JP3324614B2 - Copolycarbonate resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel copolycarbonate resin and a method for producing the same. The copolycarbonate resin of the present invention has a functional group capable of absorbing ultraviolet rays, so that it has excellent weather resistance and is non-volatile. Since it also has the performance as an ultraviolet absorber, it is suitably used for various applications.

[0002]

Conventional methods and their problems Conventionally, polycarbonate resins are excellent in heat resistance, impact resistance, etc., but are somewhat insufficient in terms of weather resistance. It was unusual and deteriorated easily. Therefore, a mixture of a polycarbonate resin and a small amount of an ultraviolet absorber has been used. However, in this case, DR Olson and K. Webb et al.
eculs, Vol. 23, No. 16, p. 3762-3768, 19
90), the thermal loss of the UV absorber is extremely large, and the UV absorber used is volatilized and reduced during extrusion or injection molding, so that it is difficult to keep the added amount constant. There are also problems such as contamination of the mold due to volatilization and deterioration of the working environment.

[0003] On the other hand, attempts have been made to lower the volatility by increasing the molecular weight of the ultraviolet absorber. For example, Tsukahara et al.
Addition of a radical polymerizable vinyl reactive group to a benzotriazole-based UV absorber, reaction with styrene to synthesize a styrene monomer of terminal vinyl benzene type, and reaction with dimethylsiloxane macromonomer to absorb graft-type UV absorption Agent (Polymer Transactions 47 [5]
361-370, 1990). However, this method has a long reaction path, is expensive as an ultraviolet absorber, and is difficult to implement industrially. Further, such olefin-based resins have a problem that their compatibility with the polycarbonate resin is not good, so that the amount of the olefin-based resin is limited to a very small amount.

The inventors of the present invention have conducted intensive studies on a method for obtaining a weather-resistant polycarbonate resin in which the above-mentioned disadvantages have been improved. As a result, by using a compound having a benzotriazole group as a part of the starting dihydric phenol, It has been found that an excellent weatherable polycarbonate resin having no volatility can be obtained. (JP-A-3-39326)

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method for obtaining a non-volatile weather-resistant polycarbonate resin. As a result, as a part of the starting dihydric phenol, the general formula (2) was used. Having an ester bond represented by
By using a compound having a benzotriazole group, it has been found that a non-volatile, weather-resistant polycarbonate resin having excellent compatibility with the resin to be blended can be obtained, and the present invention has been achieved.

That is, the present invention relates to a copolycarbonate resin having structural units represented by the following structural formulas (A) and (B), wherein the structural unit represented by the structural formula (B) in the copolycarbonate resin is But 0.1-70 mol%
And a method for producing a polycarbonate resin in a solution method, wherein a compound represented by the following general formulas (1) and (2) is used.

[0007]

[Image Omitted] Structural formula (A):

[0008]

Embedded image Structural formula (B): (In the formula, A linear C1-10, branched or cyclic alkylidene group, aryl-substituted alkylene group, an arylene group or a _{-O-, -S-, -CO-, -SO 2} - indicates, R ^{1 to} R ⁵ represent a hydrogen atom, a halogen, an alkyl group, an aryl group, or an aralkyl group, and R ⁶ represents a hydrogen atom, a halogen, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aralkyloxy group. R ⁷ and R ⁸ represent a direct bond, a linear, branched or cyclic alkylidene group;
It represents an aryl-substituted alkylene group or an aryl group, B represents an ester bond, and m represents an integer of 0 to 3. )

[0009]

Embedded image General formula (1):

[0010]

Embedded image General formula (2): (In the formula, A linear C1-10, branched or cyclic alkylidene group, aryl-substituted alkylene group, an arylene group or a _{-O-, -S-, -CO-, -SO 2} - indicates, R ^{1 to} R ⁵ represent a hydrogen atom, a halogen, an alkyl group, an aryl group, or an aralkyl group, and R ⁶ represents a hydrogen atom, a halogen, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aralkyloxy group. R ⁷ and R ⁸ represent a direct bond, a linear, branched or cyclic alkylidene group;
It represents an aryl-substituted alkylene group or an aryl group, B represents an ester bond, and m represents an integer of 0 to 3. )

Hereinafter, the configuration of the present invention will be described. The copolycarbonate resin of the present invention has a viscosity average degree of polymerization of about 30 to 200 from an oligomer having a viscosity average degree of polymerization of about 2 to 50 and having a novel constitutional unit represented by the structural formula (B) as a constitutional unit. It also includes a polymer, and this structural unit may be one or a mixture of two or more kinds.

The method for producing a copolycarbonate resin is the same as the method for producing a conventional aromatic polycarbonate resin except that a dihydric phenol having an ester bond represented by the general formula (2) and having a benzotriazole group (hereinafter simply referred to as “general Except that the dihydric phenol having a benzotriazole group of the formula (2) is abbreviated), ie, an organic solvent which is inert to the reaction in an interfacial polymerization method, an aqueous alkali solution, In the presence, a tertiary amine or a quaternary ammonium salt is reacted with phosgene using the dihydric phenolic compound represented by the general formulas (1) and (2) and a suitable molecular weight regulator (terminal terminator). In the pyridine method, a similar dihydric phenol compound and a molecular weight regulator are added to pyridine or pyridine. Beauty was dissolved in a mixed solution of an inert solvent, a method of directly obtaining a polycarbonate resin by blowing phosgene. In the interfacial polymerization method, a method of adding a dihydric phenol compound having a benzotriazole group of the general formula (2) at the time of polymerization after the phosgenation reaction,
Conversely, a method of adding a dihydric phenol compound of the general formula (1) after phosgenating a dihydric phenol compound having a benzotriazole group of the general formula (2) to form a dichloroformate, A method of adding the compound after the chemical reaction can be used as appropriate.

As the dihydric phenolic compound represented by the general formula (1), 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, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2 -Bis (4-hydroxy-
3,5- {bromophenyl) 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)-
Examples thereof include 1-phenylethane and bis (4-hydroxyphenyl) diphenylmethane. Among these, 2,2-bis (4-hydroxyphenyl) propane,
1,1-Bis (4-hydroxyphenyl) cyclohexane is preferable from the viewpoint of the thermal stability of the obtained copolycarbonate resin.

An example of the compound having a benzotriazole group of the general formula (2) is 1,2-ethanediylbis (3- (2H-benzotriazol-2-yl).
-2-hydroxybenzoate), 1,12-dodecanediyl bis (3- (2H-benzotriazole-2)
-Yl) -4-hydroxybenzoate), 1,3
-Cyclohexanediylbis (3- (5-chloro-2
H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,4-butanediylbis (3-
(2H-benzotriazol-2-yl) -4-hydroxy-5-methylphenylethanoate), 3,6-
Dioxa-1,8-octanediylbis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-
Hydroxyphenylethanolate), 1,6-hexanediyl bis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate), p-xylenediyl bis ( 3- (3- (2H-benzotriazol-2-yl)
-4-hydroxyphenyl) propionate), bis (3- (2H-benzotriazol-2-yl) -4-
Hydroxytolyl) malonate, bis (2- (3-
(2H-benzotriazol-2-yl) -4-hydroxy-5-octylphenyl) ethyl) terephthalate, bis (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-propyltoluyl) octadio Eat and so on.

In the present invention, the amount of the structural unit represented by the structural formula (B) in the copolycarbonate resin and the amount of the compound of the general formula (2) used in the production of the copolycarbonate resin is determined based on all the dihydric phenols used. 0.1 ~
If it is used in an amount exceeding 70 mol%, the polymerization reaction does not proceed smoothly. Insufficient improvement.

Examples of the terminal terminator or molecular weight regulator used in the reaction include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, pt-butylphenol, cumylphenol and tribromophenol. Besides, long-chain alkyl phenol, alkyl ether phenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, aromatic carboxylic acid, hydroxybenzoic acid alkyl ester, aliphatic carboxylic acid hydroxybenzoic acid ester, etc. Benzo having a phenolic hydroxyl group such as [(4-methyl-6-benzotriazolylphenol) -phthalimide] and 2.0-methylene [(4-t-butyl-6-benzotriazolylphenol) -phthalimide]. Triazole compounds are also exemplified. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

Solvents inert to the reaction include dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, 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. Further, if desired, ethers other than the above,
Solvents having an affinity for water, such as ketones, esters, and nitriles, may be used as long as the mixed solvent system is not completely compatible with water.

As the polymerization catalyst, trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine,
Tertiary amines such as N, N-dimethylcyclohexylamine, pyridine, quinoline and dimethylaniline; and quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride.

The copolycarbonate resin of the present invention is produced by using the above-mentioned components as essential components.
Examples of such a branching agent which can be used together to form a branched polycarbonate in the range of 0.1 to 1.0 mol%, particularly 0.1 to 1.0 mol%, include phloroglysin, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -2-heptene, 1,3,5-tri (2
-Hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2
Polyhydroxy compounds exemplified by -hydroxy-5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3 , 3-bis (4-
Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol,
Examples thereof include 5,7-dichloroisatin bisphenol and 5-bromoisatin bisphenol.

The copolycarbonate resin of the present invention may contain an antioxidant, a light stabilizer,
Coloring agents, inorganic or organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants, antistatic agents and the like may be used in combination as appropriate. Is used as an ultraviolet absorber. Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 3.4 kg of sodium hydroxide was dissolved in 42 liters of water.
While maintaining the temperature at 1,6-hexanediyl bis (3-
(3- (2H-benzotriazol-2-yl) -4-
Hydroxy-5-t-butylphenyl) propionate (hereinafter referred to as “A-1”) 2.4 kg, 2,2-bis (4-hydroxyphenyl) propane (hereinafter “BP”)
A) 6.5 kg and 8 g of hydrosulfite were dissolved. To this, 28 l of methylene chloride was added, and while stirring, 171 g of pt-butylphenol was added.
Subsequently, 3.6 kg of phosgene was blown in for 60 minutes. After the phosgene blowing was completed, the mixture was vigorously stirred to emulsify the reaction solution. After the emulsification, 8 g of triethylamine was added, and stirring was continued for about 1 hour to carry out polymerization. Separating the polymerization liquid into an aqueous phase and an organic phase,
After the organic phase was neutralized with phosphoric acid, washing with water was repeated until the pH of the washing became neutral, and 35 l of isopropanol was added to precipitate a polymer. The precipitate was filtered and then dried to obtain a powdery copolycarbonate resin (hereinafter referred to as "P-1"). The analysis results of this polycarbonate are shown in Table 1.

Examples 2 to 3 Copolycarbonate resins having the compositions shown in Table 1 were obtained in the same manner as in Example 1 . Table 1 shows these physical properties.

The description in Table 1 is as follows.・ BPA: 2,2-bis (4-hydroxyphenyl) propane ・ BPZ: 1,1-bis (4-hydroxyphenyl) cyclohexane ・ TBA: 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane A-1: 1,6-hexanediyl bis (3- (3-
(2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate) PTBP: pt-butylphenol Mv: viscosity average molecular weight (by the method of measuring polycarbonate from BPA and PTBP)

[0024]

[Table 1]

Examples 4 to 5 and Comparative Examples 1 and 2 The polycarbonate resin powder (Iupilon S-3000 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the copolycarbonate resin obtained in Examples 1 and 2 are shown in Table 2. After mixing with the composition and pelletizing with a screw 40 mmφ extruder, a test piece having a thickness of 1.6 mm was obtained by injection molding. The test piece was treated with a sunshine weather meter WEL-SUN-DC manufactured by Suga Test Instruments, and the yellowing degree (YI) was measured using an SM color computer SM-3-CH manufactured by Suga Test Instruments.
Table 2 shows the results of the measurements.

[0026]

[Table 2]

[0027]

The copolycarbonate resin produced by the production method of the present invention has the same weather resistance as the additive type ultraviolet absorber and is bonded to the main chain, so that it has a low volatility in extrusion, injection molding and the like. In addition, there is no deterioration in mechanical properties and thermal stability. In addition, since the copolycarbonate oligomer of the present invention has the above properties, molded articles such as sheets and lenses required to have weather resistance,
It can be suitably used as an agent for improving the weather resistance of paints and other resins.

────────────────────────────────────────────────── (5) References US Pat. No. 4,948,666 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY ( STN)

Claims (3)

(57) [Claims] 1. A compound represented by the following structural formulas (A) and (B)
A copolycarbonate resin having a structural unit. Embedded image Structural formula (A):Embedded image Structural formula (B):(Wherein A is a straight-chain, branched-chain or cyclic C1-C10)
Alkylidene group, aryl-substituted alkylene group, aryl
Len group or -O-, -S-, -CO-, -SO_Two-Indicates R ¹~ R^Five
Represents a hydrogen atom, a halogen, an alkyl group, an aryl group,
A alkyl group;⁶Is hydrogen atom, halogen, alkyl
Group, aryl group, aralkyl group, alkoxy group, aryl
Roxy or aralkyloxy;⁷, R⁸Is
Direct bond, linear, branched or cyclic alkylidene group,
An aryl-substituted alkylene group or an aryl group;
It shows a stele bond, and m represents an integer of 0 to 3. ) 2. The structural unit represented by the structural formula (B) is:
The copolycarbonate resin according to claim 1, which is in a range of 0.1 to 70 mol%. 3. Production of a polycarbonate resin by a solution method.
In the manufacturing method, it is represented by the following general formulas (1) and (2).
New copolycarbonate characterized by using compounds
Method of manufacturing resin. Embedded image General formula (1):Embedded image General formula (2):(Wherein A is a straight-chain, branched-chain or cyclic C1-C10)
Alkylidene group, aryl-substituted alkylene group, aryl
Len group or -O-, -S-, -CO-, -SO_Two-Indicates R ¹~ R^Five
Represents a hydrogen atom, a halogen, an alkyl group, an aryl group,
A alkyl group;⁶Is hydrogen atom, halogen, alkyl
Group, aryl group, aralkyl group, alkoxy group, aryl
Roxy or aralkyloxy;⁷, R⁸Is
Direct bond, linear, branched or cyclic alkylidene group,
An aryl-substituted alkylene group or an aryl group;
It shows a stele bond, and m represents an integer of 0 to 3. )