JPH10130383A - Terminal-modified aromatic polycarbonate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new resin giving a wet-molded article having an excellent oil resistance and durability especially to oil, alcohol, etc., by modifying the terminal of a polycarbonate with a terminal blocking agent consisting of a specific compound. SOLUTION: The molecular terminal of the objective polycarbonate derived from a disphenol has a terminal group derived from a compound of the formula (R1 is a 1-20C perfluoroalkyl; R2 and R3 are each H, F, etc.; (a) is 1-4; (c) is 0-4) and the polycarbonate has an intrinsic viscosity of 0.03-2dL/g. The bisphenol A to be used as a raw material for the objective resin is preferably 2,2-bis(4- hydroxyphenyl)propane, etc., and the compound of the formula is preferably α-p-hydroxybenzoyl-ω-prefluorooctyloxy-poly(oxyethylene), etc. The objective resin can be produced by adding the terminal blocking agent of the formula after completing the blowing of phosgene in a phosgenation process using a bisphenol and phosgene as raw materials and carrying out the polymerization reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel terminal-modified polycarbonate, and more particularly, to a polycarbonate having a terminal group having a special fluoroalkyl structure and a method for producing the same. The terminal-modified aromatic polycarbonate of the present invention by itself can provide polycarbonate sheets, films and other molded products excellent in oil stain resistance.

[0002]

2. Description of the Related Art Polycarbonate resins are known as engineering plastics exhibiting excellent transparency and mechanical strength, and are widely used in molding materials for automobiles, electricity, electronics, sundries and the like. Among them, polycarbonate films are used in various fields utilizing excellent transparency and mechanical properties. Production of polycarbonate films is broadly classified into extrusion molding and wet molding. Among them, the wet molding has an advantage that a thin film can be easily obtained and a non-oriented film can be obtained, and is used for production of a functional film.

In particular, films and sheets used in the electric and mechanical fields must be resistant to environmental pollution (dirt) by oils such as lubricating oils and organic solvents such as alcohol for cleaning. When the lubricating oil or alcohol penetrates into the polycarbonate, local cracks called stress crazes and stress cracks, which are considered to be caused by internal strain, easily occur, and strength and appearance are reduced. In an ordinary extruded film, Teflon or a fluorine-based additive having a small surface free energy and preventing the penetration and diffusion of oils is used to suppress the adhesion of oil and the like. However, when Teflon is blended with polycarbonate, the film becomes cloudy due to the difference in the refractive index, and the compatibility is poor and a transparent and strong film cannot be obtained by wet molding. Also, when a fluorine-based additive is used, a film containing the fluorine-based additive cannot be obtained in wet molding because the phase separation of the fluorine-based additive and the polycarbonate occurs due to a difference in surface free energy.

[0004]

On the other hand, polycarbonates containing a fluoroalkyl group at the molecular terminal of the polycarbonate have been developed for the purpose of improving the flowability and the releasability when injection molding an aromatic polycarbonate. However, although a wet-molded film using this material has a certain degree of water repellency, it is not sufficiently satisfactory in terms of oil stain resistance, and further oil stain resistant polycarbonates are commercially available. Had been requested.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the conventional problems, and as a result, when producing an aromatic polycarbonate, a fluoroalkyl group derived from a polyether is contained as a terminal stopper in the production of an aromatic polycarbonate. The terminal-modified aromatic polycarbonate obtained using phenol is excellent in oil stain resistance, and in particular, a wet-molded product using the terminal-modified aromatic polycarbonate of the present invention is found to have excellent durability against oil, alcohol, and the like, Based on this finding, the present invention has been completed. That is, the present invention relates to a terminal-modified aromatic compound having a molecular terminal of a polycarbonate derived from a bisphenol having a terminal group derived from a compound represented by the following general formula (1) and having an intrinsic viscosity of 0.03 to 2.0 dl / g. The present invention provides an aromatic polycarbonate.

[0006]

Embedded image

(Wherein, R ₁ represents a perfluoroalkyl group having 1 to 20 carbon atoms, and R _{2 to} R ₃ each represent hydrogen, fluorine, chlorine, bromine or an alkyl group having 1 to 8 carbon atoms. A represents a number of 1 to 4, b represents a number of 1 to 20, and c represents a number of 0 to 4.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The terminal-modified aromatic polycarbonate of the present invention basically comprises a fluoroalkyl-containing phenol derived from the compound represented by the general formula (1) as a terminal stopper. It can be obtained in the same manner as in the conventional method for producing an aromatic polycarbonate.

The bisphenols used as a raw material for deriving the terminal-modified polycarbonate of the present invention are specifically 4,4'-
Biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis ( 4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxy Phenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4 -Hydroxyphenyl) hexafluoropropane, α, ω-bis [2- (p-hydroxyphenyl)
Ethyl] polydimethylsiloxane, α, ω-bis [3-
(O-hydroxyphenyl) propyl] polydimethylsiloxane, 9,9-bis (4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 4,4 '-[1, 4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 '-[1,3-phenylenebis (1-
Methylethylidene)] bisphenol, 1,1,3-trimethyl-3-[(4-hydroxy) phenyl] -5-hydroxyindane, 3,3,3 ′, 3′-tetramethyl-2,3,2 ′, Examples include 3′-tetrahydro- (1,1′-spirobiindene) -6,6′-diol. These can be used in combination of two or more.

[0010] Of these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-
3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, α, ω-bis [3- (O-hydroxyphenyl)
[Propyl] polydimethylsiloxane.

The compound represented by the general formula (1) used as the terminal blocking agent (molecular weight regulator) of the present invention is, for example, a transesterification of an alkylene oxide adduct of a fluoroalkyl alcohol with an alkyl p-hydroxybenzoate. It can be easily produced by performing a reaction. For this reason, the number of oxyalkylene binding moieties in the terminal blocking agent of the present invention may vary during production, and may have a distribution.

As the terminal blocking agent (molecular weight regulator) of the present invention, specifically, α-p-hydroxybenzoyl-ω-perfluorobutoxy-poly (oxyethylene), α-
p-hydroxybenzoyl-ω-perfluorooctyloxy-poly (oxyethylene), α-p-hydroxybenzoyl-ω-perfluorodecyloxy-poly (oxyethylene), α-p-hydroxybenzoyl-ω-
Perfluorohexyloxy-poly (oxyethylene), α-p-hydroxybenzoyl-ω-perfluorododecyloxy-poly (oxyethylene), α-o-
Hydroxybenzoyl-ω-perfluorooctyloxy-poly (oxyethylene), α-o-hydroxybenzoyl-ω-perfluorodecyloxy-poly (oxyethylene), α-o-methyl-p-hydroxybenzoyl-ω-per Fluorooctyloxy-poly (oxyethylene), α-o-methyl-p-hydroxybenzoyl-ω-perfluorodecyloxy-poly (oxyethylene), α-p-hydroxybenzoyl-ω-perfluorooctyloxy-poly ( Oxymethylene), α-p-
Hydroxybenzoyl-ω-perfluorodecyloxy-poly (oxymethylene), α-p-hydroxybenzoyl-ω-perfluorooctyloxy-poly (oxytrimethylene), α-p-hydroxybenzoyl-ω-
Perfluorooctyloxy-poly (oxytetramethylene), α-p-hydroxybenzoyl-ω-perfluorodecyloxy-poly (oxytrimethylene), α-
p-hydroxybenzoyl-ω-perfluorooctyl-2-ethoxy-poly (oxyethylene), α-p-hydroxybenzoyl-ω-perfluorodecyl-2-ethoxy-poly (oxyethylene), α-p-hydroxybenzoyl -Ω-perfluorooctyl-3-methoxy-poly (oxyethylene) and the like. These are 2
You may use in combination of types or more. Among them, α-p-hydroxybenzoyl-ω from the viewpoint of reactivity and physical properties
-Perfluorooctyloxy-poly (oxyethylene) and α-p-hydroxybenzoyl-ω-perfluorooctyl-2-ethoxy-poly (oxyethylene) are more preferred.

The amount of the terminal blocking agent represented by the general formula (1) is 200 to 200 moles per 100 moles of the bisphenol compound.
It is in the range of 0.5 mol, preferably 100 to 2 mol.

Further, it is possible to use the phenol of the general formula (1) together with a conventional terminal blocking agent.

Conventional terminal blocking agents include phenol,
Phenols such as pt-butylphenol, cumylphenol, tribromophenol, long-chain alkylphenols, alkyletherphenols, hydroxybenzoic acid alkylesters and the like, aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic acid chlorides, aromatic acids Chloride and the like.

These conventional terminal capping agents are used in the range of maintaining the oil stain resistance in the present invention, and are all terminal capping agents (total amount of the terminal capping agent of the present invention and the conventional terminal capping agent). Is preferably less than 50 mol%, more preferably less than 30 mol%.

As the method for producing the terminal-modified aromatic polycarbonate of the present invention, a known method used for producing an aromatic polycarbonate from bisphenols, for example, a direct reaction of bisphenols with phosgene (phosgene method), or A method such as transesterification (transesterification method) between bisphenols and bisaryl carbonate can be employed. In the production of the terminal-modified polycarbonate of the present invention, the phosgene method is preferred from the viewpoint of easily forming a terminal group derived from the compound represented by the general formula (1).

In the former phosgene method, bisphenols and phosgene are usually reacted in the presence of an acid binder and a solvent inert to the reaction. As the acid binder, for example, pyridine, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and the like are used.
Further, a polymerization catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to accelerate the polycondensation reaction. Also, if desired, sodium sulfite, an antioxidant such as hydrosulfite,
A small amount of a branching agent such as phloroglucin or isatin bisphenol or an esterifying agent such as a divalent carboxylic acid or a derivative thereof may be added.

The reaction temperature is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. The reaction time varies depending on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction,
It is desirable to maintain the pH of the reaction system at 10 or higher.

On the other hand, in the latter transesterification method,
The bisphenols and the bisaryl carbonate are mixed, and the compound represented by the general formula (1) is used as a terminal blocking agent in the presence of a basic catalyst such as an alkali metal compound. Let react. The reaction temperature is usually from 150 to 350 ° C, preferably from 200 to 3 ° C.
It is performed in the range of 00 ° C. The degree of reduced pressure is preferably 1 mmHg or less at the end of the reaction, and phenols derived from the bisaryl carbonate by-produced by the transesterification are distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction, but is usually about 1 to 4 hours. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. Also, if desired, an antioxidant,
The reaction may be performed by adding a branching agent and an esterifying agent.

Solvents used in the phosgene method include dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, and dichlorobenzene. Chlorinated hydrocarbons such as chlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ether compounds such as diethyl ether can be used. These organic solvents are used as a mixture of two or more kinds. You can also. If desired, a solvent having an affinity for water such as ethers, ketones, esters, and nitriles other than those described above may be used as long as the mixed solvent system is not completely compatible with water.

The polymerization catalyst for the phosgene method includes tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline and dimethylaniline. Quaternary amines; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride.

Further, a branched agent may be used in combination with the bisphenols in the range of 0.01 to 50 mol%, particularly 0.1 to 20 mol%, to form a branched polycarbonate.
As a branching agent, phloroglucin, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-
2,1,3,5-tri (2-hydroxyphenyl) benzol,
1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tri (4-hydroxyphenyl )
Polyhydroxy compounds exemplified by -1,3,5-triisopropylbenzene and the like, and 3,3-bis (4-hydroxyphenyl) oxindole (= isatin bisphenol)
And the like.

Further, as esterifying agents, aliphatic dicarboxylic acids such as adipic acid, terephthalic acid, and aromatic dicarboxylic acids such as 5- [perfluoro (2-isopropyl-1,3-dimethyl-butenyl) oxy] isophthalic acid Polyester carbonate can also be obtained by using an acid or a derivative thereof such as acid chloride or carboxylate in the range of 0.1 to 20 mol%.

The terminal-modified polycarbonate of the present invention can be molded by a general molding method such as extrusion molding, compression molding, injection molding, blow molding or wet molding. A polymer suitable for molding is 0.03 to 2.0 dl / g. A high molecular weight substance having an intrinsic viscosity of 2.0 is preferred.
If it is not more than 03 dl / g, the mechanical strength as a molded product is insufficient.

The terminal-modified polycarbonate of the present invention is resistant to environmental pollution (dirt) of oils such as lubricating oil and organic solvents such as washing alcohol, and is suitably used as a film or sheet. Often produce films and sheets. In the present invention, a solvent used for wet molding such as a solution casting method or a casting method can be used as long as it dissolves the terminal-modified polycarbonate of the present invention and has appropriate volatility. For example, halogen solvents such as chlorobenzene and methylene chloride, hydrocarbon solvents exemplified by toluene, xylene, ethylbenzene and the like, and cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane are preferable. The concentration of the solvent is usually 1 to 30% by weight, preferably 5 to 20% by weight.

Further, the terminal-modified polycarbonate of the present invention can be arbitrarily added in order to impart oil stain resistance, mold releasability and slipperiness to the thermoplastic resin. In order to sufficiently exert the effect of addition, it is necessary to add at least 0.01% by weight or more. Examples of the thermoplastic resin include polyethylene, polypropylene, ABS, polystyrene, PMMA, polyester, polycarbonate, polyacetal, polyphenylene oxide, polyamide, polyester carbonate, and various liquid crystal polymers.

[0028]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 91.2 of 2,2-bis (4-hydroxyphenyl) propane (abbreviation: BPA) was added to 610 ml of an aqueous 8.8% (w / v) sodium hydroxide solution.
g (0.4 mol) and 0.1 g of hydrosulfite were added and dissolved. 360 ml of methylene chloride was added thereto, and 50 g of phosgene was blown in over 50 minutes while stirring at 15 ° C. After blowing, the following structure

[0030]

Embedded image

3.44 g (0.005 mol) of α-p-hydroxybenzoyl-ω-perfluorooctyloxy-poly (oxyethylene) (FPOB1 manufactured by Kyoeisha Chemical Co., Ltd.)
And agitate vigorously to emulsify the reaction solution.
0.2 ml of triethylamine was added, and the mixture was stirred at 20 to 25 ° C. for about 1 hour to carry out polymerization.

After the completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and the washing is repeated until the pH of the washing solution becomes neutral. The reaction solution was added dropwise to warm water at about 45 ° C., and 470 ml of isopropanol was further added to precipitate a polymer. After filtering the obtained precipitate,
After drying, a powdery polymer was obtained. This polymer had an intrinsic viscosity [η] of 0.75 dl / g at a temperature of 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent.

The results of the obtained above polymer was analyzed from the infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, having a carbonate bond Was confirmed. FIG. 1 shows the IR chart. When the monomer in this polycarbonate was measured by GPC analysis, FPOB
1 was 65 ppm and BPA was 20 ppm or less.

Example 2 The same procedure as in Example 1 was carried out except that the amount of FPOB1 was changed to 6.88 g (0.01 mol). The intrinsic viscosity [η] of the obtained polymer was 0.38 dl / g, and it was confirmed by infrared absorption spectrum analysis and the like that the polymer had a carbonate bond.

Example 3 In place of BPA, 107.2 g (0.4 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (abbreviation: BPZ) was used.

[0036]

Embedded image

3.78 g of α-p-hydroxybenzoyl-ω-perfluorooctyl-2-ethoxy-poly (oxyethylene) (FPOB2, manufactured by Kyoeisha Chemical Co., Ltd.)
(0.005 mol) was carried out in the same manner as in Example 1 except that it was used. The intrinsic viscosity [η] of the obtained polymer was 0.70 dl / g, and it was confirmed by infrared absorption spectroscopy and the like that the polymer had a polycarbonate bond.

Example 4 The procedure of Example 1 was repeated, except that 102.4 g (0.4 mol) of 2,2-bis (4-hydroxy-3-methylphenyl) propane (abbreviation: DMBPA) was used instead of BPA. Was. The intrinsic viscosity [η] of the obtained polymer was 0.69 dl / g, and it was confirmed by infrared absorption spectrum and the like that this polymer had a polycarbonate bond.

Example 5 91.2 g of BPA was mixed with 45.6 g (0.2 mol) of BPA and 40.4 g (0.2 mol) of bis (4-hydroxyphenyl) ether (abbreviation: DHPE)
The procedure was performed in the same manner as in Example 1 except for changing to. The intrinsic viscosity [η] of the obtained polymer was 0.77 dl / g, and it was confirmed by infrared absorption spectrum and the like that this polymer had a polycarbonate bond.

Example 6 Along with BPA, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane (abbreviation: S
i) The procedure was the same as in Example 1 except that 18.1 g (0.01 mol) was added. The intrinsic viscosity [η] of the obtained polymer is 0.68 dl / g
The infrared absorption spectrum and the like confirmed that this polymer had a polycarbonate bond.

Comparative Example 1 The same operation as in Example 1 was performed except that FPOB1 was not used. However, it became an ultra-high molecular weight compound during polymerization, and a solvent-insoluble gel was generated. Analysis not possible due to solvent insolubility.

Comparative Example 2 The procedure of Example 1 was repeated, except that FPOB1 was replaced by 0.75 g (0.005 mol) of pt-butylphenol (PTBP), a typical terminal blocking agent. The intrinsic viscosity [η] of the obtained polymer was 1.01 dl / g, and it was confirmed by infrared absorption spectrum and the like that the polymer had a polycarbonate bond.

Comparative Example 3 Instead of FPOB2, pt-butylphenol (abbreviation: PTB)
P) The same operation as in Example 3 was carried out except that 0.75 g (0.005 mol) was used. The intrinsic viscosity [η] of the obtained polymer is 0.86 dl.
/ g, it was confirmed from infrared absorption spectrum and the like that this polymer had a polycarbonate bond.

Comparative Example 4 The following structure was used instead of FPOB1.

[0045]

Embedded image

The procedure was performed in the same manner as in Example 1 except that 3.28 g (0.005 mol) of perfluorodecyl salicylate (abbreviation: PFDS) was used. The intrinsic viscosity [η] of the obtained polymer was 0.94 dl / g, and it was confirmed by infrared absorption spectrum and the like that this polymer had a polycarbonate bond.

The compositions and analytical values of the polycarbonate resins of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1. Table 2 shows a comparison of oil contamination resistance of the wet molded products of Examples 1 to 6 and Comparative Examples 2 to 4. In addition, FIGS. 1 and 2 show infrared absorption spectra of the polycarbonates of Example 1 and Example 2.

[0048]

[Table 1] Examples and Comparative Examples Example 1 Actual 2 Actual 3 Actual 4 Actual 5 Actual 6 Terminal sealant FPOB1 FPOB1 FPOB2 FPOB1 FPOB1 FPOB1 (× 10 ^-2 mol) 0.5 1.0 0.5 0.5 0.5 0.5 Bisphenol BPA BPA BPZ DMBPA BPA BPA (mol) 0.4 0.4 0.4 0.4 0.2 0.4 Bisphenol --- --- --- --- DHPE Si (mol) --- --- --- --- 0.2 0.01 Intrinsic viscosity (dl / g) 0.75 0.38 0.70 0.69 0.77 0.68 IR (Carbonate bond) Yes Yes Yes Yes Yes Yes Yes Residual FPOB concentration (ppm) 65 89 ND ND 72 ND Examples and comparative examples Ratio 1 Ratio 2 Ratio 3 Ratio 4 Terminal sealant --- PTBP PTBP PFDS (× 10 ^-2 mol) --- 0.5 0.5 0.5 Bisphenol BPA BPA BPZ BPA (mol) 0.4 0.4 0.4 0.4 Bisphenol --- --- --- --- (mol) --- ---- ---- Intrinsic viscosity (dl / g) --- 1.01 0.86 1.05 IR (carbonate bond) --- Yes Yes Yes Residual FPOB concentration (ppm) --- --- --- ---

The abbreviations in the table are described below. BPA: 2,2-bis (4-hydroxyphenyl) propane BPZ: 1,1-bis (4-hydroxyphenyl) cyclohexane DMBPA: 2,2-bis (4-hydroxy-3-methylphenyl) propane DHPE: bis ( 4-hydroxyphenyl) ether Si: α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane PTBP: pt-butylphenol PFDS: salicylic acid perfluorodecyl ester FPOB1: α-p-hydroxybenzoyl-ω- Perfluorooctyloxy-poly (oxyethylene) FPOB2: α-p-hydroxybenzoyl-ω-perfluorooctyl-2-ethoxy-poly (oxyethylene) IR: Absorption by carbonyl near 1770 cm ⁻¹ from infrared absorption spectrum , And absorption by an ether bond near 1240 cm ^-1 . Residual FPOB: FPOB1 and FPOB2 components were separated and quantified by GPC manufactured by Waters. ND is below the detection limit and below 60 ppm. Intrinsic viscosity: 20 ° C of 0.5g / 100cc dichloromethane resin solution
, And the limiting viscosity [η] (dl / g) was determined with the Huggins constant set to 0.45.

[0050]

[Table 2] Drop size of each drop (mm) Examples and Comparative Examples Methanol n-heptane Example 1 8.0 9.5 Example 2 8.0 9.5 Example 3 8.0 9.0 Example 4 8.0 9.0 Example 5 8.0 9.5 Example 6 8.0 9.0 Comparative Example 2 34.0 20.0 Comparative Example 3 12.0 17.0 Comparative Example 4 9.0 10.5

Test pieces: Each sample was dissolved in dichloromethane to make a 12 wt / vol% resin solution, and wet molding was performed on a glass plate. The film obtained by wet molding was used as a test piece after drying. (Film thickness: about 40 μm) Droplet diameter: 25 μl each of methanol and heptane were vertically dropped on the obtained film (air surface). Measure the maximum diameter of the circular spread of the droplet in each of the vertical and horizontal directions,
The average value was defined as the droplet diameter. The smaller the droplet, the more it repels oil and shows oil stain resistance.

[0052]

The molded article using the terminal-modified aromatic polycarbonate of the present invention has a small surface free energy and prevents adhesion and diffusion of oils. Ideal for goods. Further, as a polymer additive containing fluorine, it can be used as an agent for improving the releasability, lubricity and oil resistance of various plastics.

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of the polycarbonate obtained in Example 1.

FIG. 2 shows an infrared absorption spectrum of the polycarbonate obtained in Example 3.

Claims (7)

[Claims] 1. A molecular terminal of a polycarbonate derived from a bisphenol has a terminal group derived from a compound represented by the following general formula (1), and has an intrinsic viscosity of 0.03 to 2.0 d.
l / g, a terminal-modified aromatic polycarbonate. Embedded image (Wherein, R ₁ represents a perfluoroalkyl group having 1 to 20 carbon atoms; R _{2 to} R ₃ each represent hydrogen, fluorine, chlorine, bromine or an alkyl group having 1 to 8 carbon atoms; 1
-4, b represents a number of 1-20, and c represents a number of 0-4. ) 2. A compound represented by the general formula (1):
R ₁ represents a perfluoroalkyl group having 6 to 20 carbon atoms, R ₂ to R ₃ represent hydrogen, terminal-modified aromatic polycarbonate according to claim 1, wherein. 3. The compound represented by the general formula (1)
α-p-hydroxybenzoyl-ω-perfluorooctyloxy-poly (oxyethylene) or α-p-hydroxybenzoyl-ω-perfluorooctyl-2-
The terminal-modified aromatic polycarbonate according to claim 1, which is ethoxy-poly (oxyethylene). 4. The bisphenols are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 2,2-bis (4-hydroxy-3-methylphenyl) propane , 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, α, ω-bis [3- (o-hydroxyphenyl) Propyl] polydimethylsiloxane. 5. A method for producing a polycarbonate by a phosgene method using bisphenols and phosgene as raw materials,
The method for producing a terminal-modified aromatic polycarbonate according to claim 1, wherein a terminal blocking agent comprising the compound represented by the general formula (1) is added after phosgene blowing is completed, and a polymerization reaction is subsequently performed. 6. A method for producing a polycarbonate by a phosgene method using bisphenols and phosgene as raw materials,
The polymerization reaction is carried out by adding a terminal blocking agent comprising the compound represented by the general formula (1) after the completion of phosgene blowing, then bringing the reaction mixture into an emulsified state, further adding a catalyst, and performing a polymerization reaction. For producing terminal-modified aromatic polycarbonates. 7. A wet molded product using the terminally modified aromatic polycarbonate according to claim 1 as a raw material.