JPH07196904A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin composition useful for a building material, etc., having sufficient weather resistance by mixing a polycarbonate resin with a benzotriazole compound as an ultraviolet absorber and a coumarin compound or a naphthalimide compound as a fluorescent blightener. CONSTITUTION:(A) 100 pts.wt. of a polycarbonate resin is mixed with (B) 5-25 pts.wt. of a benzotriazole compound of formula I (R1 is an alkyl, nitro or an alkoxyl (s) is 1-4; Z is a halogen or an alkyl) or formula II (t is 1-3) [e.g. 2(2'- hydroxy-5'-methylphenyl)benzotriazole, etc.) as an ultraviolet absorber and (C) 0.1-10 pts.wt. of one or more a coumarin compound of formula III [R2 is amino (derivative) or OH; R3 and R4 are H, an alkyl or phenyl) (e.g. 3-phenyl-7-amino- coumarin) and a naphthalimide compound of formula IV (R5 and R6 are H or an alkoxy; R7 is H or an alkyl) (e.g. 4-methoxy-N-methylnaphthalimide) as a fluorescent blightener to give the objective resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having a wide range of uses such as building materials, electric parts materials, and decorative materials.

[0002]

2. Description of the Related Art Generally, a molded article made of a polycarbonate resin has heat resistance,
It has excellent impact resistance and is used in a wide range of applications, but it has some problems in terms of weather resistance, and it may cause harmful yellowing and the like when exposed to, for example, ultraviolet rays.

Therefore, conventionally, a resin composition in which various light stabilizers are contained alone or in plural kinds in a polycarbonate resin is used. Among them, a resin composition containing a benzotriazole type ultraviolet absorber is weather resistant. Since it exhibits a relatively excellent effect, it is frequently used, but it does not yet have sufficient weather resistance, and further improvement is desired.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a polycarbonate resin composition capable of obtaining a molded article having sufficient weather resistance.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object, and as a result, use a resin composition containing a specific ultraviolet absorber and a fluorescent brightening agent in a polycarbonate resin. The molded product thus obtained was found to have sufficient weather resistance, and the present invention was completed.

That is, the polycarbonate resin composition of the present invention is based on 100 parts by weight of the polycarbonate resin.
The following general formula (Ia) or (Ib);

[Chemical 5]

[Chemical 6] (Wherein R ₁ represents an alkyl group, a nitro group or an alkoxyl group, s represents an integer of 1, 2, 3 or 4, t represents an integer of 1, 2 or 3, and Z represents a halogen atom. Or 5 to 25 parts by weight of an ultraviolet absorber composed of a benzotriazole compound represented by the following general formula (II) and (III);

[Chemical 7] (However, in the above formula, R ₂ represents an amino group, a derivative thereof or a hydroxyl group, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group or a phenyl group.)

[Chemical 8] (Wherein, R ₅ and R ₆ in the above formula represent a hydrogen atom or an alkoxy group, and R ₇ represents a hydrogen atom or an alkyl group), and one or two of a coumarin compound and a naphthalimide compound The gist of the present invention is to contain 0.1 part by weight to 10 parts by weight of the fluorescent whitening agent.

The polycarbonate resin used in the present invention is not particularly limited, and for example, those produced from a bisphenol compound by a well-known method can be used, and various types of resins can be used in combination. Does not matter. The polycarbonate resin has an average molecular weight of 10,000 to 50,000, preferably 200.
It is preferable to use one having a size of about 00 to 40,000.

Specific examples of the ultraviolet absorber comprising the benzotriazole compound represented by the above general formula (Ia) or (Ib) are represented by the following structural formula (Ia-1).
-(2'-hydroxy-5'-methylphenyl) benzotriazole, represented by the following structural formula (Ia-2) 2-
(2'-hydroxy-3'-tert-butyl-5'-
Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-nitro-5'-methylphenyl) benzotriazole represented by the following structural formula (Ia-3), and the following structural formula (Ia- 2- (2) represented by 4)
′ -Hydroxy-5′-propoxyphenyl) benzotriazole, 2,2 represented by the following structural formula (Ib-1)
′ -Methylenebis (4-methyl-6-benzotriazol-2-ylphenol), 2,2′-methylenebis [4- (1,1,3, which is represented by the following structural formula (Ib-2).
3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.

[0009]

[Chemical 9]

[Chemical 10] In the resin composition of the present invention, the content of the ultraviolet absorber is set to 5 to 25 parts by weight, preferably 10 to 12 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the content is less than 5 parts by weight, the resulting molded article cannot be effectively prevented from being deteriorated by ultraviolet rays, and when it exceeds 25 parts by weight, a bleeding phenomenon occurs in the benzotriazole compound.
It is difficult to obtain a molded product having a good appearance, which is not preferable.

Specific examples of the coumarin compound (fluorescent whitening agent) represented by the above general formula (II) include the following structural formula (II-
3-phenyl-7-amino-coumarin represented by 1),
3-phenyl-7- represented by the following structural formula (II-2)
(Imino-1 ', 3', 5'-triazine-2'-diethylamino-4'-chloro) -coumarin, 3-phenyl-7- (imino-1 represented by the following structural formula (II-3).
′, 3 ′, 5′-triazine-2′-diethylamino-
4′-methoxy) -coumarin, 3-phenyl-7-naphthotriazole-coumarin represented by the following structural formula (II-4), 4-methyl-7 represented by the following structural formula (II-5)
-Hydroxy-coumarin, and the like.

[0011]

[Chemical 11] Further, specific examples of the naphthalimide compound (fluorescent whitening agent) represented by the above general formula (III) include the following structural formula (III-
An example is 4-methoxy-N-methylnaphthalimide represented by 1).

[0012]

[Chemical 12] In the resin composition of the present invention, the content of the fluorescent whitening agent is set to 0.1 parts by weight to 10 parts by weight, preferably 0.2 parts by weight to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. Is good. When the content is less than 0.1, the resulting molded article cannot be effectively prevented from being deteriorated by ultraviolet rays. When the content exceeds 10 parts by weight, a bleeding phenomenon occurs in the fluorescent whitening agent. It is difficult to obtain a molded product having a good appearance, which is not preferable.

The optical brightener of the present invention may be composed of only a coumarin compound, a naphthalimide compound, or both a coumarin compound and a naphthalimide compound. .

In addition to the above-mentioned components, the resin composition of the present invention may further contain additives such as an antioxidant, a release agent, a colorant, an antistatic agent, a lubricant and a flame retardant, if necessary. It may be contained.

[0015]

EXAMPLES Examples of the present invention and comparative examples for deriving the effects thereof will be described below.

<Examples 1 to 8>

[Table 1] Polycarbonate resin (Product name "Upilon E200
0F ", manufactured by Mitsubishi Gas Chemical Co., Inc.) and 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] ( A benzotriazole compound consisting of a product name "Mark LA-31", manufactured by Adeka Argus Chemical Co., Ltd., and 3-phenyl-7- (imino-1 ', 3)
′, 5′-Triazine-2′-diethylamino-4′-
Chloro) -coumarin (trade name "Hakkol PYB-
D ", manufactured by Hakkor Chemical Co., Ltd.) and a coumarin compound at the ratios shown in Table 1 above.
They were mixed until uniform, and they were extrusion-molded with a single-screw extruder (50 mm diameter, L / D30) to obtain sheet-shaped molded products with a thickness of 1 mm.

The molded product thus obtained was treated with a sunshine weatherometer for 3000 hours, and then the yellowness was measured according to JIS K 7103 to obtain the yellowing degree (ΔYI). The presence or absence of bleeding was observed. The results are also shown in Table 1 above.

<Comparative Examples 1 to 4>

[Table 2] The same polycarbonate resin, benzotriazole compound, and coumarin compound as those in Examples 1 to 8 were used in Table 2 above.
Each of them was mixed in the proportions shown in Table 1, and a sheet-like molded article was obtained in the same manner as above, and after the same treatment, the same evaluation was performed. The results are also shown in Table 2 above.

<Examples 9 to 16>

[Table 3] Polycarbonate resin of the same kind as described above, benzotriazole compound of the same kind as described above, and 4-methoxy-N-methylnaphthalimide (trade name "DiaresinBril"
and a naphthalimide compound consisting of "Liant Yellow 6G" manufactured by Mitsubishi Kasei Co., Ltd., respectively, in the proportions shown in Table 3 above, to obtain a sheet-shaped molded article in the same manner as above, and after performing the same treatment , And evaluated in the same manner. The results are also shown in Table 3 above.

<Comparative Examples 5 to 7> Polycarbonate resins, benzotriazole compounds and coumarin compounds of the same types as in Examples 9 to 16 were blended in the proportions shown in Table 2 above, and molded into a sheet in the same manner as above. After obtaining a product and performing the same treatment, the same evaluation was performed. The results are also shown in Table 2 above.

<Examples 17 to 24>

[Table 4] A polycarbonate resin of the same kind as the above, a benzotriazole compound of the same kind as the above, a coumarin compound part of the same kind as the above, and a naphthalimide compound of the same kind as the above are shown in Table 4 above.
Each of them was mixed in the proportions shown in Table 1, and a sheet-like molded article was obtained in the same manner as above, and after the same treatment, the same evaluation was performed. The results are also shown in Table 4 above.

<Comparative Examples 8 to 10> Polycarbonate resins, benzotriazole compounds, coumarin compounds and naphthalimide compounds of the same types as described above were blended in the proportions shown in Table 2 above, and sheet-like molded articles were prepared in the same manner as above. Was obtained, the same treatment was performed, and then the same evaluation was performed. The results are also shown in Table 2 above.

<Evaluation> As can be understood from the above results, the molded articles of Examples 1 to 24 according to the present invention have a low degree of yellowing, no bleeding, and good weather resistance and appearance. On the other hand, the molded products of Comparative Examples 1 to 10 which do not satisfy the requirements of the present invention have a large degree of yellowing or the occurrence of bleeding and are inferior in weather resistance and the like. I know there is.

The molded products of Examples 1 to 24 also had excellent properties inherent to polycarbonate such as excellent heat resistance and impact resistance.

[0025]

As described above, according to the polycarbonate resin composition of the present invention, 5 to 25 parts by weight of the ultraviolet absorber composed of a benzotriazole compound, 100 parts by weight of the polycarbonate resin, the coumarin compound and 0.1 to 10 parts by weight of a fluorescent whitening agent consisting of one or two kinds of naphthalimide compounds,
Therefore, it is possible to obtain a molded article having sufficient weather resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09K 3/00 104 C

Claims (1)

[Claims] 1. The following general formula (Ia) or (Ib) per 100 parts by weight of the polycarbonate resin; [Chemical 2] (Wherein R ₁ represents an alkyl group, a nitro group or an alkoxyl group, s represents an integer of 1, 2, 3 or 4, t represents an integer of 1, 2 or 3, and Z represents a halogen atom. Or an alkyl group) 5 to 25 parts by weight of an ultraviolet absorber composed of a benzotriazole compound represented by the following general formulas (II) and (III); (However, in the above formula, R ₂ represents an amino group, a derivative thereof, or a hydroxyl group, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, or a phenyl group.) (Wherein, R ₅ and R ₆ in the above formula represent a hydrogen atom or an alkoxy group, and R ₇ represents a hydrogen atom or an alkyl group), and one or two of a coumarin compound and a naphthalimide compound A polycarbonate resin composition comprising 0.1 part by weight to 10 parts by weight of a fluorescent whitening agent comprising