KR20080012797A - Halogen-containing polycarbonate resin composition, method for producing halogen-containing polycarbonate resin, and medical instruments using halogen-containing polycarbonate resin composition - Google Patents

Abstract

A halogen-containing polycarbonate resin composition is provided to realize excellent color tone stability and transparency under ionizing radiation such as gamma rays, and to prevent yellowing in medical instruments subjected to radiation sterilization. A halogen-containing polycarbonate resin composition comprises a halogen-containing polycarbonate resin, a carboxylate and a phosphorus compound. The halogen-containing polycarbonate resin composition has a chromaticness index b of 3.50 or less in the Hunter's color difference formula in the Lab color coordinate system, after 2 days from the irradiation of gamma rays with 25 kGy in the absence of oxygen, and shows a variance in haze of 10% or less.

Description

HALOGEN-CONTAINING POLYCARBONATE RESIN COMPOSITION, METHOD FOR PRODUCING HALOGEN-CONTAINING POLYCARBONATE RESIN, AND MEDICAL INSTRUMENTS USING HALOGEN-CONTAINING POLYCARBONATE RESIN COMPOSITION}

The present invention relates to a halogen-containing polycarbonate resin composition and the like, and more particularly, to a polycarbonate resin composition and the like excellent in transparency and color stability under γ-ray irradiation.

In the production of a polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A or BPA) by the interfacial method as a raw material, the organic of resin obtained by polymerization reaction Purification of the resin by washing the solvent solution with an aqueous washing solution such as water or an aqueous acid solution, concentrating the organic solvent solution of the resin after purification, and obtaining the resin by differentiating or granulating it in warm water have.

On the other hand, in the case of producing a halogen-containing polycarbonate resin for the purpose of flame-retardation of the resin, to produce a polycarbonate resin containing a relatively large amount of halogen of the amount required for the flame retardant, for example about 4% by weight In other words, it is known that the organic solvent solution of the resin obtained by the polymerization reaction is more difficult to clean and granulate than the case where only bisphenol A is used as the raw material.

Moreover, the polycarbonate resin with many halogen content produced in this way has a problem that melt fluidity is inferior compared with the polycarbonate resin which uses only bisphenol A as a raw material.

For example, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) ethane (hereinafter sometimes referred to as tetrabromobisphenol A or TBA) and bisphenol A are reacted with a carbonate oligomer. The 10 wt% methylene chloride solution of the polycarbonate resin having a bromo content of 4 wt% or more (see Patent Document 1), when attempting to clean on an industrial scale, generates an emulsion, and the organic solvent solution of the resin and the aqueous washing solution are not separated. Even if separated, a large amount of dirt layer (intermediate layer) is produced, resulting in low cleaning efficiency. For this reason, since impurities in the resin are not sufficiently removed, the resulting resin is poor in color tone, low in heat stability, and a viscous gelled material is produced even at the time of concentrated differentiation, and thus it is difficult to be differentiated. Manufacturing is difficult.

Moreover, by copolymerizing two specific carbonate oligomers, there has been proposed a production method in which a resin having an excellent melt flow property can be easily obtained, which facilitates the cleaning of the organic solvent solution of the halogen-containing polycarbonate resin and the concentration accompanying the concentration ( See Patent Document 2).

However, in these manufacturing methods, although the washing | cleaning property of the organic solvent solution of resin is excellent, there exists a problem in molecular weight stability of obtained resin, and the granulation accompanying molecular weight fall may become difficult.

Therefore, as a method of solving this problem, the applicant has disclosed a method of mixing and polymerizing a BPA oligomer and a (BPA and TBBPA) copolymerization oligomer (see Patent Document 3).

By using such a method, it was achieved to efficiently produce a halogen-containing flame-retardant polycarbonate resin that is excellent in molecular weight stability, detergency, differentiation, and the like and has good quality.

On the other hand, since polycarbonate resin is excellent in mechanical and thermal characteristics, and also excellent in transparency and hygiene, it is used for various medical components. Here, the medical part includes a container package for accommodating and packaging a syringe, a surgical instrument, an intravenous syringe, a surgical instrument, an artificial lung, an artificial kidney, an anesthesia absorbing device, an intravenous connector and accessories, a blood centrifuge device, and the like. Medical devices, surgical instruments, surgical instruments, and the like.

These medical parts are usually completely sterilized. Specifically, contact treatment with ethylene oxide, heat treatment in an autoclave, or treatment with ionizing radiation such as gamma (γ) rays or electron beams may be mentioned. Among these, the use of ethylene oxide is not preferable because of environmental problems related to the toxicity, instability and disposal of ethylene oxide itself. In the case of using an autoclave, the resin may be degraded during high temperature treatment, the energy cost is high, and the components after the treatment need to be dried before use because moisture remains. Has its drawbacks. Therefore, sterilization by ionizing radiation, which is capable of low temperature treatment and is relatively inexpensive, is widely used in place of these methods.

However, when the ionizing radiation is irradiated to the aromatic polycarbonate resin, the optically transparent resin inherently discolors yellow. For this reason, the method of canceling yellow by mixing a blue colorant in a resin, the method of adding a boron type compound (refer patent document 4), the method of adding a polyether polyol or its alkyl ether (refer patent document 5), etc. It is proposed.

Above all, even if these methods are used, the effect of preventing yellowing of the aromatic polycarbonate resin may be insufficient. Moreover, when the predetermined amount of yellowing inhibitor is added to the aromatic polycarbonate resin, the strength of the resin may be remarkably impaired.

Therefore, the present applicant carries out irradiation treatment such as γ ray by adding 0.1 wt% to 5 wt% of polypropylene glycol having a molecular weight of about 4,500 to a halogenated aromatic polycarbonate resin containing 0.1 wt% to 10 wt% of halogen. Even if it was reported about the medical components using the material with little color tone or physical property deterioration (refer patent document 6).

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-196907

[Patent Document 2] Japanese Unexamined Patent Publication No. 57-155233

[Patent Document 3] Japanese Unexamined Patent Publication No. 2005-179549

[Patent Document 4] Japanese Patent Application Laid-Open No. 61-215651

[Patent Document 5] Japanese Patent Application Laid-Open No. 62-135556

[Patent Document 6] Japanese Patent Application Laid-open No. Hei 6-24591

However, if further studies are conducted, yellowing of the resin is reduced when the medical component using the halogenated aromatic polycarbonate resin composition as described in Patent Document 6 is subjected to irradiation treatment such as gamma ray, but the sterilization of the medical component is performed. It has been found that the resin yellows and the color tone decreases due to ionizing radiation irradiation such as gamma rays under more stringent conditions. For this reason, the method of obtaining the material with less color tone and physical property deterioration is calculated | required.

This invention is made | formed in order to solve the subject at the time of developing the halogen containing polycarbonate resin used for the application to which ionizing radiation, such as (gamma) rays, is irradiated.

That is, an object of the present invention is to provide a halogen-containing polycarbonate resin composition excellent in transparency and color tone stability under ionizing radiation irradiation such as gamma rays.

Another object of the present invention is to provide a method for producing a halogen-containing polycarbonate resin having excellent ionization radiation resistance.

Another object of the present invention is to provide a medical device using a halogen-containing polycarbonate resin composition excellent in ionizing radiation resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, when the surface polycondensation is carried out using the mixture of a carbonate oligomer which does not contain a halogen, and a halogen-containing aromatic dihydroxy compound, it is a color stability with respect to (gamma) ray irradiation. This favorable halogen-containing polycarbonate resin was found to be obtained, and the present invention was completed based on these findings.

Thus, according to the present invention, a halogen-containing polycarbonate resin composition containing a halogen-containing polycarbonate resin and a carboxylic acid ester and a phosphorus compound, which has a color difference formula of Hunter of Lab color system after 2 days of 25 kGy gamma-ray irradiation The chromaticness index b in is 3.50 or less, and the change rate of soaking (haze) is 10% or less, The halogen-containing polycarbonate resin composition is provided.

Here, 0.01 weight part-1 weight part of carboxylic acid ester, and 0.01 weight part-1 weight part of phosphorus compound are added to the halogen containing polycarbonate resin composition to which this invention is applied to 100 weight part of halogen-containing polycarbonate resins. desirable.

Moreover, it is preferable that halogen content of halogen containing polycarbonate resin is 0.1 weight%-2 weight%.

It is also preferable that the carboxylic acid ester is an aliphatic carboxylic acid ester and the phosphorus compound is a phosphorous acid ester.

The molded object using the halogen-containing polycarbonate resin composition to which this invention is applied can be used especially as a medical apparatus excellent in ionizing radiation resistance with respect to (gamma) ray irradiation.

Next, according to the present invention, as a method for producing a halogen-containing polycarbonate resin, an oligomer synthesis step of synthesizing a carbonate oligomer by reacting an alkali metal or an alkaline earth metal compound of a halogen-free aromatic dihydroxy compound with carbonyl chloride and And a polymerization step of polymerizing an carbonate oligomer synthesized by an oligomer synthesis step and an alkali metal or alkaline earth metal compound of a halogen-containing aromatic dihydroxy compound and / or a halogen-containing aromatic dihydroxy compound, and a carbonate oligomer in the polymerization step The ratio (CF / BPX) of the terminal chloroformate concentration (CF) and the halogen-containing aromatic dihydroxy compound concentration (BPX) in the compound is 10 to 60 (equivalent ratio), and the terminal hydroxyl group concentration (OH) and the halogen in the carbonate oligomer. Aromatic Dihydroxyl The method of producing a halogen-containing polycarbonate resin, characterized in that ratio (OH / BPX) of the compound concentrations (BPX) is 4.5 ~ 27 (equivalent ratio) is provided.

It is preferable that ratio (CF / OH) of terminal chloroformate concentration (CF) in a carbonate oligomer used here and terminal hydroxyl group concentration (OH) in a carbonate oligomer is 1.5-3.0 (equivalent ratio).

Moreover, it is preferable that a carbonate oligomer has a repeating unit shown to following structural formula (1).

In addition, the halogen-containing aromatic dihydroxy compound is preferably tetrabromobisphenol A represented by compound (2).

Moreover, halogen content of halogen containing polycarbonate resin is 0.1 weight%-2 weight%, It is characterized by the above-mentioned.

According to the present invention, a halogen-containing polycarbonate resin composition excellent in transparency and color tone stability under gamma ray irradiation is obtained.

EMBODIMENT OF THE INVENTION Hereinafter, the best form (following embodiment of this invention) for implementing this invention is demonstrated in detail. In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary.

In addition, in this embodiment, the "halogen content" of a polycarbonate resin means the density | concentration of the halogen atom couple | bonded with the principal chain part (phenyl group) of an oligomer or a polymer except a terminal chloroformate group.

In addition, "it does not contain a halogen" (Hereinafter, it may be called "halogen-free.") Means that it does not have the halogen atom couple | bonded with the main chain part (phenyl group) of polycarbonate resin, and it is a terminal chloroformate. It is not intended to exclude oligomers having groups. In addition, the terminal chloroformate group participates in the polymerization reaction, and is almost completely consumed by the completion of the polymerization, and the color tone stability of the polymer is related to the halogen atom bonded to the main chain portion (phenyl group).

The following two types are mentioned as a manufacturing method of halogen containing polycarbonate resin.

(1) A method of synthesizing a halogen-containing carbonate oligomer with a halogen-free aromatic dihydroxy compound, a halogen-containing aromatic dihydroxy compound and carbonyl chloride, and polycondensing the halogen-containing carbonate oligomer.

(2) A method of reacting a halogen-free aromatic dihydroxy compound with carbonyl chloride to synthesize a halogen-free carbonate oligomer, and reacting the halogen-free carbonate oligomer with a halogen-containing aromatic dihydroxy compound.

In this embodiment, the method of said (2) is demonstrated. Moreover, compared with the method of (1), the method of (2) has the advantage that the polymerization time can be shortened.

The method for producing a halogen-containing polycarbonate resin to which the present embodiment is applied is an oligomer synthesis step of synthesizing a halogen-free carbonate oligomer by reacting an alkali metal or alkaline earth metal compound of a halogen-free aromatic dihydroxy compound with carbonyl chloride. And a polymerization step of polymerizing an alkali metal or alkaline earth metal compound of the halogen-free carbonate oligomer and the halogen-containing aromatic dihydroxy compound and / or the halogen-containing aromatic dihydroxy compound. Hereinafter, each process is demonstrated.

(Oligomer Synthesis Process)

In the oligomer synthesis step in the present embodiment, the halogen-free carbonate oligomer is made by reacting an alkali metal or an alkaline earth metal compound of a halogen-free aromatic dihydroxy compound with carbonyl chloride by a known interfacial polymerization method or a solution polymerization method. To synthesize.

Here, the halogen-free carbonate oligomer has a viscosity average molecular weight (Mv) of several hundreds to thousands, and a ratio (CF / OH) to the terminal chloroformate concentration (CF) to the terminal hydroxyl group concentration (OH) is 1.5 to 3.0 (equivalent ratio). Preferably it is 2.0-3.0.

Below, an aromatic dihydroxy compound is illustrated. As an aromatic dihydroxy compound, it is 1,1-bis (4-hydroxyphenyl) ethane, bis (4-methyl-2-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl, for example). ) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4 -Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) methane,

4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, bis (4-hydroxyphenyl) phenylmethane , 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) Propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec -Butyl-4-hydroxyphenyl) propane, bisphenolfluorene, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane,

4,4 '-[1,4-phenylene-bis (2-propylidene) -bis (3-methyl-4-hydroxyphenyl)], 1,1-bis (3-phenyl-4-hydroxyphenyl ) Cyclohexane, 4,4'-dihydroxyphenyl ether, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol, bis (3-methyl-4-hydroxyphenyl) methane, 1,1 -Bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -3-methyl-butane,

Bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane, 3,3-bis (3,5-dimethyl-4-hydroxyphenyl) Pentane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) nonane, 1,1-bis (3-methyl-4-hydroxy Phenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane,

2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, bis (4 -Hydroxyphenyl) diphenylmethane, terpendiphenol, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-methyl-4-hydroxy- 5-tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (3,5-di-tert-butyl-4-hydroxyphenyl) Methane, bis (3,5-di-sec-butyl-4-hydroxyphenyl) methane,

1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-di-tert-butylphenyl) ethane, 1,1-bis ( 3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, bis (2-hydroxy-3,5-di-tert -Butyl-6-methyl phenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, 4,4-bis (4-hydroxyphenyl) pentanoic acid,

α, α′-bis (4-hydroxyphenyl) acetic acid butyl ester, 2,2-bis (3-nitro-4-hydroxyphenyl) propane, 3,3′-dimethyl-4,4′-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol, 3,3', 5,5'-tetra-tert-butyl-4,4'-biphenol, bis (4-hydrate Hydroxyphenyl) ketone, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4- Hydroxyphenyl) sulfone,

Bis (4-hydroxyphenyl) thioether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) thioether, bis (3,5-dimethyl-4- Hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) thioether, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-phenylmethane, 2 , 2-bis (3-methyl-4-hydroxyphenyl) dodecane, 2,2-bis (3-methyl-4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4 Hydroxyphenyl) dodecane,

1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -1-phenyl Ethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-di-tert-butyl Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) propanoic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propanoic acid ethyl ester, 1,3-bisphenol, 1,3-biscresol , 2,2 ', 3,3', 5,5'-hexamethyl-4,4'-biphenol, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane,

Bis (2-hydroxy-3-allylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-5 -tert-butylphenyl) ethane, bis (2-hydroxy-5-phenyl phenyl) methane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis (2- Methyl-4-hydroxy-5-cyclohexylphenyl) methane,

2,2-bis (4-hydroxyphenyl) pentadecane, 2,2-bis (3-methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-4-hydroxy Phenyl) pentadecane, 1,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2 , 2-bis (3-styryl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1- (p-nitrophenyl) ethane,

3,3 ', 5,5'-tetra-tert-butyl-2,2'-biphenol, 2,2'-diallyl-4,4'-biphenol, 1,1-bis (4-hydroxy Phenyl) -3,3-dimethyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5,5-tetramethylcyclohexane, 1,1-bis (4-hydrate Hydroxyphenyl) -3,3,4-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5-ethylcyclohexane, 1,1-bis (4-hydroxyphenyl ) -3,3,5-trimethylcyclopentane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5 -Diphenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,

Resorcinol, hydroquinone, 1,2-hydroxybenzene, 1,4-bis (4-hydroxyphenyl) -p-mentane, 1,4-bis (3-methyl-4-hydroxyphenyl) -p Terpenediphenols such as -mentane and 1,4-bis (3,5-dimethyl-4-hydroxyphenyl) -p-mentane; and the like can be given. Among these compounds, bisphenol A is preferable.

In addition, in this embodiment, it is not limited to these aromatic dihydroxy compound mentioned above, Another aromatic dihydroxy compound can also be used. Moreover, these aromatic dihydroxy compounds can be used by one type or plurality.

Moreover, you may substitute a part of aromatic dihydroxy compound mentioned above by another aliphatic dihydroxy compound in the range which does not substantially impair the characteristic. Such dihydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, dodecanediol, neopentylglycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexane, and the like. Can be mentioned.

(Alkali metal or alkaline earth metal compound)

In this embodiment, an aromatic dihydroxy compound forms a water phase with water and an alkali metal or alkaline-earth metal compound. As an alkali metal or alkaline-earth metal compound, hydroxide is preferable normally, For example, sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. are mentioned, Among these, sodium hydroxide is especially preferable.

The ratio of the alkali metal or alkaline earth metal compound to the aromatic dihydroxy compound is usually 1.0 to 1.5 (equivalent ratio), preferably 1.02 to 1.04 (equivalent ratio). When the proportion of the alkali metal or alkaline earth metal compound is excessively large or excessively small, the resulting oligomer end group is affected, and as a result, the condensation reaction tends to be abnormal. In addition, a small amount of reducing agents such as hydrosulfite may be added to the aqueous phase.

In the oligomer synthesis step in the present embodiment, an organic solvent is usually used. The organic solvent includes any inert organic solvent which dissolves the reaction products such as carbonyl chloride and carbonate oligomer, polycarbonate and the like at the reaction temperature and the reaction pressure and does not form a solution with water. do.

Aliphatic hydrocarbons such as hexane and n-heptane as inert organic solvents; Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane and 1,2-dichloroethylene; Aromatic hydrocarbons such as benzene, toluene and xylene; Chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and chlorotoluene; In addition, substituted aromatic hydrocarbons such as nitrobenzene and acetophenone are included.

Among these, chlorinated hydrocarbons such as methylene chloride or chlorobenzene are preferably used. These inert organic solvents can be used alone or as a mixture with other solvents.

(Carbonyl chloride)

Carbonyl chloride (hereinafter sometimes referred to as CDC) used in the present embodiment is usually used in the liquid or gas phase. From the viewpoint of temperature management, the CDC is preferably a liquid phase, and a reaction pressure capable of maintaining the liquid phase at the reaction temperature is selected. The preferred amount of CDC is suitably selected by the reaction conditions, in particular, the reaction temperature and the concentration of the metal salt of the aromatic dihydroxy compound in the water phase. Although not particularly limited, it is usually from 1.05 mol to 1 mol of the aromatic dihydroxy compound. 1.30 mol, Preferably it is 1.20 mol-1.25 mol. When the amount of CDC used is too small, the ratio (CF / OH) of the terminal chloroformate concentration (CF) in the carbonate oligomer and the terminal hydroxyl group concentration (OH) in the carbonate oligomer tends to be less than 1.5. In addition, when the amount of CDC used is excessively large, the loss of CDC increases, and (CF / OH) tends to exceed 3.0.

In addition, in this embodiment, arbitrary branching also can be used as a raw material of polycarbonate in an oligomer synthesis process. The branching agent used can be selected from various compounds having three or more functional groups. Suitable branching agents include compounds having three or more phenolic hydroxyl groups, for example 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy Hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane and 1,4-bis (4,4'-dihydrate Oxytriphenylmethyl) benzene is mentioned. Moreover, 2, 4- dihydroxy benzoic acid, trimesic acid, and cyanuric chloride which are compounds which have three functional groups can also be used. Among these, those having three or more phenolic hydroxyl groups are preferable. Although the usage-amount of a branching agent changes also with the branching degree made into the objective, it is normally used in the quantity of 0.05 mol%-2 mol% with respect to aromatic diols.

In addition, in the oligomer synthesis process in this embodiment, monophenols are normally used as a chain stopper. As monophenols used as a chain stopper, Phenol; alkyl phenols having 1 to 20 carbon atoms such as p-t-butylphenol and p-cresol; halogenated phenols such as p-chlorophenol and 2,4,6-tribromophenol. Although the usage-amount of monophenols also changes with the molecular weight of the target condensate, it is normally used in the quantity of 0.5 mol%-10 mol% (0.005 times-0.1 times) with respect to an aromatic dihydroxy compound.

The molecular weight of the polycarbonate is determined by the addition amount of a chain stopper such as monophenol, but from the viewpoint of molecular weight controllability, the addition time is preferably from immediately after the end of the consumption of the carbonate-forming compound to the beginning of the molecular weight extension. . When monophenols are added in the presence of a carbonate-forming compound, many condensates (carbonated diphenyls) of monophenols are produced, and polycarbonate resin of a target molecular weight is hard to be obtained, which is not preferable. On the other hand, when the addition of monophenols is extremely slowed, not only the molecular weight control is difficult, but also a resin having an unusual form on the low molecular side of the molecular weight distribution, and there are many disadvantages such as causing sagging during molding. Not.

In the present embodiment, when the two-phase interfacial condensation method is employed, it is particularly preferable to form an emulsion by bringing the organic phase and the aqueous phase into contact with each other prior to contact with carbonyl chloride. In order to form an emulsion, it is preferable to use dynamic mixers, such as a homogenizer, a homomixer, a colloid mill, a jetjet mixer, an ultrasonic emulsifier, and a mixer, such as a static mixer, in addition to the stirrer which has a normal stirring blade. Emulsions usually have a droplet diameter of 0.01 μm to 10 μm and have emulsion stability.

An emulsification state can be normally expressed by Weber number or P / q (additional power value per unit volume). The web number is preferably 10,000 or more, more preferably 20,000 or more, and most preferably 35,000 or more. Moreover, as an upper limit, about 1,000,000 or less is enough. The P / q is preferably 200 kg · m / liter or more, more preferably 500 kg · m / liter or more, and most preferably 1,000 kg · m / liter or more.

Contact between the emulsion and carbonyl chloride (CDC) is preferably carried out under mixed conditions weaker than the above-mentioned emulsification conditions in the sense of suppressing dissolution of the CDC into the organic phase. The web number is less than 10,000, preferably less than 5,000, more preferably less than 2,000. Moreover, as P / q, it is less than 200 kg.m / liter, Preferably it is less than 100 kg.m / liter, More preferably, it is less than 50 kg.m / liter. Contact of the CDC can be achieved by introducing the CDC into a tubular reactor or a crude reactor.

In an oligomerization reaction, it can carry out in presence of a condensation catalyst. The addition is preferably carried out after the CDC is consumed, and the condensation catalyst can be arbitrarily selected from many condensation polymerization catalysts used in the two-phase interfacial condensation method. Among them, trialkylamine, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine and N-isopropylmorpholine are suitable, in particular triethylamine and N Ethyl piperidine is particularly suitable.

The reaction temperature at the time of obtaining an oligomer is 80 degrees C or less, Preferably it is 60 degrees C or less, More preferably, it is the range of 10 degreeC-50 degreeC. Moreover, although reaction time also depends on reaction temperature, it is 0.5 minutes-10 hours normally, Preferably they are 1 minute-2 hours. If the reaction temperature is too high, side reactions are not controlled, and the CDC raw unit deteriorates. On the other hand, if it is too low, the reaction control phase is a preferable situation, but the refrigeration load is increased and the cost increases by that amount, which is not preferable.

The oligomer concentration in an organic phase should just be a range in which the oligomer obtained is soluble, and is specifically about 10-40 weight%. It is preferable that the ratio of an organic phase is the volume ratio of 0.2-1.0 with respect to the aqueous alkali or alkaline-earth metal salt solution of an aromatic dihydroxy compound, ie, an aqueous phase.

(Polymerization process)

In the polymerization step in the method for producing a halogen-containing polycarbonate resin to which the present embodiment is applied, the interface-condensation of the halogen-free carbonate oligomer and the halogen-containing aromatic dihydroxy compound synthesized in the oligomer synthesis step described above is carried out in a conventional manner. The sum is performed. At this time, an aqueous alkali metal or alkaline earth metal salt solution of a halogen-containing aromatic dihydroxy compound and / or a halogen-containing aromatic dihydroxy compound is added during interfacial polycondensation.

In a preferred embodiment of the polymerization step, the organic phase in which the halogen-free carbonate oligomer is dissolved is separated from the aqueous phase, and the concentration of the halogen-free carbonate oligomer is adjusted as necessary by adding the above-mentioned inert organic solvent. In this case, the amount of solvent is adjusted so that the density | concentration of the halogen containing polycarbonate resin in the organic phase obtained by polycondensation may be 5 to 30 weight%.

Subsequently, a solution containing a water phase and a halogen-containing aromatic dihydroxy compound newly containing water and an alkali metal hydroxide is added, and in order to adjust the polycondensation conditions, a condensation catalyst is preferably added, according to the interfacial polycondensation method. Complete polycondensation. As for the ratio of the organic phase and water phase at the time of polycondensation, organic phase: water phase = 1: 0.2-1 grade is preferable by volume ratio.

(Halogen-containing aromatic dihydroxy compound)

Examples of the halogen-containing aromatic dihydroxy compound used in the polymerization step include tetrabromobisphenol A (TBA), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 -Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-tetrabro Mother-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-tetrachloro-4-hydroxyphenyl) propane, and the like. Among these, tetrabromobisphenol A (TBA) is preferable.

The amount of the halogen-containing aromatic dihydroxy compound used in the halogen-free carbonate oligomer is a ratio of the terminal chloroformate concentration (CF) and the halogen-containing aromatic dihydroxy compound concentration (BPX) in the halogen-free carbonate oligomer (CF / BPX). ) = 10-60 (equivalent ratio), Preferably it is 20-50 (equivalent ratio), and ratio of the terminal hydroxyl group concentration (OH) and halogen-containing aromatic dihydroxy compound concentration (BPX) in a halogen-free carbonate oligomer (OH / BPX) is 4.5-27 (equivalent ratio), Preferably it is 4.5-20 (equivalent ratio). When (CF / BPX) or (OH / BPX) is excessively large or excessively small, there is a tendency that the polymerization reaction is not completed or the introduction rate of the halogen-containing aromatic dihydroxy compound is lowered.

(Alkali metal or alkaline earth metal compound)

In the polymerization process to which the present embodiment is applied, the halogen-containing aromatic dihydroxy compound forms an aqueous phase together with water and an alkali metal or alkaline earth metal compound. As an alkali metal or alkaline-earth metal compound, a hydroxide is preferable normally, For example, sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. are mentioned, Among these, sodium hydroxide is especially preferable.

In this case, the ratio of the alkali metal or alkaline earth metal compound to the halogen-containing aromatic dihydroxy compound is preferably 1.0 to 1.5 (equivalent ratio), more preferably 1.0 to 1.05. When the proportion of the alkali metal or alkaline earth metal compound is excessively small, the halogen-containing aromatic dihydroxy compound tends not to form an aqueous solution. When the proportion of the alkali metal or alkaline earth metal compound is excessively large, the solubility of the halogen-containing aromatic dihydroxy compound tends to be lowered. Moreover, you may add a small amount of reducing agents, such as hydrosulfite, to an aqueous phase.

Moreover, although alkali hydroxides, such as sodium hydroxide and potassium hydroxide, are mentioned as an alkali compound added at a superposition | polymerization process, sodium hydroxide is industrially preferable. The amount of the alkali compound may be equal to or greater than the amount that always maintains alkalinity during the polymerization reaction, and may be added in a batch at the time of starting the polymerization reaction, or may be appropriately divided and added during the polymerization reaction. When the amount of the alkali compound is excessively large, there is a tendency for the hydrolysis reaction that is a side reaction to proceed. Therefore, after completion of the polymerization reaction, the concentration of the alkali compound in the aqueous phase is preferably 0.05N or more, preferably 0.05N to 0.10N.

This alkali amount also contains the quantity of the excess alkali or alkaline-earth metal in the alkali or alkaline-earth metal salt aqueous solution of said halogen containing aromatic dihydroxy compound.

The polymerization reaction temperature in a polymerization process is normally around normal temperature, and reaction time is 0.5 hour-5 hours, Preferably it is about 1 hour-3 hours. After completion of the polymerization reaction, washing is performed with an alkali such as sodium hydroxide until the remaining terminal chloroformate group concentration (CF) is 0.1 μeq / g or less.

Thereafter, the impurities are removed by pickling and washing with a conventional method, and then the halogen-containing polycarbonate resin of the granules is separated by removing the organic solvent.

As a method for obtaining a solid polycarbonate resin from an organic solvent solution of a halogen-containing polycarbonate resin, a method (kneader method) for evaporating an organic solvent from a organic solvent solution of a halogen-containing polycarbonate resin (kneader method), a solvent and a non-solvent A method of precipitating a halogen-containing polycarbonate resin by mixing, supplying an organic solvent solution of the halogen-containing polycarbonate resin to a granulation tank having a stirring blade, heating while maintaining the suspended state in water to evaporate the organic solvent to enter the halogen-containing polycarbonate resin The method (assembly method) of obtaining an upper body is mentioned. Especially, the granulation method is more preferable from the viewpoint of workability, such as drying and pelletization by melt extrusion. Hereinafter, the granulation method will be described.

(Assembly method)

In the granulation method, a granulation tank having two or more stir blades is preferably used. In a granulation tank having only one stage of agitation blades, it is also different depending on the position of the blade. However, block solids are generated on the lower wall surface of the granulation tank, or the flow state of the water slurry surface is deteriorated. There may be a case. The shape of the stirring blade is not particularly limited, and a conventional stirring blade can be used.

In addition, the presence or absence of a baffle plate in the assembly tank does not particularly affect, but it is necessary to consider that there is no staying part in the tank, and it is preferable that the baffle plate is not used or the cross section of the baffle plate is round or elliptical.

In addition, as a supply position of the organic-solvent solution of a halogen-containing polycarbonate resin, the water in between the horizontal surface containing the bottom or bottom of the stirring blade located in the upper part, and the horizontal surface containing the top or top of the stirring blade located in the lower part is desirable. Specifically, in the case where the distance between the two horizontal planes is h, it is preferable to select a position separated by 0.1 h or more from the two horizontal planes, preferably 0.2h, more preferably near the middle of the two horizontal planes. It is good to feed on.

When there are three or more stages of stirring blades, you may divide and supply the organic solvent solution of halogen-containing polycarbonate resin in the water between each stirring blades.

The supply position of the organic-solvent solution of halogen-containing polycarbonate resin is 0.3 d-0.9 d position from the center of a tank, Preferably it is 0.4 d-0.8 d position, when a bath radius is set to d in the radial direction. In the portion of 0.9d to 1d, rock-like solids are easily formed, and in the portion of 0 to 0.3d, vapor of the organic solvent generated from the polymer solution is less likely to be uniformly dispersed in the tank, and the dolby ) Is not preferred.

Moreover, when supplying a polymer solution to a gaseous-phase part in a tank, it becomes unpreferable because it becomes a film form on a liquid level or causes coarse aggregate generation.

In the granulation tank, at least a portion of the polymer granules-containing water slurry extracted from the discharge pipe is pulverized by using a wet mill, circulated through the circulating water slurry introduction pipe, and replenishment water is supplied from the feed water introduction pipe. The organic solvent solution of the halogen-containing polycarbonate resin is continuously supplied from the polymer solution introduction tube.

The position of the polymer solution introduction pipe is supplied to the middle portion of the two-stage blade in addition to the tip of the blade of the assembly tank.

The temperature at the time of evaporating the organic solvent in the granulation tank can be selected within the range between the azeotropy point of the organic solvent and water and below the boiling point of water. Or a block of polycarbonate resin in the bath, and, on the contrary, if it is too high, the bulk density of the resulting halogen-containing polycarbonate resin granules tends to be small.

In the case of evaporating a solvent such as methylene chloride, a solid halogen produced from a wet milled product of the halogen-containing polycarbonate resin particulate circulated in the granulation tank and the organic solvent solution of the supplied halogen-containing polycarbonate resin Since the halogen-containing polycarbonate resin granules in which the containing polycarbonate resin is coalesced are formed, the granules are continuously discharged from the lead pipe as water slurry containing them.

The amount of the halogen-containing polycarbonate resin granule in the granulation tank is 5% by weight to 50% by weight, preferably 10% by weight to 45% by weight, with respect to the water slurry in the granulation tank in terms of stirring and handling of the water slurry. More preferably, it is good to set it as about 15 to 40 weight%, the quantity of the organic solvent solution of the halogen-containing polycarbonate resin introduce | transduced into a granulation tank, the quantity of replenishment water, and the halogen containing poly extracted from a granulation tank. It is good to control the quantity of the carbonate resin granule containing water slurry, and to maintain the amount of halogen-containing polycarbonate resin granules to a constant value within the said range.

In the present embodiment, at least a part of the water slurry extracted from the discharge pipe is wet-pulverized with a wet mill, circulated through a granulation tank, and a product halogen-containing polycarbonate resin particulate-containing water slurry is extracted.

As the wet grinder used for the wet grinding treatment, any type of liquid grinder can be used as long as it can grind the solid in the liquid. It is preferable to have a conveyance action of the water slurry together with the grinding, for example, the stirring blade has a high speed. Rotary type is suitable. Commercial products of the electronic type include Tokushukika Kogyo Co., Ltd., trademark, pipeline homomixer or homomixline mill, and the latter commercial products include Komatsu Genoa Co., Ltd., brand, disintegrator, etc. have.

Grinding by the wet grinding treatment is preferably carried out so that the halogen-containing polycarbonate resin granules in the water slurry have a particle diameter of 0.1 mm to 4 mm, preferably about 0.2 to 2 mm. The amount which circulates this wet-pulverized water slurry to a granulation tank is 50 weight%-99.5 weight% of the water slurry extracted from a granulation tank, Preferably it is about 70 weight%-98 weight%. When the amount of water slurry circulated in the granulation tank is excessively small, the particle diameter of the halogen-containing polycarbonate resin granules formed in the granulation tank tends to become larger and more uneven, and thus the desired product is not obtained or continuous operation. This causes problems such as becoming impossible. On the contrary, in excessively many cases, the acquisition amount of the product tends to decrease.

The water slurry for obtaining the halogen-containing polycarbonate resin granules of the product is extracted through the discharge tube from the water slurry after the wet grinding treatment, and may be extracted from the granulation tank or the discharge tube. In order to acquire a halogen containing polycarbonate resin granular material from a halogen containing polycarbonate resin granular material containing slurry, what is necessary is just to isolate | separate and dry a granular body by means, such as beveling, filtration, and centrifugation.

(Halogen-containing polycarbonate resin composition)

The halogen-containing polycarbonate resin composition to which the present embodiment is applied is obtained by containing a carboxylic acid ester and a phosphorus compound in the halogen-containing polycarbonate resin obtained by the above-described production method. You may add other adjuvant to the composition of this embodiment as needed in the range which does not impair the objective and effect of this invention, such as at least 1 type of adjuvant selected from a ultraviolet absorber, a flame retardant, a coloring agent, and an antistatic agent.

In addition, the halogen-containing polycarbonate resin composition to which the present embodiment is applied has a chromaticity index b of 3.50 or less in the color difference formula of Hunter of Lab color system after 2 days of 25 kGy gamma ray irradiation under oxygen blocking, preferably 3.30 or less, and the change rate of the soak (Haze) is 10% or less, Preferably it is 9% or less, It is characterized by the above-mentioned.

Here, the chromaticity index b in the color difference formula of the Hunter of the Lab color system is calculated | required based on JISZ8730.

In addition, the immersion Haze is the ratio (Td / Tt) of the diffuse light transmittance Td and the total light transmittance Tt (JIS K-7105).

The halogen content of the halogen-containing polycarbonate resin is 0.1% by weight to 2% by weight, and preferably 0.5% by weight to 1.5% by weight. Examples of the halogen include chlorine (Cl) and bromine (Br).

Next, the component mix | blended with a halogen containing polycarbonate resin composition is demonstrated.

(Phosphorus compound)

It is preferable that it is a trivalent phosphorus compound as a phosphorus compound, and it is especially preferable that the at least 1 acid group of phosphorous acid is the phosphite ester esterified by the phenol which has at least one phenol and / or a C1-C25 alkyl group.

As a specific example of a phosphite ester, it is 4,4'- butylidene-bis (3-methyl-6-t-butylphenyl- tritridecyl) phosphite, 1,1, 3- tris (2- Methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, trisnonylphenylphosphite, dinonylphenylpentaerythritoldiphosphite, tris (2,4-di-t-butylphenyl) phosphite , Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-ethylidene- Bis (4,6-di-t-butylphenyl) fluorinated phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) octylphosphite, bis (2,4-dicumylphenyl A phosphite ester which consists of a pentaerythritol diphosphite, a monononyl phenol, and a dinonyl phenol, etc. are mentioned.

Among these phosphorus compounds, tris (2,4-di-t-butylphenyl) phosphite is particularly preferable.

The amount of the phosphorus compound added is 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the halogen-containing polycarbonate resin. When the addition amount of the phosphorus compound is excessively large, there is a tendency to be colored at the time of molding. If the addition amount of the phosphorus compound is excessively small, the addition effect is insufficient. Moreover, a phosphorus compound may not only use individually but may use 2 or more types together.

(Carboxylic acid ester)

As carboxylic acid ester used by this embodiment, aliphatic carboxylic acid ester is preferable. Carboxylic acid components constituting the aliphatic carboxylic acid esters include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachinic acid, behenic acid, lignoseric acid, sertoic acid, Melic acid, tetraliacontanic acid, montanic acid, glutaric acid, adipic acid, azelaic acid, etc. are mentioned.

Examples of the alcohol component include various saturated or unsaturated monohydric alcohols, polyhydric alcohols, and the like.

Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neo Pentylene glycol, ditrimethylol propane, dipentaerythritol, glycerin and the like.

Among these aliphatic carboxylic acid esters, Glycerine fatty acid esters, such as glycerin monopalmitate, glycerin monostearate, glycerin distearate, and glycerin tristearate; Pentaerythritol fatty acid esters such as pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and pentaerythritol tetrastearate are preferred, and glycerin monostearate is particularly preferred. And pentaerythritol tetrastearate are preferable.

The addition amount of carboxylic acid ester is 0.01 weight part-1 weight part with respect to 100 weight part of halogen containing polycarbonate resin, Preferably it is 0.05 weight part-0.5 weight part. When the amount of the carboxylic acid ester added is excessively large, decomposition gas is generated and the soaking (Haze) tends to deteriorate. If the amount of the carboxylic acid ester added is too small, the releasability at the time of molding tends to deteriorate. Moreover, several carboxylic acid ester can be used together.

(Method for producing a halogenated polycarbonate resin composition)

The timing and addition method of adding the above-mentioned phosphorus compound and carboxylic acid ester, and the adjuvant used as needed to a halogenated polycarbonate resin are not specifically limited. For example, as addition time, the middle of kneading | mixing of polycarbonate resin, etc. are mentioned before pelletizing after inactivating the catalyst used for superposition | polymerization in the middle of a polymerization reaction, and at the end of a polymerization reaction with a catalyst deactivator. The halogen-containing polycarbonate resin and the auxiliary agent in solid state such as pellets or powder may also be kneaded with an extruder or the like.

Especially, it is preferable to add at the time of kneading | mixing in the extruder for manufacturing a halogen containing polycarbonate resin composition, and it is preferable.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples unless the gist thereof is exceeded. In addition, each measured value in an Example is calculated | required by the following method.

(1) Terminal chloroformate group concentration (CF) of carbonate oligomer

After diluting the carbonate oligomer solution with methylene chloride, aniline and pure water were added, and phenolphthalein was used as an indicator, and titrated with sodium hydroxide (NaOH) of prescribed degree, and obtained.

(2) Terminal hydroxyl group concentration (OH) of carbonate oligomer

After diluting the carbonate oligomer solution with methylene chloride, titanium tetrachloride and acetic acid solution were added to develop color, and the absorbance at wavelength 546 nm was measured using a spectrophotometer (UV-1600 manufactured by Shimadzu Corporation). Moreover, the extinction coefficient was calculated | required about the methylene chloride solution of bisphenol A used at the time of carbonate oligomer manufacture, and the terminal phenolic hydroxyl group (OH) concentration of the carbonate oligomer was measured based on these.

(3) Viscosity Average Molecular Weight (Mv)

The halogen-containing polycarbonate resin was dissolved in dichloromethane, and the solution of concentration (C) 6.00 g / L was adjusted. Subsequently, using the Uberode capillary viscometer, the dripping time (t ₀ ) of the solvent (dichloromethane) and the dripping time (t) of the sample solution were measured in the constant temperature water bath set at 20.0 ° C, and the intrinsic viscosity was measured. [η] was obtained.

Next, based on these measured values, the viscosity average molecular weight (Mv) was computed according to the following formula (i)-(v).

(i) η _sp = (t / t ₀ )-1

(Ii) C = 6.00 (g / L)

(Iii) a = 0.28 × η _sp + 1

(V) b = 10 × (η _sp / C)

(Iii) [η] = b / a

(V) Mv = 51400 × [η] exp 1.205

(4) Terminal chloroformate group concentration (CF) of halogen-containing polycarbonate resin

About 1 g of a halogen-containing polycarbonate resin is precisely weighed, 20 ml of methylene chloride is added to dissolve, and 2 ml of 4- (p-nitrobenzyl) pyridine (concentration: 1 wt% methylene chloride solution) is added thereto to develop color. Absorbance at a wavelength of 440 nm was measured using a spectrophotometer (UV-1600, manufactured by Shimadzu Corporation). Moreover, the extinction coefficient was calculated | required using the methylene chloride solution of phenylchloroformate, and the amount of chloroformate groups of halogen-containing polycarbonate resin was quantified based on these measured values.

(5) Halogen content (bromine atom content) of halogen containing polycarbonate resin

About 1 g of halogen-containing polycarbonate resin was precisely weighed and dissolved in 25 ml of tetrahydrofuran, and then measured by fluorescent X-ray (SEA2010L type).

(6) Color of halogen-containing polycarbonate resin

In accordance with JIS Z8722, the halogen-containing polycarbonate resin composition before and after irradiation of 25 kGy gamma ray was dried at 130 ° C. for 5 hours, and injected at 360 ° C. by an injection molding machine to have a length of 100 mm × width of 100 mm × thickness of 3 mm. Each press sheet was shape | molded and the chromaticness index b in the color difference formula of the Hunter of a Lab colorimeter was measured using the color tester (CM-3700d by Konica Minoruta Co., Ltd.) (unit: none).

(7) Biliary of Halogen-Containing Polycarbonate Resin (Solution: Haze)

In accordance with JIS K-7105, the halogen-containing polycarbonate resin composition before and after irradiation of 25 kGy gamma ray was dried at 130 ° C. for 5 hours, and then injected at 360 ° C. using an injection molding machine to length 100 mm × width 100 mm × thickness The 3 mm press sheets were each shape | molded, and the Haze change rate before and after (gamma) ray irradiation was calculated | required from the Haze value measured using the Haze Mita (model NDH-1001DP of Nippon Denshoku Co., Ltd. make) (unit%). The smaller this value is, the better the ionizing radiation is.

(Example 1)

100 kg of BPA, 145 kg of 25% by weight aqueous sodium hydroxide solution and 496 kg of demineralized water were dissolved in 35 L in a presence of 0.11 kg of hydrosulfite in a 700 L dissolution tank equipped with a 700 L stirring blade and jacket to prepare an aqueous BPA aqueous solution (aqueous phase). It was. Subsequently, this aqueous BPA aqueous solution (water phase) was supplied to a stainless steel pipe having an inner diameter of 6 mm and an outer diameter of 8 mm at a flow rate of 119 kg / hr.

At the same time, methylene chloride (organic phase) at 20 ° C was supplied to the stainless steel pipe at a flow rate of 59.2 kg / hr, and an aqueous BPA aqueous alkali solution (water phase) and methylene chloride (organic phase) were mixed in the stainless steel pipe.

Subsequently, this mixture is emulsified using a homo mixer (manufactured by Tokushukika Co., Ltd., product name TK Homomixline Flow LF-500 type), to prepare an emulsion of a mixture of an aqueous BPA aqueous solution (water phase) and methylene chloride (organic phase). It was.

Subsequently, an emulsion of BPA aqueous alkali solution (water phase) and methylene chloride (organic phase) was taken out of the homomixer by a pipe having an inner diameter of 6 mm × an outer diameter of 8 mm, and thereafter, an inner diameter of 6 mm × 34 m in length connected to the pipe. Was introduced into a pipe reactor (manufactured by polytetrafluoroethylene). In addition, the liquefied carbonyl chloride was supplied at a flow rate of 8.52 kg / hr by a pipe (cooled to 0 ° C) separately connected to this pipe reactor, and the above-mentioned BPA aqueous alkali solution (aqueous) / methylene chloride (organic phase) emulsion was added. And liquefied carbonyl chloride were contacted.

The emulsion described above was brought into contact with the liquefied carbonyl chloride during the flow of the inside of the pipe reactor at a vessel speed of 1.7 m / sec for 20 seconds, and chloroformation and oligomerization reactions were performed.

The reaction temperature in this case was adjusted so that it might be set to 60 degreeC, respectively, and external cooling was performed to 35 degreeC before entering into the next oligomerization tank. In this way, the oligomerized emulsion obtained from the pipe reactor is further led to a reactor with an internal volume of 50 liters of stirrer, and stirred at 30 ° C. under a nitrogen gas atmosphere to oligomerize to form Na of unreacted BPA present in the water phase. After the salt was consumed completely, the aqueous phase and the organic phase were left still to obtain a methylene chloride solution of the oligomer. At the time of oligomerization, 2% aqueous solution of triethylamine (hereinafter referred to as "2% TEA") and 16% methylene chloride solution of pt-butylphenol (hereinafter referred to as "16% PTBP") were each 0.273 kg / At 2.57 kg / hr, added to the oligomerization bath. The terminal chloroformate group concentration (CF) and terminal hydroxyl group concentration (OH) at this time are shown in Table 1.

65.5 kg of the dichloromethane solution of the oligomer and 34.8 kg of dichloromethane for dilution were injected into the reactor with a volume of 200 L of Paudora wing, while stirring and stirring. What mix | blended 0.270 kg of TBA) and 0.317 kg of 2 weight% triethylamine aqueous solution was added, and it stirred at 25 degreeC, and performed copolymerization reaction for 120 minutes.

After completion of the copolymerization reaction, 34.9 kg of dichloromethane and 8.00 kg of demineralized water were added, followed by stirring for 30 minutes to wash, and then the stirring was stopped and the organic phase (I) and the aqueous phase were separated by a centrifuge. 30 kg of 0.1 N hydrochloric acid was added to the separated organic phase (I), followed by stirring for 30 minutes. After extraction of triethylamine and a small amount of the remaining alkaline components, stirring was stopped to separate the aqueous phase and the organic phase (II). Further, 30 kg of demineralized water was added to the separated organic phase (II) and stirred for 30 minutes, and then stirring was stopped to separate the aqueous phase and the organic phase (III). Subsequently, 30 kg of demineralized water was added to the organic phase (III) again and stirred for 30 minutes, and then the stirring was stopped to separate the aqueous phase and the organic phase (IV).

Four liters of turbine blades were continuously supplied with 20 liters / hour of a dichloromethane solution of the halogen-containing polycarbonate resin obtained above to a 50 liter jacketed granulation tank equipped with a stirrer at two stages. 30 liters / hour of water was introduced, and methylene chloride was evaporated at an internal temperature of 47 ° C. and a stirring speed of 400 rpm while maintaining a suspended state in water to form a halogen-containing polycarbonate resin granule.

Subsequently, a part of the water slurry containing the halogen-containing polycarbonate resin granules extracted from the granulation tank was wet-pulverized, and a 35 liter / hour water slurry was extracted while circulating through the granulation tank to maintain the contents of the granulation tank at 50 liters. . The granular polycarbonate resin obtained by this method has a high bulk density and stably obtains a desired halogen-containing polycarbonate resin granule without adhering agglomeration of particles and generation of block solids in a granulation tank.

The extracted water slurry separated the polycarbonate resin granules by filtration, and was dried at 140 ° C. for 48 hours in a clean oven. The viscosity average molecular weight (Mv) and bromine (Br) concentration of the obtained polycarbonate resin are shown in Table 1.

Next, 0.5 weight part of polypropylene glycol (Mw = 2,000) and the phosphorus compound (tris (2,4-di-tert- butylphenyl) phosphite) 0.05 weight part with respect to 100 weight part of dried halogen containing polycarbonate resin granular bodies. Parts, carboxylic acid ester (glycerine monostearate) 0.1 parts by weight, 1,4-bis (2,6-diethyl-4-hydroxyphenyl) aminoanthraquinone 1.5 × 10 ^-5 parts by weight, and 1,8- A halogen-containing polycarbonate resin composition was prepared by adding 1.5 × 10 ⁻⁵ parts by weight of bis (p-methylamino) phenylanthraquinone with a twin screw extruder and melt kneading. Table 1 shows the chromaticity index b and the opacity (haze) change rate according to the color difference equation of Hunter in the Lab color system after 2 days of gamma ray irradiation on the prepared halogen-containing polycarbonate resin composition.

(Comparative Example 1)

According to Example 1 (column) of Unexamined-Japanese-Patent No. 2005-179549, the halogen containing polycarbonate resin obtained by superposing | polymerizing the following (i) halogen free BPA and (ii) halogen containing BPA was obtained. Then, the halogen containing polycarbonate resin composition was prepared by operation similar to Example 1 with the twin screw extruder. The b value and Haze change rate of the obtained composition are shown in Table 1.

(i) Halogen-free BPA whose number average molecular weight (Mn) is 650 and ratio (CF / OH) of terminal chloroformate group concentration (CF) and terminal hydroxyl group concentration (OH) is 4.0.

(Ii) Halogen-containing BPA whose number average molecular weight (Mn) 3891, ratio (CF / OH) of terminal chloroformate concentration (CF) and terminal hydroxyl group concentration (OH) is 22.4, and bromine (Br) content is 14.4 weight%.

(Comparative Example 2)

Terminal chloroformate group concentration (CF), terminal hydroxyl group concentration (OH), ratio of terminal chloroformate group concentration (CF) to terminal hydroxyl group concentration (OH) (CF / OH) when synthesizing a carbonate oligomer, and the amount of TBA added Is changed as shown in Table 1, and the amount of water and alkali is adjusted so that the amount of residual alkali at the end of polymerization is equivalent to that of Example 1, and the same operations as in Example 1 were performed to otherwise carry out a halogen-containing polycarbonate resin composition. It prepared. The b value and Haze change rate of the obtained composition are shown in Table 1.

(Comparative Example 3)

The addition amount of TBA was adjusted so that it might become the ratio shown in Table 1, and the operation similar to Example 1 was carried out otherwise, and the halogen containing polycarbonate resin composition was prepared. The molecular weight of the obtained halogen-containing polycarbonate resin did not increase even if the polymerization reaction time passed 120 minutes. The b value and Haze change rate of the obtained composition are shown in Table 1.

In addition, TBA in Table 1 shows the density | concentration of tetrabro mobisphenol A which is a halogen containing aromatic dihydroxy compound, and it corresponds to halogen containing aromatic dihydroxy compound concentration (BPX).

From the result of Table 1, the halogen containing polycarbonate resin composition (Example 1) to which this embodiment is applied shows the numerical value of b value after (gamma) ray irradiation, and Haze change rate before and after (gamma) ray irradiation is small, and ionizing radiation is favorable. Able to know.

On the other hand, ratio (CF / TBA) of terminal chloroformate concentration (CF) and tetrabromobisphenol concentration (TBA), and ratio of terminal hydroxyl group concentration (OH) and tetrabromobisphenol concentration (TBA) (OH / TBA) In the case where both of the conditions are excessively small (Comparative Example 1), it can be seen that the Haze change rate is increased and the ionizing radiation is not improved.

Moreover, it turns out that a desired polymer is not obtained when (CF / TBA) and (OH / TBA) are both too large (comparative example 3).

In addition, even under conditions where the terminal chloroformate concentration (CF) and the terminal hydroxyl group concentration (OH) (CF / OH) are excessively small (Comparative Example 2), it is understood that the Haze change rate is increased so that the ionizing radiation is not improved. have.

As mentioned above, as described in detail, the halogen-containing polycarbonate resin excellent in the color tone stability at the time of ionizing radiation can be efficiently manufactured by the manufacturing method of the halogen-containing polycarbonate resin to which this embodiment is applied, and it uses it. It can be used for various medical instruments such as housing material for artificial dialysis.

Claims (9)

A halogen-containing polycarbonate resin composition containing a halogen-containing polycarbonate resin and a carboxylic acid ester and a phosphorus compound, 2 days after irradiation of gamma rays of 25 kGy under oxygen blocking, the chromaticity index b in the color difference equation of the Hunter of the Lab colorimeter is 3.50 or less, and the change rate of the soak (haze) is 10% or less. Halogen-containing polycarbonate resin composition. The method of claim 1, 0.01 weight part-1 weight part of said carboxylic acid ester, and 0.01 weight part-1 weight part of phosphorus compounds with respect to 100 weight part of said halogen-containing polycarbonate resins, The halogen-containing polycarbonate resin composition characterized by the above-mentioned. The method of claim 1, Halogen content of the said halogen-containing polycarbonate resin is 0.1 weight%-2 weight%, The halogen-containing polycarbonate resin composition characterized by the above-mentioned. The method of claim 1, The halogen-containing polycarbonate resin composition, wherein the carboxylic acid ester is an aliphatic carboxylic acid ester, and the phosphorus compound is a phosphite ester. A medical device formed by molding using the halogen-containing polycarbonate resin composition according to claim 1. As a manufacturing method of the halogen containing polycarbonate resin used for the halogen containing polycarbonate resin composition of Claim 1, An oligomer synthesis step of synthesizing a carbonate oligomer by reacting an alkali metal or an alkaline earth metal compound of an aromatic dihydroxy compound containing no halogen with carbonyl chloride, and It has a polymerization process which polymerizes the alkali metal or alkaline-earth metal compound of the said carbonate oligomer synthesize | combined by the said oligomer synthesis process, and a halogen containing aromatic dihydroxy compound and / or a halogen containing aromatic dihydroxy compound, The ratio (CF / BPX) of the terminal chloroformate concentration (CF) and the halogen-containing aromatic dihydroxy compound concentration (BPX) in the carbonate oligomer in the polymerization step is 10 to 60 (equivalent ratio), and the The ratio (OH / BPX) of the terminal hydroxyl group concentration (OH) in the carbonate oligomer to the halogen-containing aromatic dihydroxy compound concentration (BPX) is 4.5 to 27 (equivalent ratio), The ratio (CF / OH) of the terminal chloroformate concentration (CF) in the carbonate oligomer and the terminal hydroxyl group concentration (OH) in the carbonate oligomer is 1.5 to 3.0 (equivalent ratio). . The method of claim 6, The said carbonate oligomer has a repeating unit represented by Structural formula (1), The manufacturing method of the halogen-containing polycarbonate resin characterized by the above-mentioned. [Formula 1]

The method of claim 6, The said halogen-containing aromatic dihydroxy compound is tetrabromobisphenol A represented by the compound (2), The manufacturing method of the halogen-containing polycarbonate resin characterized by the above-mentioned. [Formula 2]

The method of claim 6, The halogen content of the said halogen containing polycarbonate resin is 0.1 weight%-2 weight%, The manufacturing method of the halogen containing polycarbonate resin characterized by the above-mentioned.