JPH05247197A - Polycarbonate resin having improved adhesivity to metal - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin useful as optical discs, optical cards, various deposited films, etc., having excellent adhesivity to deposited metal films. CONSTITUTION:A polycarbonate resin obtained by using a cyano group or nitro group-containing end terminator, having an amount of cyano group or nitro group of one or more groups based on 100 carbonate units.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin having excellent adhesion to metal. More specifically, it relates to a polycarbonate resin having excellent adhesion to a vapor-deposited metal film.

[0002]

2. Description of the Related Art Conventionally, a polycarbonate resin has been widely used as a substrate for an information recording medium in the field of optical disks and the like. However, the aluminum vapor deposition film formed on the substrate of the polycarbonate resin does not have sufficient adhesion to the substrate, and there remains a problem that the aluminum vapor deposition film peels off during long-term storage under high temperature and high humidity.

In order to remedy the above-mentioned drawbacks, polycarbonate resins using various end terminators have been investigated. For example, JP-A-63-179301 and JP-A-6-
3-182350 proposes a method of using a salicylic acid ester, a hydroxybenzoic acid ester, or the like as a terminal stopper. However, since such an end-capping agent has an ester group, it has a drawback that hydrolysis is likely to occur in a normal interfacial polymerization method, and transesterification occurs in a melt-polymerization method, so that it does not function as an end-terminating agent.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin which is useful for optical discs, optical cards, various vapor deposition films, vapor deposition plastic reflecting mirrors and the like and which has excellent adhesion to vapor deposited metal films. ..

The inventor of the present invention aims to achieve the above object.
As a result of diligent studies on the terminal terminator of the polycarbonate resin, it was found that the terminal modified polycarbonate resin using the terminal terminator having a cyano group or a nitro group as the terminal terminator is extremely excellent in adhesion to the vapor-deposited metal film. This has led to the completion of the present invention.

[0006]

The present invention is a polycarbonate resin modified with an end-capping agent having at least one cyano group or nitro group, the amount of said cyano group or nitro group per 100 carbonate units. The present invention relates to a polycarbonate resin having one or more excellent metal adhesion.

The polycarbonate resin of the present invention comprises a carbonate unit 1 having a cyano group or a nitro group at the terminal.
It is a polycarbonate resin provided with one or more per 00 pieces. If the amount of the cyano group or the nitro group does not reach the above amount, the adhesion with the vapor-deposited metal film is insufficient and the object of the present invention cannot be achieved.

The polycarbonate resin having excellent metal adhesion can be produced by any method. For example, as described below, it is produced by reacting one or more dihydric phenols with a carbonate precursor and an end-capping agent having at least one cyano group or nitro group.

As the dihydric phenol used here,
For example, bis (4-hydroxyphenyl) methane, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis ( 4-hydroxy-
3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5-dichloro-4-hydroxyphenyl) oxide, p, p'-dihydroxydiphenyl, 3,3'-dichloro-4, 4 '
-Dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy Examples thereof include -3-methylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like. Particularly, 2,2-bis (4-hydroxyphenyl) propane is preferable.

A preferred method for producing a polycarbonate resin having excellent metal adhesion is an interfacial polycondensation reaction using phosgene. In this method, dihydric phenol is usually dissolved in an aqueous solution of an acid binder and phosgene is added in the presence of a solvent. React. As the acid binder, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used, and as the solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are preferably used. The reaction is usually 0 to 40 ° C, preferably 20 to 30 ° C for 10 minutes to 1
It will be finished in about 0 hours. The pH of the reaction system is preferably maintained at 10 or higher. Also, a catalyst may be used to accelerate the reaction. Examples of the catalyst include tertiary amines such as triethylamine, pyridine, tetra-n-butylammonium bromide, and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds.

The terminating agent having a cyano group or a nitro group is selected within a range in which a polycarbonate having a desired viscosity average molecular weight can be obtained, and may be used from the start of the reaction,
It may be added after the oligomer is produced. When the reactivity of the terminal terminator is low, the organic layer may be taken out from the reaction mixture after the oligomer is produced, added to this, sufficiently reacted and then returned to the original state to restart the polymerization. Further, an antioxidant can be added if necessary.

Examples of the terminator used here include 2-cyanophenol, 3-cyanophenol and 4-cyanophenol.
Cyanophenol, 2-cyanomethylphenol, 3-
Cyanomethylphenol, 4-cyanomethylphenol
2-nitrophenol, 3-nitrophenol, 4
-Nitrophenol, 3,4-dicyanophenol, picric acid, 2-methyl-4-nitrophenol, 3-methyl-4-cyanophenol, 3-methoxy-4-cyanophenol, 3-ethoxy-4-cyanophenol,
3-phenoxy-4-cyanophenol, 4-hydroxy-3-cyanobenzophenone, 4-hydroxy-3-
Cyanophenyl phenyl sulfide, 4-hydroxy-
3-cyanophenyl phenyl sulfoxide, 4-hydroxy-3-cyanophenyl phenyl sulfone, 4-benzyl-2-cyanophenol, 4-hydroxy-4'-
Examples thereof include phenols such as cyanodiphenyl, 4-hydroxy-2′4′6′-trinitrodiphenyl, 1-hydroxy-5-cyanonaphthalene, acid chlorides such as 4-cyanobenzoyl chloride.

The amount used is such that a predetermined amount of cyano group or nitro group is bonded to the terminal of the polycarbonate resin,
The amount is 1 to 20 mol%, preferably 2 to 15 mol% based on the dihydric phenol usually used. Further, if a predetermined amount of cyano group or nitro group is ensured, an ordinary terminal terminator such as p-tert-butylphenol may be used in combination.

Another preferable method for producing a polycarbonate resin having excellent metal adhesion is a transesterification reaction using a carbonic acid diester. In this method, a dihydric phenol, a carbonic acid diester, and a cyano acid are prepared under an inert gas atmosphere. It is carried out by mixing an end terminating agent having a group or a nitro group, stirring the mixture with heating, and distilling the produced alcohol or phenol. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate,
Examples thereof include diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferable. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the produced alcohol or phenol to complete the reaction.

As the terminal terminator, in addition to the terminal terminators having a phenolic hydroxyl group exemplified in the above-mentioned interfacial polymerization method, benzoic acid esters such as 4-cyanobenzoic acid phenyl ester and 4-nitrobenzoic acid phenyl ester,
Examples include 4-cyanobenzoic acid and 4-nitrobenzoic acid. The amount used is such that a predetermined amount of cyano group or nitro group is bonded to the terminal of the polycarbonate resin, and is usually 1 to 20 mol%, preferably 2 to 15 mol% based on the dihydric phenol usually used. Further, a terminal stopper such as p-tert-butylphenol may be used in combination.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal salts of hydroxides of boron and aluminum, alkaline earth metal salts, Quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron compounds,
Examples thereof include catalysts used for usual transesterification reaction of silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. Such catalysts may be used alone or in combination of two or more.
The amount of the catalyst used is 0.00 with respect to the dihydric phenol as a raw material.
It is selected in the range of 01 to 1% by weight, preferably 0.0005 to 0.5% by weight.

The terminal-modified polycarbonate resin having a predetermined amount of cyano group or nitro group thus obtained can be used as it is as a molding material, or can be added to an ordinary unmodified polycarbonate resin in the amount of cyano group or nitro group. May be mixed so as to satisfy the above predetermined amount and used as a molding material. The degree of polymerization is not particularly limited, but when the terminal-modified polycarbonate resin is used as it is as a molding material, the viscosity average molecular weight is usually 100.
It is in the range of 00 or more, preferably 13,000 to 40,000, and when it is used as a mixture with an ordinary unmodified polycarbonate resin, a lower molecular weight one can be used.

[0018]

EXAMPLES The present invention will be further described below with reference to examples. In the examples,% and parts are% by weight and parts by weight unless otherwise specified. The adhesion test was measured by a cross cut test according to JIS H4001.

[0019]

Example 1 2,2-bis (4-hydroxyphenyl)
Propane 100 parts, 48% sodium hydroxide aqueous solution 85
Parts and 400 parts of distilled water were charged and dissolved in a reactor equipped with a stirrer. To this, 330 parts of methylene chloride was added, the mixed solution was cooled to 20 ° C., and 50 parts of phosgene was blown thereinto over 40 minutes. Then, a solution prepared by dissolving 6.37 parts of 4-cyanophenol in methylene chloride was added to the reaction solution, and 4
12 parts of 8% sodium hydroxide aqueous solution and 0.15 parts of triethylamine were added and stirred for 2 hours. After completion of the reaction, a lower layer methylene chloride solution of polycarbonate is separated from the reaction solution, and the solution is washed with an aqueous hydrochloric acid solution and distilled water, and then methylene chloride is removed by evaporation to give 100 cyano groups at the end of carbon unit units. Polycarbonate resin having 3.3 pieces per one was obtained. The viscosity average molecular weight of the obtained resin was 15,300. The obtained resin is extruded with a uniaxial vent type extruder to form pellets, and the pellets are used to obtain a resin temperature of 340 ° C., a mold temperature of 110 ° C., and an outer diameter of 130 mm,
A 1.2 mm thick disc is injection molded and 2 x 10 is formed on this disc.
An aluminum layer of about 1000 angstrom was vacuum-deposited at a vacuum degree of ^-5 Torr, and a protective film made of an ultraviolet curable resin was further formed, and then an aluminum adhesion test was conducted. As a result, the peeled portion was 10/100. .

[0020]

Comparative Example 1 An unmodified polycarbonate resin having a viscosity average molecular weight of 15,000 was obtained in the same manner as in Example 1 except that 4.0 parts of 4-tert-butylphenol was used instead of 6.37 parts of 4-cyanophenol. . When this resin was used for molding, vapor deposition and aluminum adhesion test in the same manner as in Example 1, the peeled portion was 95/100.

[0021]

Example 2 10 parts of the polycarbonate resin having a cyano group at the terminal obtained in Example 1 and 20 parts of the unmodified polycarbonate resin obtained in Comparative Example 1 were mixed to obtain a terminal cyano group. Car
A mixed resin having 1.1 units per 100 unit units was obtained. Molded in the same manner as in Example 1 using this mixed resin,
As a result of vapor deposition and an aluminum adhesion test, the peeled portion was 25/100.

[0022]

Example 3 The procedure of Example 1 was repeated except that 7.43 parts of 4-nitrophenol was used instead of 6.37 parts of 4-cyanophenol. A polycarbonate resin having 3.6 units per 100 units was obtained. When this resin was molded, vapor-deposited and tested for aluminum adhesion in the same manner as in Example 1, the peeled portion was 5/100.

[0023]

Example 4 A viscosity average molecular weight of 19000 was obtained in the same manner as in Example 1 except that 3.56 parts of 4-cyanomethylphenol was used instead of 6.37 parts of 4-cyanophenol.
A polycarbonate resin having 2.7 cyanomethyl groups per terminal at 100 carbon units was obtained. When this resin was molded, vapor-deposited and tested for aluminum adhesion in the same manner as in Example 1, the peeled portion was 35/100.

[0024]

Comparative Example 2 90 parts of the polycarbonate resin obtained in Comparative Example 1 was mixed with 10 parts of the polycarbonate resin having a cyano group at the terminal obtained in Example 1 to cover the terminal cyano group. Bonnet
A mixed resin having 0.3 units per 100 units was obtained. Using this mixed resin, molding and vapor deposition were carried out in the same manner as in Example 1 and an aluminum adhesion test was conducted. As a result, the peeled portion was 70/100.

[0025]

Example 5 2,2-bis (4-hydroxyphenyl)
100 parts of propane, 96 parts of diphenyl carbonate and 4 parts of 4-cyanobenzoic acid phenyl ester as an end-stopping agent were placed in a reactor equipped with a stirrer and purged with nitrogen to 160 ° C.
After being melted by stirring, dibutyl tin oxide 0.0
1 part was added and the temperature was gradually raised to 280 ° C. over 1 hour and the pressure was also reduced to 10 mmHg to distill off the produced phenol. Then, the pressure was adjusted to 0.1 mmHg and the reaction was carried out for 1 hour to obtain a polycarbonate resin having 3.2 cyano groups at the ends per 100 carbon units. The viscosity average molecular weight of the obtained resin was 15,800. When this resin was used for molding, vapor deposition and aluminum adhesion test in the same manner as in Example 1, the peeled portion was 5/100.

[0026]

Example 6 A nitro group at the terminal is a carbon unit 100 in the same manner as in Example 4 except that 4 parts of 4-nitrobenzoic acid phenyl ester is used in place of 4 parts of 4-cyanobenzoic acid phenyl ester. A polycarbonate resin having a viscosity average molecular weight of 14,500 was obtained, which had 3.5 pieces per piece. When the obtained resin was molded and vapor-deposited in the same manner as in Example 1 and an aluminum adhesion test was conducted, no peeling occurred at all.

[0027]

Comparative Example 3 An unmodified polycarbonate resin having a viscosity average molecular weight of 15100 was obtained in the same manner as in Example 4 except that 4 parts of benzoic acid phenyl ester was used instead of 4 parts of 4-cyanobenzoic acid phenyl ester. When this resin was used for molding, vapor deposition and aluminum adhesion test in the same manner as in Example 1, the peeled portion was 90/100.

[0028]

INDUSTRIAL APPLICABILITY The polycarbonate resin having a predetermined amount of cyano group or nitro group at the end of the present invention has excellent adhesion to an aluminum film, and is suitable for use in optical disks, optical cards, various vapor deposition films, vapor deposition plastic reflecting mirrors, etc. It is particularly useful as a more stable base material for metal vapor deposition because of its excellent adhesion to the vapor deposited metal film. Further, the terminal-modified polycarbonate resin of the present invention can be blended with an unmodified polycarbonate resin to improve the adhesion to the vapor-deposited metal film.

Claims (1)

[Claims] 1. A polycarbonate resin modified with an end terminating agent having at least one cyano group or nitro group, wherein the amount of the cyano group or nitro group is 1 or more per 100 carbonate units. Excellent polycarbonate resin.