JP3329346B2 - Weather resistant polycarbonate resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of a polycarbonate resin having a clear hue, and more particularly, to a polycarbonate resin containing a specific phosphonite derivative to improve the discoloration resistance and the weather resistance, and to improve the transparency. And a polycarbonate resin molded product having excellent color clarity.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as engineering plastics having excellent mechanical strength, heat resistance, transparency, flame retardancy, dimensional stability, and electrical properties, such as automotive parts and various precision machine parts. I have. Coloring resins with dyes and pigments for the purpose of changing market requirements and appearance is generally widely practiced. In this case, the commercial value of the polycarbonate resin is determined not only by its inherent properties but also by its hue, color tone, color vividness and the like.

[0003] Therefore, the coloration does not adversely affect the physical properties of the polycarbonate resin, and the coloring temperature is high.
(.Degree. C.) and excellent dyeability, heat resistance and weather resistance are exclusively used. Examples of such dyes and pigments include anthraquinone dyes, indigoid dyes, perinone dyes, and phthalocyanine pigments. Among them, anthraquinone dyes, which are often used for blue, purple and green coloring of transparent products, have heat resistance at the processing temperature of polycarbonate resin.
Insufficient weather resistance, easy discoloration, and insufficient dyeing of molded articles.

[0004] In order to prevent this discoloration, a method using a phosphite-based heat stabilizer (Japanese Patent Publication No. 38-16240),
A method using a cyclic phosphite (Japanese Patent Publication No. 51-21430), a method using a phosphite and phosphorous acid in combination (Japanese Patent Publication Nos. 1-18332 and 1-18333), and a method using trimethyl phosphate in combination (Japanese Patent Application Laid-Open No. 52-147655), a method using phosphite and glycerol in combination (Japanese Patent Publication No. 47-404).
No. 46) and a method in which a compound having a hydroxyl group or polyalkylene glycol is used in combination with a phosphite-based stabilizer (Japanese Patent Publication Nos. 51-44552 and 1-50257).

A method using tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite as a phosphonite-type stabilizer (Japanese Patent Publication No. 62-10578, Japanese Patent Publication No.
62-10579) has been proposed. However, although these methods can improve the color development of the dye, they cannot simultaneously improve the weather resistance and hue stability, and have the disadvantage that discoloration or white turbidity occurs during use.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin molded article having a clear hue, improved weather resistance and hue stability, and excellent in discoloration and fading.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the conventional problems, and as a result, by blending a specific phosphonite compound with a polycarbonate resin, the polycarbonate resin was originally formed. Has excellent transparency,
The present inventors have found that a polycarbonate resin molded article having good weatherability and good coloration of the dye can be obtained without impairing the mechanical properties, heat resistance, and the like, and has reached the present invention.

That is, the present invention relates to a polycarbonate resin
100 parts by weight of tetrakis (2,4-di-t-butyl-5
-Methylphenyl) -4,4'-biphenylenediphosphonite
The present invention relates to a molded article of a polycarbonate resin containing 0.001 to 5 parts by weight, and further contains at least one kind of anthraquinone-based dye 0.00001 to 0.1 parts by weight and a weathering resistance containing an organic carboxylic ester having an iodine value of 15 or less. The present invention relates to a polycarbonate resin molded product having excellent properties.

The polycarbonate resin of the present invention is a thermoplastic aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound or a small amount thereof with a phosgene or carbonic acid diester. Or it is a copolymer.

Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) 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-tert-butyl-4-)
Hydroxyphenyl) propane, 2,2-bis (3-bromo-4
Bis (hydroxyaryl) alkanes exemplified by hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and the like; 1,1-bis (4-
Bis (hydroxyaryl) cycloalkanes exemplified by hydroxyphenyl) cyclopentane, 1,1-bis (hydroxyphenyl) cyclohexane and the like; 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1 Bis (hydroxyaryl) arylalkanes exemplified by 1,1-bis (4-hydroxyphenyl) diphenylmethane and the like; 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3 ' Dihydroxydiaryl ethers exemplified by -dimethyldiphenyl ether; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-
Dihydroxydiaryl sulfides exemplified by 3,3'-dimethyldiphenyl sulfide; dihydroxydiaryls exemplified by 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide -Disulfides exemplified by 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone
Rusulfones: hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, etc., and bisphenol A is particularly preferred.

The polycarbonate resin in the present invention may be a branched polycarbonate resin. In order to obtain a branched aromatic polycarbonate resin, phloroglucin and 2,6-dimethyl-2,4,6-tri (4-
Hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6
-Tri (4-hydroxyphenyl) heptene-2, 1,3,5-tri (2-hydroxyphenyl) benzene, 1,1,1-tri (4-
Hydroxyphenyl) ethane, 2,6-bis (2-hydroxy
-5-methylbenzyl) -4-methylphenol, α, α ',
α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and 1- [α-methyl-α- (4′-hydroxy) as disclosed in JP-A-62-146920. Phenyl) ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α-
(4'-hydroxyphenyl) ethyl] -3- [α ', α'-bis (hydroxyphenyl) ethyl] benzene and other polyhydroxy compounds, and 3,3-bis (4-hydroxyaryl) Oxyindole (isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-
Bromoisatin is exemplified.

When synthesizing a polycarbonate using phosgene, a terminal terminator or a molecular weight regulator can be usually used. Examples of the terminal terminator or molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, and are usually phenol, p-tert-butylphenol, bromophenol, chlorophenol, fluorophenol,
In addition to tribromophenol, trichlorophenol, etc., long-chain alkylphenol, aliphatic or aromatic carboxylic acid chloride, aliphatic carboxylic acid, aromatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxybenzoate Examples thereof include acid aryl esters and alkyl ether phenols.

Further, the present invention relates to a polycarbonate resin obtained by reacting an aryl or alkyl carbonate such as diphenyl carbonate with the above bisphenols in the presence of a transesterification catalyst. It is valid. As the transesterification catalyst, an alkali or alkaline earth metal compound, a quaternary ammonium salt, a phosphonium salt, a borate compound and the like can be applied.

It is important that the phosphonite compound used in the present invention improves the dyeability and weather resistance without impairing the dyeability and transparency of the polycarbonate resin. For this purpose, not only is the color development of the dye improved, but also after mixing and molding with the polycarbonate resin, the transparency of the polycarbonate resin is not impaired. Must not occur.

The phosphonite compound that can be used in the present invention that meets such conditions is tetrakis (2,4-di-t-butyl-5-methylphenyl) -4, represented by the following structural formula (A). 4'-biphenylenediphosphonite. The addition amount of the phosphonite compound is appropriately selected depending on the transparency and weather resistance, and is usually 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polycarbonate resin.
1 part by weight.

[0016]

Embedded image

The anthraquinone dye used in the present invention is a dye having an anthraquinone skeleton.
These dyes are classified on pages 7 to 40. Specific examples include anthraquinone blue, anthraquinone violet, anthraquinone green and the like, but are not necessarily limited thereto. These anthraquinone-based dyes can be used in combination of two or more, and can be used in combination with other dyes and pigments. In the present invention, the amount of the anthraquinone-based dye used is 0.000001 to 0.1 part by weight of at least one anthraquinone-based dye per 100 parts by weight of the polycarbonate resin, but is 0.00001 to 0.1 part by weight.
01 parts by weight is preferred.

The release agent used in the present invention is an organic carboxylic acid ester having an iodine value of 15 or less and having a low unsaturated bond content. The iodine value is measured according to Japanese Industrial Standard (JIS) K-3331. The above-mentioned organic carboxylic acid esters can be synthesized from aliphatic or aromatic saturated carboxylic acids having 8 or more carbon atoms, unsaturated carboxylic acids and alcohols.
And alcohols are preferably polyhydric alcohols. Specifically, for example, pentaerythrityltetrakis (stearate), monoglyceride stearate, monoglyceride behenate, beeswax having a low iodine value, trimethylolpropane tris (stearate),
Examples include, but are not necessarily limited to, lauryl laurate, stearyl stearate, and behenyl behenate.

A release agent having a high degree of unsaturation such as an iodine value exceeding 15 is not preferred because discoloration occurs during molding and weather resistance is deteriorated. In the case of a carboxylic acid ester having a small number of carbon atoms, the releasing effect is small, and it is liable to cause mold contamination due to volatile matters, and the risk of impairing the appearance of the molded product is not preferred. The amount of the release agent used is appropriately selected according to the purpose, and two or more types can be used in combination. Specifically, polycarbonate resin 10
It is 0.001 to 5 parts by weight with respect to 0 parts by weight, but preferably 0.01 to 1 part by weight is used.

The molded article of the present invention has substantially a haze (cloudiness) of about 1 regardless of the thickness or coloring degree of the molded article.
It is a transparent molded article of 0 or less, and is a transparent molded article having a light color and a low haze. Injection molding,
Extrusion molding, sheet molding, film molding, compression molding, blow molding, rotational molding and the like can be mentioned.

Further, the molded article of the present invention contains polycarbonate
Addition of other additives for the purpose of modifying resin, additives that do not impair the colorability, transparency, and weather resistance of the molded article, such as light stabilizers, heat stabilizers, flame retardants, and antistatic agents , Plasticizer,
A release agent, a lubricant, and other auxiliary materials can be used in combination.

[0022]

The present invention will be described below with reference to examples and comparative examples. The parts in the examples and comparative examples are parts by weight, and the heat resistance hue stability and the weather resistance were evaluated by the following methods.

Heat resistance evaluation method: A pellet of each composition was injected into an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .; Neomat 350 /
120; resin temperature 320 ° C, mold temperature 80 ° C, holding pressure 1000Kg / c
m ² ), 5 molded articles of 50 × 60 mm and 3 mm thickness were continuously molded, and after retaining the resin in the cylinder for 20 minutes, 5 molded articles were molded. This molded product was visually inspected by a color evaluation method described later.

Weather resistance evaluation method: Weather resistance was determined by pelletizing each composition with an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .; Neomat 350/120; resin temperature 290 ° C, mold temperature 80 ° C, holding pressure).
A molded article having a size of 50 × 60 mm and a thickness of 3 mm was continuously molded at 1000 kg / cm ² ), and the molded article was subjected to a weather resistance promotion test.

Weathering Acceleration Test: Initial Transparency: The transparency of the untreated molded article was measured using a haze meter, HM-100, manufactured by Murakami Color Research Laboratory Co., Ltd. It was measured. Aging resistance: Hot air circulation dryer PH-2 manufactured by Tabai Co., Ltd.
After aging at 120 ° C. for 720 hours using a mold 00, the molded product was visually inspected by the color evaluation method described later. Moisture and heat resistance: Haze was measured after treating with steam at 121 ° C for 100 hours.

Color evaluation method: The color evaluation of the molded product was judged by visual inspection by the hue (the type of color visually) and the color tone (the sharpness of the color visually). The judgment result of the color tone was displayed as follows. A: Good (has the original hue of the dye, and the color is clear) B: Normal C: Poor (hue changes or fades or lacks sharpness)

EXAMPLES 1-5 , COMPARATIVE EXAMPLES 1-5 Prepared by reacting almost equimolar amounts of 2,2-bis (4-hydroxyphenyl) propane with phosgene in an organic solvent together with triethylamine, caustic soda and phenol. To 100 parts by weight of the obtained polycarbonate homopolymer, a predetermined amount of an additive shown in Table 1 was added, mixed with a V-type blender, and then pelletized at 290 ° C. with a 50 mm extruder. The obtained pellets were molded and evaluated by the methods described above. The results are shown in Tables 1 to 3.

The following dyes were used as the anthraquinone dyes in Tables 1 to 3. Purple: Solvent Violet 13 Blue: Solvent Blue 94 Green: Solvent Green 3

The abbreviations in Tables 1 to 3 are shown below. Phosphonite compounds Compound A: tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite

[0030]

Embedded image Compound B: tetrakis (2,4-di-t-butylphenyl) -4,
4'-Biphenylenediphosphonite (Sand Co., Ltd.
(Product name Sandstar P-EPQ)

[0031]

Embedded image

Other stabilizer AO-1: pentaerythrityl [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (made by Asahi Denka Co., Ltd., trade name ADK STAB AO-60) AO-2: Tris (nonylphenyl) phosphite (made by Asahi Denka Co., Ltd., trade name ADK STAB 1178) AO-3: Tris (2 , 4-Di-t-butylphenyl) phosphite (Adeka Stab 2112, manufactured by Asahi Denka Co., Ltd.) UV: 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole (manufactured by Chemipro Chemical Co., Ltd.) , Trade name Chemisorb 78)

Release Agent The release agents used are shown in the table below. The iodine value of the release agent was measured according to Japanese Industrial Standards (JIS) K-3331.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

As described above, the molded article of the present invention containing a specific phosphonite compound and an anthraquinone dye has a good color tone, little discoloration of the dye at the time of molding and use, and has a high heat resistance. It is excellent in weather resistance, transparency and the like.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Daisuke Sanada 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref. Examiner, Plastics Center, Mitsubishi Gas Chemical Company, Inc. Satoshi Morikawa (56) References JP-A-5-178870 ( JP, A) JP-A-53-126055 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00

Claims (5)

(57) [Claims] 1 to 100 parts by weight of a polycarbonate resin, 0.001 to 5 parts by weight of tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite and at least one of Anthraquinone dye 0.0000
A weather-resistant polycarbonate resin molded product containing 01 to 0.1 parts by weight. (2) tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite is 0.01%
The polycarbonate resin molded product according to claim 1, wherein the amount is from 5 to 5 parts by weight. 3. The polycarbonate according to claim 1, wherein 0.001 to 5 parts by weight of an organic or carboxylic acid ester release agent having an iodine value of 15 or less, which is an aliphatic or aromatic carboxylic acid ester having 8 or more carbon atoms. Resin molded products. 4. The method according to claim 3, wherein the release agent is 0.01 to 1 part by weight.
The molded article as described. 5. Anthraquinone dyes 0.00001 to 0.001
The polycarbonate resin molded product according to claim 1, which is in parts by weight.