic layer is 2～4, obtains the dichloromethane solution that molecular end has the oligopolymer of chloroformic acid ester group.Add ethylene dichloride in resulting oligomer solution, total amount is 450ml.

Then, with following solution, mix, this solution is by 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxy-benzene content: 49 quality ppm) 24g is dissolved in the aqueous sodium hydroxide solution 150ml of 8 quality % concentration (as antioxidant, add 100mg sodium bisulfite (0.57 mmole, with respect to 1 mole of the xenol of raw material, be 0.0044 mole)) solution, add inward molecular weight regulator p-tert-butylphenol 0.3g (the xenol aqueous solution).

Add the xenol aqueous solution in above-mentioned oligomer solution, mixed, on one side this mixed solution of high degree of agitation, add the triethylamine aqueous solution 2ml of 7 quality % concentration on one side as catalyzer, under the state of 28 ℃ of maintenances, limit continues to stir, and interfacial polycondensation reaction 1.5 hours is carried out on limit.After reaction finishes, with 1 liter of diluting reaction resultant of methylene dichloride, then by the order of 1 liter, 1 liter, 1.5 premium on currency 2 times, 0.01 regulation hydrochloric acid 1 time, water 2 times, cleaned, obtained polymers soln.

Then, prepare to be equipped with in addition the band baffle plate container of agitating vane, drop into inward 2 liters of methyl alcohol.The agitating vane methyl alcohol in stirred vessel fully for one side, one side splashes into 1 liter of above-mentioned polymers soln at leisure with the speed that forms particle, by redeposition, carry out the sheet processing.After splashing into end, one side keeps enough stirring velocitys, after one side stirs 10 minutes, then 2 liters of methyl alcohol of additional input, then continue to stir 5 minutes.Carry out filtration drying to resulting, as the copolymerization PC (PC-4-1) that estimates use.

(evaluation of copolymerization PC)

PC-4-1, under this state (powder), is carried out to YI mensuration (according to JIS K 7105).

Then, PC-4-1 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.In addition, utilize ¹after H-NMR is analyzed the chemical structure of PC-4-1, be confirmed to be the copolymerization PC that following chemical formula (5) means.

Again, utilize the minor axis forcing machine of 50mm φ, 280 ℃ of cylinder temperature, under revolution speed of screw 100rpm, the sheet of PC-4-1 is melt extruded, carry out granulating.After under 120 ℃, this particle being carried out to the drying treatment of 5 hours, use the metal pattern (S55C minute surface #1000) of 20 * 50 * 3mm, carry out injection molding forming, make the test film (20 * 50 * 3mm) that physical property measurement is used.This test film (injection molding forming product) is carried out to the mensuration (all according to JIS K 7105) of YI (according to JIS K 7105) and total light penetration.These evaluation results are judged with following benchmark.

The YI:2 of injection molding forming product is following is A (very good), below 4, is B (good), and surpassing 4 is C (bad).

In total light penetration: more than 89%, being B (good), is C (bad) less than 89%.

(manufacture of Electrophtography photosensor)

The embodiment 1-1 of the manufacture of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

(evaluation of Electrophtography photosensor)

The embodiment 1-1 of the evaluation of the Electrophtography photosensor in the present embodiment and above-mentioned the 1st embodiment carries out the samely.Therefore explanation is omitted.

[embodiment 4-2]

In the manufacture of the copolymerization PC of embodiment 4-1, the temperature when making polycondensation is 15 ℃, and other manufacture copolymerization PC (PC-4-2) the samely with embodiment 4-1.PC-4-2 being dissolved in methylene dichloride, making the solution of concentration 0.5g/dl, measure the reducing viscosity [η sp/C] under 20 ℃, is 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-2, confirm that its structure is identical with PC-4-1.

For PC-4-2 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-3]

In the manufacture of the copolymerization PC of embodiment 4-1, before carrying out polycondensation, use the nitrogen replacement reaction vessel, making oxygen partial pressure is after 5000Pa, carries out polycondensation, in addition, other and embodiment 4-1 similarly manufacture copolymerization PC (PC-4-3).

PC-4-3 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-3, confirm that its structure is identical with PC-4-1.

For PC-4-3 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-4]

In the manufacture of the copolymerization PC of embodiment 4-1, except the biphenol compound of using as comonomer, use 4,4 '-dihydroxybiphenyl (acetone recrystallize item for disposal, trihydroxy-biphenyl content: 8 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 23 quality ppm) 24g, temperature while making polycondensation is outside 15 ℃, and other manufacture copolymerization PC (PC-4-4) the samely with embodiment 4-1.PC-4-4 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-4, confirm that its structure is identical with PC-4-1.

For PC-4-4 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-5]

In the manufacture of the copolymerization PC of embodiment 4-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1,1-bis(4-hydroxyphenyl) cyclohexane 87g, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-4-5) the samely with embodiment 4-1.PC-4-5 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-5, be confirmed to be the copolymerization PC that following (7) mean.For PC-4-5 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-6]

In the manufacture of the copolymerization PC of embodiment 4-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 1, two (4-hydroxy phenyl) the ethane 69g of 1-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-4-6) the samely with embodiment 4-1.PC-4-6 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.83dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-6, be confirmed to be the copolymerization PC that following (8) mean.For PC-4-6 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-7]

In the manufacture of the copolymerization PC of embodiment 4-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (4-hydroxy phenyl) the butane 79g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-4-7) the samely with embodiment 4-1.PC-4-7 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-7, be confirmed to be the copolymerization PC that following (9) mean.For PC-4-7 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[embodiment 4-8]

In the manufacture of the copolymerization PC of embodiment 4-1, except by 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 74g of 2-change to 2, two (3-methyl-4-hydroxy phenyl) the propane 83g of 2-, the aqueous sodium hydroxide solution 550ml of 6 quality % concentration is changed to outside the potassium hydroxide aqueous solution 550ml of 1.5 regulations, other manufacture copolymerization PC (PC-4-8) the samely with embodiment 4-1.PC-4-8 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-8, be confirmed to be the copolymerization PC that following (10) mean.For PC-4-8 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[comparative example 4-1]

Except as comonomer, with biphenol compound, using 4,4 '-dihydroxybiphenyl (trihydroxy-biphenyl content: 321 quality ppm, the 3-tertiary butyl-4,4 '-dihydroxybiphenyl content: 49 quality ppm) outside 24g, manufacture copolymerization PC (PC-4-9) the samely with embodiment 4-1.PC-4-9 is dissolved in methylene dichloride, makes the solution of concentration 0.5g/dl, measure the reducing viscosity [η under 20 ℃ _sp/ C], be 0.82dl/g.Utilize again, ¹after H-NMR is analyzed the chemical structure of PC-4-9, confirm that its structure is identical with PC-4-1.

For PC-4-9 and by this copolymerization PC the same with embodiment 4-1 the Electrophtography photosensor manufactured carry out the evaluation same with embodiment 4-1.

[evaluation result]

Table 7 and table 8 mean the evaluation result of embodiment 4-1～4-8 and comparative example 4-1.

[table 7]

[table 8]

Utilizability on industry

Copolycarbonate of the present invention can be aptly for field of electronic materials such as optical material purposes or Electrophtography photosensors.

Claims (7)

1. a Copolycarbonate, contain the monomeric unit that 0.1～50 % by mole of monomeric unit that following formula (1) means and following formula (2) mean and form, it is characterized in that, there is the content of biphenyl phenols of the structure that following formula (3) means below 90 quality ppm, the end of described Copolycarbonate is stopped by the end terminator

In formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12,

In formula, R ³, R ⁴the aryl or the halogen atom that mean independently respectively hydrogen atom, carbonatoms 1～6 aliphatic alkyl, carbonatoms 6～12, mean-O-of X ,-S-,-SO-,-SO ₂-,-CO-, 9,9-fluorenylidene, following formula (2a), (2b), (2c) and any bonding radical (2d) meaned,

In formula, R ⁵, R ⁶mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6 or the aryl of carbonatoms 6～12, again, R ⁵, R ⁶bonding and form the ring alkylidene group of carbonatoms 4～12 mutually,

In formula, R is the alkyl of hydrogen atom or carbonatoms 1～3, again, in R, has at least one to be the alkyl of carbonatoms 1～3,

In formula, bonding position can be adjacent,, right any one,

In formula, R ⁷～R ¹²mean independently respectively the alkyl of hydrogen, carbonatoms 1～4 or the bonding radical formed by singly-bound or alkylidene group, wherein, R ⁷～R ¹²in two be bonding radical, remaining is the alkyl of hydrogen or carbonatoms 1～4,

In formula, R ¹, R ²mean independently respectively the aliphatic alkyl of hydrogen atom, carbonatoms 1～6, aryl or the halogen atom of carbonatoms 6～12.

2. a molding, is characterized in that, by Copolycarbonate melt-shaping claimed in claim 1, formed.

3. a molding, is characterized in that, by Copolycarbonate wet forming claimed in claim 1, formed.

4. an optical material, is characterized in that, contains Copolycarbonate claimed in claim 1.

5. an optical material, is characterized in that, contains claim 2 or molding claimed in claim 3.

6. an Electrophtography photosensor, is characterized in that, contains Copolycarbonate claimed in claim 1.

7. an Electrophtography photosensor, is characterized in that, contains claim 2 or molding claimed in claim 3.