JP3211843B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition having improved weather resistance. More specifically, the present invention relates to a polycarbonate resin composition having excellent weather resistance and excellent heat-melt stability by adding an ultraviolet absorbing polycarbonate resin and an antioxidant to a polycarbonate resin.

[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 the case of this method, D.I. R. Olson and K.C. K. Webb et al. (Macromolecules, Vol. 2).
3, No. 16, p. 3762-3768, 1990)
As described above, the thermal loss of the ultraviolet absorber is extremely large, and the ultraviolet absorber to be used is difficult to keep its added amount constant because it is volatilized and reduced during extrusion or injection molding. There are problems such as contamination of the mold due to volatility 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 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 an olefin-based resin has a problem that its compatibility with the polycarbonate resin is not good, so that the amount of addition thereof is limited to a very small amount.

Further, Japanese Patent Application Laid-Open Nos.
JP-A-39326 discloses that a phenolic compound having a benzotriazole group is used to obtain a low-emission, ultraviolet-absorbing polycarbonate resin having excellent weather resistance. However, this UV-absorbing polycarbonate resin has a point that the stability at the time of melting by heating is slightly inferior, and there is a problem that the hue is deteriorated at the time of molding.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method for obtaining a weather-resistant polycarbonate resin having the above-mentioned disadvantages, and as a result, have been able to stabilize the polycarbonate resin by using an ultraviolet-absorbing polycarbonate resin as an ultraviolet absorber. (A) a phosphorus-based antioxidant,
(B) It has been found that by blending one or more stabilizers selected from phenolic antioxidants, a weather-resistant polycarbonate resin having excellent stability during heating and melting can be obtained, and the present invention has been achieved. did.

That is, the present invention relates to (A) a polycarbonate resin, (B) an ultraviolet-absorbing polycarbonate resin, and (C) one or more selected from (a) a phosphorus-based antioxidant and (b) a phenol-based antioxidant. An object of the present invention is to provide a polycarbonate resin composition obtained by adding two or more kinds.

The polycarbonate resin used in the present invention is obtained by reacting an aromatic dihydroxy compound (a compound as exemplified by the general formula (1)) or a small amount thereof with a phosgene or carbonic acid diester. The obtained thermoplastic aromatic polycarbonate polymer or copolymer which may be branched.

In order to obtain a branched aromatic polycarbonate resin, 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.

In the case of the phosgene method polycarbonate,
A terminal terminator or a molecular weight regulator may be used. Examples of the terminal terminator or the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group.
In addition to -t-butylphenol, tribromophenol and the like, long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, alkyl ether phenols and the like are exemplified.

The ultraviolet absorbing polycarbonate resin used in the present invention comprises (1) structural formulas (A) and (B)
Or (2) a polycarbonate resin having a structural unit represented by the structural formula (A) and having a terminal group represented by the structural formula (C) Or (3) having the structural units represented by the structural formulas (A) and (B), and having the structural formula (C)
, Of course, these ultraviolet-absorbing polycarbonate resins may be used alone, or two or more of them may be used. (Below)

[0011]

Embedded image Structural formula (A):

[0012]

Embedded image Structural formula (B):

(Wherein A is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an arylene group or -O-, -S-, -CO-, -SO _2- And R ^{1 to} R ⁸ represent a hydrogen atom, a halogen, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aralkyloxy group, and B represents a direct bond, an alkylidene group, an aryl-substituted alkylene group, or an arylene. Group, —O—, —S—, —CO—, —SO ₂ — or —R ⁹ —X—R ¹⁰ —Y
—R ¹¹ — (R ⁹ , R ¹⁰ , and R ¹¹ represent a direct bond, an alkylidene group, an aryl-substituted alkylene group, or an arylene group;
X and Y represent a direct bond or an ester bond, and at least one of them represents an ester bond. ). ) (Margin below)

[0014]

Embedded image Structural formula (C):

(Wherein R ^{12 to} R ¹⁴ represent a hydrogen atom, a halogen atom, a nitro group or an alkyl group, an alkoxy group or an allyl group having 1 to 20 carbon atoms, p is an integer of 1 to 10,
q represents 1 or 2. )

The ultraviolet absorbing polycarbonate resin is disclosed in, for example, JP-A-1-201330 and JP-A-3-39.
326, which is suitably obtained by the method described in 326, and using a compound represented by the general formula (1), (2) and / or (3).

[0017]

Embedded image General formula (1):

[0018]

Embedded image General formula (2): (Where A, R ^{1 to} R ⁸ , B, R ⁹ , R ¹⁰ , R ¹¹ and X, Y are the same as described above)

[0019]

Embedded image General formula (3): It is. (In the formula, R ^{12 to} R ¹⁴ , p and q are the same as described above.)

The compounds represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxy). Phenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2
-Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4
-Hydroxyphenyl) propane, 2,2-bis (3-
Cyclohexyl-4-hydroxyphenyl) propane,
Bis (hydroxyaryl) alkanes exemplified by 1,1-bis (4-hydroxyphenyl-1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane and the like; 1,1-bis (4-hydroxyphenyl) cyclopentane , 1,1-bis (4-hydroxyphenyl) cyclohexane and the like, bis (hydroxyaryl) cycloalkanes; 4,4′-dihydroxydiphenyl ether 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like Dihydroxydiaryl ethers exemplified by: 4,4'-dihydroxydiphenyl sulfide, dihydroxydiaryl sulfides exemplified by 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and the like; 4,4'-dihydroxydiphenyl Sulfoxide, 4, 4'-dihydroxy-3,
Dihydroxydiarylsulfoxides exemplified by 3′-dimethyldiphenylsulfoxide and the like; dihydroxydiarylsulfones exemplified by 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; Hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like can be mentioned. Among these, in particular, 2,2-bis (4-
(Hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are preferred.

An example of the compound represented by the general formula (2) is bis (3- (2H-benzotriazole-2).
-Yl) -2-hydroxy-5-methylphenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl ) Methane, bis (3- (2H-
Benzotriazol-2-yl) -2-hydroxy-5
-Cumylphenyl) methane, bis (3- (2H-benzotriazol-2-yl) -2-hydroxy-5-octylphenyl) methane, 1,1-bis (3- (2H-benzotriazol-2-yl)- 2-hydroxy-5
Methylphenyl) octane, 1,1-bis (3- (2H
-5-chlorobenzotriazol-2-yl) -2-hydroxy-5-methylphenyl) octane, 1,2-
Ethanediyl bis (3- (2H-benzotriazol-2-yl) -2-hydroxybenzoate), 1,
12-dodecanediyl bis (3- (2H-benzotriazol-2-yl) -4-hydroxybenzoate)
1,3-cyclohexanediyl bis (3- (5
-Chloro-2H-benzotriazol-2-yl) -2
-Hydroxybenzoate), 1,4-butanediyl bis (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-methylphenylethanoate), 3,6-dioxa-1,8-octanediyl
Bis (3- (5-methoxy-2H-benzotriazol-2-yl) -4-hydroxyphenylethanoate), 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-hydroxytoluyl) malonate, bis (2- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-octyl) Phenyl) ethyl) terephthalate, bis (3- (2H-
Benzotriazol-2-yl) -4-hydroxy-5
-Propyl toluyl) octadioate and the like.

Examples of the compound represented by the general formula (3) include 2- (2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-methylphenol and 2- (2H-benzotriazole- 2-yl)
-6-phthalimidoethyl-4-methylphenol,
2- (2H-benzotriazol-2-yl) -6-phthalimidooctyl-4-methylphenol, 2-
(2H-benzotriazol-2-yl) -6-phthalimidomethyl-4-t-butylphenol, 2- (2
H-benzotriazol-2-yl) -6-phthalimidomethyl-4-cumylphenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (phthalimidomethyl) phenol and the like.

In addition to the ultraviolet absorbing polycarbonate resin used in the present invention, an ultraviolet absorbing agent may be appropriately added and used according to the purpose of use.

Examples of the phenolic antioxidant include 1,1-bis (5-tert-butyl-2-methyl-4)
-Hydroxyphenyl) butane, 1,1,3-tris (5-t-butyl-2-methyl-4-hydroxyphenyl) butane, octadecyl-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis (3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate), 2,2-thio-diethylenebis (3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate), 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1 -Dimethylethyl) -2,4.
8,10-tetraoxaspiro [5.5] undecane,
1,3,5-trimethyl-2,4,6-tris (3
5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, triethylene glycol-bis (3- (3-t -Butyl-5-methyl-
4-hydroxyphenyl) propionate), 1,6
-Hexanediol-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate),
2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,3
5-triazine, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N'-bis (3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyl) hydrazine, 2,2′-thiobis (4-methyl-6-t
-Butylphenol), 3,5-di-t-butyl-4
-Hydroxybenzylphosphonate-diethyl ester, 4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-thiobis- (2-methyl-6-t-butylphenol), 2, 2'-methylenebis- (4-methyl-6-t-butylphenol),
2,2′-ethylidenebis (4,6-di-t-butylphenol) and the like, and these may be used alone or in combination of two or more.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, and tris (2-ethylhexyl) phosphite ,
Tris (tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite,
Monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra phosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite 4,4'-butylidene-bis (3-methyl-6-
t-butylphenyldi (tridecyl) phosphite),
Tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite, distearylpentaerythritol diphosphite Phosphite, tris (4
-T-butylphenyl) phosphite, tris (2,
4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene phosphonite, bis (2,4-di -T-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-t-
Butylphenyl) octyl phosphite, ethyl diethyl phosphonoacetate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, hexamethylphosphoric triamide, and the like. And two or more kinds may be used in combination.

The composition of the present invention may further comprise,
Other additives that impart desired properties may be added. For example, flame retardants, heat stabilizers, antistatic agents, plasticizers, release agents, lubricants, compatibilizers, foaming agents, glass fibers, carbon fibers,
One or more reinforcing agents such as ceramic whiskers, fillers, dyes and pigments may be added and contained.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples.

[0028]

【Example】

Synthesis Example-1 3.7 kg of sodium hydroxide was dissolved in 42 l of water, and
While maintaining the temperature at ° C, 3.6 kg of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “BPA”) and bis (3- (2H-benzotriazol-2-yl) -2
10.5 kg of -hydroxy-5-octylphenyl) methane (hereinafter referred to as "A-1") and 8 g of hydrosulfite were dissolved. To this, 28 l of methylene chloride was added and, while stirring, 960 g of pt-butylphenol.
(Hereinafter referred to as “PTBP”) was added, and then 4.0 kg of phosgene was blown in for 60 minutes. After the injection of phosgene, the mixture was vigorously stirred to emulsify the reaction solution.
Was added and stirring was continued for about 1 hour to carry out polymerization. The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water was washed repeatedly until the pH of the washing became neutral. Then, 35 l of isopropanol was added to precipitate the polymer. Was. By filtering the precipitate and then drying,
A powdered polycarbonate resin having an intrinsic viscosity of 0.07 dl / g was obtained (hereinafter referred to as "P-1").

Synthesis Example 2 In Synthesis Example 1, 3.6 kg of BPA and A-11
0.5kg to BPA 7.3kg, PTBP 960g
To 2- (2H-benzotriazol-2-yl) -6-
Phthalimidomethyl-4-methylphenol (hereinafter referred to as "A
-2 kg) to obtain a polycarbonate resin having an intrinsic viscosity of 0.09 dl / g (hereinafter referred to as "P-2").

Synthesis Example-3 In Synthesis Example-1, 3.6 kg of BPA was replaced by 5.8 kg.
10.5 kg of A-1 in 1,6-hexanediyl
To 4.9 kg of bis (3- (3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate) (hereinafter referred to as “A-3”),
A polycarbonate resin having an intrinsic viscosity of 0.13 dl / g was obtained in the same manner except that 960 g of PTBP was changed to 1.4 kg of A-2, respectively (hereinafter referred to as “P-3”).

Examples 1-9, Comparative Examples 1-3 Polycarbonate resin powder (manufactured by Mitsubishi Gas Chemical Company, Ltd.)
100 parts of Iupilon (S-3000) at the composition ratio shown in Table 1, and mixed with a tumbler type blender.
Pellets were formed with a 40 mmφ extruder. 4g of these pellets
Was placed in a test tube, dried at 120 ° C. for 1 hour under a nitrogen stream, and then subjected to a melting test at 340 ° C. for 1 hour in a nitrogen stream. After the completion of the melting test, the resin in the test tube was dissolved in 25 ml of methylene chloride, and the hue of the solution was visually compared with the color of a platinum-cobalt chromaticity standard solution, and measured as an APHA value. Table 1 shows the APHA values before and after the melting test.

Next, a plate-shaped molded product having a thickness of 1.6 mm was obtained by injection molding using the above-mentioned pellets. Using this test piece, the sample was treated with a sunshine weather meter WEL-SUN-DC manufactured by Suga Test Machine,
Table 1 shows the results of measuring the degree of yellowing (YI value) using an M color computer SM-3-CH. Table 1
Is described below.

P-1: UV-absorbing polycarbonate resin obtained by Synthesis Example-1 P-2: UV-absorbing polycarbonate resin obtained by Synthesis Example-2 P-3: Obtained by Synthesis Example-3 UV-absorbing polycarbonate resin B-1: pentaerythrityl-tetrakis (3-
(3,5-di-t-butyl-4-hydroxyphenyl)
B-2: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl) -2,4 , 8,
10-tetraoxaspiro [5.5] undecane C-1: tris (2,4-di-t-butylphenyl)
Phosphite C-2: tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenephosphonite C-3: bis (2,4-di-t-butylphenyl) pentaerythritol di Phosphite ・ U-1: 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol "Ratio" represents a comparative example. (Hereinafter the margin)

[0034]

[Table 1]

[0035]

According to the polycarbonate resin composition of the present invention, the use of an ultraviolet-absorbing polycarbonate resin as an ultraviolet absorber and the use of a phosphorus-based antioxidant and / or a phenol-based antioxidant prevent the generation of volatile substances. It is suppressed, has excellent weather resistance, and has excellent stability when melted by heating. Therefore, it is useful for various molding materials that are required to have weather resistance and thermal stability.

Continuation of the front page (56) References JP-A-1-201330 (JP, A) JP-A-3-39326 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64 / 00-64/42 C08L 69/00

Claims (8)

(57) [Claims] 1. One or two or more selected from (1) a polycarbonate resin, (2) an ultraviolet-absorbing polycarbonate resin, and (3) (a) a phosphorus-based antioxidant and (b) a phenol-based antioxidant. And a polycarbonate resin composition comprising: 2. An ultraviolet absorbing polycarbonate resin,
The polycarbonate resin composition according to claim 1, which is a co-polycarbonate resin having structural units represented by the following structural formulas (A) and (B). Embedded image Structural formula (A): 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 ⁸ represent a hydrogen atom, a halogen, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aralkyloxy group, and B represents a direct bond, an alkylidene group, an aryl-substituted alkylene group, an arylene group, O-, -S-, -C
O-, -SO ₂ - or ^{-R 9 -X-R 10 -Y-} R 11 - (R 9, R
¹⁰ and R ¹¹ represent a direct bond, an alkylidene group, an aryl-substituted alkylene group, or an arylene group, X and Y represent a direct bond or an ester bond, and at least one of them represents an ester bond. ). ) 3. The polycarbonate resin having an ultraviolet absorbing ability has a structural unit represented by the above structural formula (A) and has a terminal group represented by the following structural formula (C). The polycarbonate resin composition according to the above. Embedded image Structural formula (C): (Wherein R ^{12 to} R ¹⁴ represent a hydrogen atom, a halogen atom, a nitro group or an alkyl group, an alkoxy group or an allyl group having 1 to 20 carbon atoms, p is an integer of 1 to 10, q is 1 or 2)
Is shown. ) 4. A polycarbonate resin having an ultraviolet absorbing ability has the structural units represented by the structural formulas (A) and (B) and has a terminal group represented by the structural formula (C). The polycarbonate resin composition according to claim 1, which is a polycarbonate resin. 5. The ultraviolet absorbing polycarbonate resin,
A co-polycarbonate resin comprising the structural formulas (A) and (B) and / or (C), wherein the structural unit comprising the structural formulas (B) and / or (C) is in the range of 0.1 to 70 mol%. The polycarbonate resin composition according to claim 1, which is: 6. The polycarbonate resin composition according to claim 1, wherein the intrinsic viscosity of the ultraviolet absorbing polycarbonate resin in methylene chloride at 25 ° C. is 0.4 dl / g or less. 7. Polycarbonate resin 50 to 99.99
The UV-absorbing polycarbonate resin was added in an amount of 0.
The polycarbonate resin composition according to claim 1, wherein the composition is added in an amount of from 01 to 50 parts by weight. 8. The polycarbonate resin composition according to claim 1, wherein 0.005 to 1 part by weight of an antioxidant is added to 100 parts by weight of the composition comprising the polycarbonate resin and the ultraviolet absorbing polycarbonate resin.