JPH101602A - Light resistant polycarbonate-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition not yellowing by exposure to light over a long period of time, having a stable color tone and suitable for an trimming part of an automobile, etc., by simultaneously using a specific yellow dyestuff with a light-stabilizer. SOLUTION: This light resistant polycarbonate-based resin composition is obtained by blending 100 pts.wt. polycarbonate-based resin consisting of (A) 1-100wt.% polycarbonate resin and (B) 0-99wt.% thermoplastic resin capable of mixing and mulling with the component (A), with (C) 0.05-2 pt.wt. light- stabilizer and (D) 0.0005-0.2 pt.wt. yellow dyestuff having a property of changing to white color on exposure to light. Further, it is preferable to use a polybutyleneterephthalate, a polyethyleneterephthalate, an acrylonitrile-EPDM- styrene copolymer or an acrylonitrile-butadiene-styrene copolymer as the component (B), a compound having a benzotriazole, a benzophenone or a piperidine skeleton in molecule thereof as the component (C) and solvent yellow 157 of a color index number as the component (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-resistant polycarbonate resin composition. More specifically, the present invention provides a polycarbonate resin composition capable of preventing discoloration upon exposure to light and maintaining a stable color tone for a long period of time.

[0002]

2. Description of the Related Art Polycarbonate alloys composed of a polycarbonate resin and a thermoplastic resin kneaded with the polycarbonate resin have a problem that they discolor when exposed to light and take on a yellow tint (yellowing). Therefore, when articles molded from these are exposed outdoors or the like for a long period of time, there is a problem that yellowing occurs due to light and the color tone of the molded article changes. In order to solve this, it has been attempted to blend a light stabilizer such as an ultraviolet absorber into a polycarbonate resin or a polycarbonate alloy.

[0003]

However, at present, it has not been possible to sufficiently prevent yellowing of a molded article when exposed to light by this method alone. The present invention solves this problem.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a specific yellow dye together with a light stabilizer, it is possible to achieve a long term. The present inventors have found that they do not turn yellow even when exposed to light and maintain a stable color tone, and have completed the present invention.

That is, the present invention relates to a method of producing a resin based on 100 parts by weight of a polycarbonate resin comprising 1 to 100% by weight of a polycarbonate resin (A) and 0 to 99% by weight of a thermoplastic resin (B) kneaded with the polycarbonate resin. 0.05 to 2 parts by weight of a stabilizer (C) and 0.000 of a yellow dye (D) having a property of whitening when exposed to light
An object of the present invention is to provide a light-resistant polycarbonate resin composition containing 5 to 0.2 parts by weight.

Hereinafter, the present invention will be described in detail. The polycarbonate resin (A) used in the present invention can be obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A).

As the above dihydroxydiaryl compounds, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) are used in addition to bisphenol A.
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane 1,1-bis (4- Hydroxy-
3-tert-butylphenyl) propane, 2,2-bis (4
-Hydroxy-3-bromophenyl) propane, 2,2
-Bis (4-hydroxy-3,5-dibromophenyl)
Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis ( Bis (hydroxyaryl) cycloalkanes such as 4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3
Dihydroxy diaryl ethers such as' -dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide; 4,4'-dihydroxy diphenyl sulfoxide; 4,4'-dihydroxy-3,3'-dimethyl Examples thereof include dihydroxydiarylsulfoxides such as diphenylsulfoxide, and dihydroxydiarylsulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone.

These may be used alone or as a mixture of two or more kinds. In addition, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be used in combination.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having three or more valences as shown below may be mixed and used. Phloroglucin, 4,6-dimethyl-2,4,6-tri-
(4-hydroxyphenyl) -heptene, 2,4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -Ethane and 2,2-bis-
[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity-average molecular weight of the polycarbonate resin (A) is not particularly limited, but is usually 10,000 to 100,000, preferably 15,000, in view of moldability and strength.
３５35,000. In producing such a polycarbonate resin, a molecular weight, a catalyst and the like can be used as necessary.

The thermoplastic resin (B) used in the present invention
Are aromatic polyesters such as polybutylene terephthalate and polyethylene terephthalate, and polystyrene (P
S), high impact polystyrene (HIPS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS),
Acrylonitrile-EPDM-styrene copolymer (AE
S) and other styrene copolymers. These may be used alone or in combination of two or more. Preferably, at least one thermoplastic resin selected from polybutylene terephthalate, polyethylene terephthalate and AES resin is used. The thermoplastic resin (B) is contained in a mixture of the thermoplastic resin (B) and the polycarbonate resin (A) in an amount of 0 to 9%.
9% by weight. Preferably, it is 0 to 60% by weight, more preferably 0 to 45% by weight.

The light stabilizer (C) used in the present invention includes benzotriazole light stabilizers, benzophenone light stabilizers, piperidine light stabilizers and the like. These may be used alone or in combination of two or more.

The light stabilizer (C) is used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin (A) or a mixture thereof with the thermoplastic resin (B). If it is less than 0.05 part by weight, the light resistance is poor, and if it exceeds 2 parts by weight, the effect reaches saturation, which is not preferable. A more preferred range is 0.3 to 1 part by weight.

The yellow dye (D) used in the present invention
Has a property of whitening when exposed to light. Examples of yellow dyes having such properties include Solvent Yellow 157, Solvent Green 5, Disperse Yellow 201, Disperse Orange 47, and Pigment Yellow. 180, Pigment Orange 43 and the like. These may be used alone or in combination of two or more.

The amount of the yellow dye (C) used is 0.0005 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin (A) or a mixture of the polycarbonate resin (A) and the thermoplastic resin (B). If it is less than 0.0005 parts by weight, light resistance is poor,
On the other hand, when the amount exceeds 0.2 parts by weight, the color tone is changed because the decoloring effect is too large, which is not preferable. A preferred range is 0.001 to 0.1 parts by weight. More preferably, it is 0.001 to 0.003 parts by weight.

Mixing of a polycarbonate resin (A), a thermoplastic resin (B) kneadable with the polycarbonate resin, a light stabilizer (C) and a yellow dye (D) having a property of whitening when exposed to light. There are no particular restrictions on the method,
Any mixers, such as tumblers, ribbon blenders,
A method of mixing with a high-speed mixer or the like and melt-kneading with an extruder or the like is exemplified.

At the time of mixing, if necessary, other additives,
For example, a release agent, a filler, an impact modifier, an antistatic agent, an antioxidant, a flame retardant, and a dye / pigment can be blended.

The light-resistant polycarbonate resin composition of the present invention can be used for applications where light is exposed outdoors, for example, for automobile exterior parts (wheel caps, door handles,
It can be suitably used for bumpers, door mirrors, and the like.

[0019]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “part” and “%”
Means parts by weight and% by weight, respectively, unless otherwise specified.

Test Method The obtained plate sample was tested using a weather meter (Sunshine Super Long Life Weather Meter WEL-SUN-HCH-B manufactured by Suga Test Instruments) under conditions of a black panel temperature of 63 ° C. and rainfall. 200
Irradiate for 400 hours.

Evaluation Method The change in hue after irradiation compared to before irradiation was measured using a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory) under red light, green and blue under a D65 light source (correlated color temperature of about 6504K). The respective stimulus values X, Y, and Z are obtained, and are calculated by the following equation as the degree of change in yellow tint relative to the plate sample before irradiation, that is, the degree of yellowing (変 YI). ΔYI = YI0−YI1 YI = 100 (1.28X−1.06Z) / Y YI0: Plate sample before irradiation YI1: Plate sample after irradiation The color difference (ΔE *) is the same as the plate sample before irradiation. It is a measure of the color shift with respect to the color, and from the tristimulus values X, Y, Z of the color obtained by the above-mentioned spectrophotometer, L * (lightness),
It is converted into a * (chromaticity from reddish to greenish) and b * (chromaticity from yellowish to bluish) and calculated by the following equation. ΔE * = √ ((L0 * −L1 *) 2+ (a0 * −a1 *) 2
+ (B0 * -b1 *) 2) L0 *, a0 *, b0 *: Plate sample before irradiation L1 *, a1 *, b1 *: Plate sample after irradiation, ie, ΔYI (yellowing degree), ΔE * The value of (color difference) is 0
The closer to, the closer the hue to that before irradiation, and the smaller the change in color with light irradiation.

Example-1 The components shown in Table 1 and titanium oxide white (S
1.05 parts of RCL-128 manufactured by CM and 0.01 parts of carbon black (MA-600B manufactured by Mitsubishi Chemical) are dry-mixed using a tumbler. Next, using a 40 mm single screw extruder, the mixture was melt-mixed at a set temperature of 250 ° C.
Was obtained. The obtained pellet 1 is injection-molded at a set temperature of 250 ° C. using a 4-ounce injection molding machine,
A 3.2 × 55 × 45 mm plate sample 1 was obtained.
The light resistance of the obtained plate sample 1 was evaluated by the test method and the evaluation method described above. Table 1 shows the results. As a comparative example, the same operation was performed to obtain composition 2 and plate sample 2. Composition 2 was toned to the same color as composition 1 using titanium oxide white and carbon black. Table 1 shows the results.

[0023]

[Table 1] * 1: Sumitomo Dow polycarbonate resin (200-1)
3) * 2: Benzotriazole light stabilizer (Chemisorb 79 manufactured by Chemipro Kasei) * 3: Piperidine light stabilizer (Kimasorb 944FD manufactured by Ciba Geigy) * 4: Sumiplasto Lemon Yellow HG manufactured by Sumitomo Chemical Co., Ltd.
N

Example 2 Compositions 3 to 6 and plate samples 3 to 6 were obtained in the same manner as in Example 1, except that the components shown in Table 2 and the composition ratio were changed. Table 2 shows the results of each light resistance evaluation.

[0025]

[Table 2] * 5: AES resin manufactured by Sumika ABS Latex (U
B-500P) * 6: ABS resin manufactured by Sumika ABS Latex (K
−2540A)

Example 3 Except for using the components shown in Table 3 and their composition ratios, and using 0.5 part of titanium oxide white and 1.4 parts of titanium oxide yellow (TY-70 manufactured by Ishihara Sangyo) as a coloring agent. The same operation as in Example 1 was performed to obtain compositions 7 to 8 and plate samples 7 to 8. Composition 8 was toned to the same color as composition 7 using titanium oxide white and titanium oxide yellow.
Table 3 shows the results.

[0027]

[Table 3] * 7: Polybutylene terephthalate (600FP made of polyplastic) * 8: Impact modifier (S-2001 manufactured by Mitsubishi Rayon) * 9: Macrolex Yellow 6G manufactured by Bayer

Example-4 Components shown in Table 4, their composition ratios, and 0.002 parts of Disperse Violet 28 (Sumiplast Violet RR manufactured by Sumitomo Chemical Co., Ltd.) as a coloring agent, Solvent Blue 97 (Macrolex Blue RR manufactured by Bayer) 0.
Except for using 0006 parts and 1.4 parts of titanium oxide white, the same operation as in Example 1 was carried out, and compositions 9-1 to 9-1 were used.
0 and plate samples 9-10 were obtained. Composition 10 was toned to the same color as composition 9 using Disperse Violet 28, Solvent Blue 97 and titanium oxide white. Table 4 shows the results.

[0029]

[Table 4] * 10 Sumitomo Chemical Industries Sumiplast Yellow FL7G

Example-5 All of the examples were the same as those shown in Table 5 except that 0.003 part of iron oxide red (120ED manufactured by Toda Kogyo) and 1.05 part of titanium oxide white were used as the coloring agents and the components shown in Table 5. The same operation as in -1 was performed to obtain Compositions 11 to 12 and Plate Samples 11 to 12. In addition, composition 12
Is a composition 11 using iron oxide red and titanium oxide white.
And the same color. Table 5 shows the results.

[0031]

[Table 5] * 11: Polyethylene terephthalate (NE manufactured by Unitika)
S-1240) * 12: Benzophenone light stabilizer (Sumisorb 130 manufactured by Sumitomo Chemical Co., Ltd.) * 13: PV Fast Yellow HG manufactured by Hoechst

Example-6 Components shown in Table 6, their composition ratios and 0.0062 parts of Disperse Violet 28 (Sumiplast Violet RR manufactured by Sumitomo Chemical Co., Ltd.) as a coloring agent, Solvent Blue 97 (Macrolex Blue RR manufactured by Bayer)
Except that 0.0031 part, 1.4 parts of titanium oxide white and 0.01 part of carbon black were used, all examples were performed.
By performing the same operations as in Example 1, compositions 13 to 15 and plate samples 13 to 15 were obtained. Compositions 14 and 15 were Disperse Violet 28 and Solvent Blue 9
7. Toned in the same color as Composition 13 using titanium oxide white and carbon black. Table 6 shows the results.

[0033]

[Table 6] * 14: Bayer Macrolex Orange R * 15: Hoechst PV Fast Orange GRL * 16: Yellow dye that does not whiten when exposed to light (Olaset Yellow GHS from Ciba Geigy)

[0034]

The polycarbonate resin composition of the present invention has a small discoloration when exposed to light and maintains a stable color tone for a long period of time. It can be suitably used.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 55/02 LMF C08L 55/02 LMF 67/02 LPE 67/02 LPE 101/00 LTA 101/00 LTA

Claims (4)

[Claims] 1. Polycarbonate resin (A) 1 to 100
Light stabilizer (C) 0.05 to 100 parts by weight of a polycarbonate resin comprising 0 to 99% by weight of a thermoplastic resin (B) kneaded with the polycarbonate resin.
A light-resistant polycarbonate resin composition comprising 2 parts by weight and 0.0005 to 0.2 part by weight of a yellow dye (D) having a property of whitening when exposed to light. 2. The thermoplastic resin (B) is composed of polybutylene terephthalate, polyethylene terephthalate, acrylonitrile-EPDM-styrene (AES) copolymer or acrylonitrile-butadiene-styrene copolymer (AB).
The light-resistant polycarbonate-based resin composition according to claim 1, wherein S). 3. The light stabilizer (C) is a compound having a benzotriazole, benzophenone or piperidine skeleton in the molecule.
The light-resistant polycarbonate resin composition according to the above. 4. The yellow dye (D) is Solvent Yellow 157, Solvent Green 5, Disperse Yellow 201, Disperse Orange 47, Pigment Yellow 180 or Pigment Orange 43 having a color index number. 1, Claim 2
Or the light-resistant polycarbonate resin composition according to claim 3.