JPH0733969A - Weatherable molded object of polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin molding reduced in discoloration and having improved weatherability, transparency, and a bright color by incorporating a specific phosphonite derivative into a polycarbonate resin. CONSTITUTION:The molding is obtained from a composition which comprises 100 pts.wt. polycarbonate resin and 0.001-5 pts.wt. tetrakis(2, 4-di-t-butyl-5- methylphenyl) 4,4'-biphenylenediphosphonite and which may optionally contain 0.000001-0.1 pt.wt. at least one anthraquinone dye and 0.001-1 pt.wt. organic carbonic ester having an iodine value of 15 or smaller as a release agent. The molding has a good color tone, undergoes little dye discoloration during molding and use, and is excellent in heat resistance, weatherability, transparency, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin molded product having a clear hue. More specifically, by incorporating a specific phosphonite derivative into the polycarbonate resin, the discoloration resistance and weather resistance are improved and the transparency is improved. , A polycarbonate resin molded product having excellent color clarity.

[0002]

Polycarbonate resins have been widely used as engineering plastics having excellent mechanical strength, heat resistance, transparency, flame retardancy, dimensional stability, and electrical characteristics, for example, automobile parts and various precision machine parts. There is. In addition, it is generally widely practiced to color a resin with a dye or pigment for the purpose of changing market requirements or appearance. In that case, the commercial value of the polycarbonate resin is determined by the hue, the color tone, the vividness of the color, etc., in addition to the inherent properties.

Therefore, the coloring does not adversely affect the physical properties of the polycarbonate resin, and its high processing temperature (about 3
Dyes and pigments that are resistant to (00 ° C) and have excellent dyeability, heat resistance, and weather resistance are used exclusively. Examples of such dyes and pigments include anthraquinone dyes, indigoid dyes, perinone dyes, phthalocyanine pigments, and the like. Among them, anthraquinone dyes, which are often used for coloring blue, purple and green of transparent products, are heat-resistant at processing temperature of polycarbonate resin,
The weather resistance is insufficient, discoloration is likely to occur, and the dyeing of molded products is often insufficient.

In order to prevent this discoloration, a method using a phosphite type heat stabilizer has been conventionally used (Japanese Patent Publication No. 38-16240),
Method using cyclic phosphite (Japanese Patent Publication No. 51-21430), method using phosphite and phosphorous acid (Japanese Patent Publication 1-18332, Japanese Patent Publication 1-18333), and trimethyl phosphate used together Method (JP-A-52-147655), method using phosphite and glycerol together (JP-B-47-404)
46), and a method in which a compound having a hydroxyl group or polyalkylene glycol is used in combination with a phosphite stabilizer (Japanese Patent Publication No. 51-44552 and Japanese Patent Publication No. 1-50257).

Further, 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 improve the weather resistance and the hue stability at the same time, and have the drawback that discoloration or white turbidity occurs during the period of use.

[0006]

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

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the conventional problems, and as a result, by blending a specific phosphonite compound with a polycarbonate resin, a polycarbonate resin is originally obtained. Has excellent transparency,
The inventors have found that a polycarbonate resin molding having good color development of dyes and weatherability can be obtained without impairing mechanical properties, heat resistance, etc., and arrived at the present invention.

That is, the present invention is a polycarbonate resin
Tetrakis (2,4-di-t-butyl-5) based on 100 parts by weight
-Methylphenyl) -4,4'-biphenylenediphosphonite
Regarding a polycarbonate resin molded product containing 0.001 to 5 parts by weight, a weather resistance obtained by further adding at least one anthraquinone dye 0.00001 to 0.1 part by weight and a release agent composed of an organic carboxylic acid 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 diester of phosgene or carbonic acid. Alternatively, it is a copolymer.

Examples of aromatic dihydroxy compounds 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-tertiary-butyl-4-
Hydroxyphenyl) propane, 2,2-bis (3-bromo-4)
-Hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, and other bis (hydroxyaryl) alkanes; 1,1-bis (4-
Bis (hydroxyaryl) cycloalkanes exemplified by hydroxyphenyl) cyclopentane and 1,1-bis (hydroxyphenyl) cyclohexane; 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; 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiary exemplified by 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide -Sulfoxides; dihydroxy diary-exemplified by 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc.
Examples of the sulfones include hydroquinone, resorcin, and 4,4'-dihydroxydiphenyl, with bisphenol A being most preferred.

The polycarbonate resin in the present invention may be a branched polycarbonate resin. To obtain a branched aromatic polycarbonate resin, phloroglucin, 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 etc. are illustrated.

When synthesizing a polycarbonate using phosgene, an end terminating agent or a molecular weight modifier can usually be used. Examples of the terminal terminator or molecular weight modifier include compounds having a monovalent phenolic hydroxyl group, usually phenol, p-tertiary 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, hydroxybenzoic acid Examples thereof include acid aryl esters and alkyl ether phenols.

The present invention also 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 an ester exchange 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 or 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 that purpose, not only the color developability of the dye is improved, but also the transparency of the polycarbonate resin is not impaired even if it is mixed with the polycarbonate resin and then molded, and it becomes cloudy under high temperature and high humidity conditions. Need not occur.

The phosphonite compound which can be used in the present invention which meets the above conditions is tetrakis (2,4-di-t-butyl-5-methylphenyl) -4, represented by the following structural formula (A). It is 4'-biphenylenediphosphonite. The addition amount of the phosphonite compound is appropriately selected depending on the transparency and weather resistance, but 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]

[Chemical 1]

The anthraquinone dye used in the present invention is a dye having an anthraquinone skeleton and is edited by the Japan Society for the Promotion of Science, Dyeing Process 120th Committee, "New Dyeing Process Course 1" 3
The dyes are classified into pages 7 to 40. Specific examples thereof include anthraquinone blue type, anthraquinone violet type, and anthraquinone green type, but are not necessarily limited thereto. These anthraquinone 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 dye used is 0.000001 to 0.1 part by weight of at least one anthraquinone dye per 100 parts by weight of the polycarbonate resin, but 0.00001 to 0.
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 a small content of unsaturated bonds. The iodine value is measured according to Japanese Industrial Standard (JIS) K-3331. The above-mentioned organic carboxylic acid ester is an aliphatic or aromatic saturated carboxylic acid having 8 or more carbon atoms, unsaturated carboxylic acid and alcohol.
It is an ester of alcohol, and the alcohol is preferably a polyhydric alcohol. Specifically, for example, pentaerythrityl tetrakis (stearate), stearic acid monoglyceride, behenic acid monoglyceride, beeswax having a low iodine value, beeswax, trimethylolpropane tris (stearate),
Examples thereof include lauryl laurate, stearyl stearate, behenyl behenate, and the like, but are not necessarily limited thereto.

A release agent having a high degree of unsaturation with an iodine value of more than 15 is not preferred because it causes discoloration during molding and poor weather resistance. Further, 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 contamination of the mold with volatile matter, and there is a high risk of impairing the appearance of the molded product, which is not preferable. The amount of the release agent used is appropriately selected according to the purpose, and two or more kinds can be used in combination. Specifically, polycarbonate resin 10
The amount is 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 0 parts by weight.

The molded article of the present invention has a haze (cloudiness) of substantially 1 regardless of the thickness and the coloring degree of the molded article.
It is a transparent molded product of 0 or less, which is a light-colored transparent molded product having a low haze. As the molding method of the molded product, 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 includes a polycarbonate panel.
Other additives for the purpose of modifying the resin are additives that do not impair the coloring, transparency, and weather resistance of the molded product, such as light stabilizers, heat stabilizers, flame retardants, antistatic agents. , Plasticizer,
A release agent, a lubricant, and other auxiliary materials can be used in combination.

[0022]

EXAMPLES Examples and comparative examples will be described below. The parts in the examples and comparative examples are parts by weight, and the heat-resistant hue stability and weather resistance were evaluated by the following methods.

Heat resistance evaluation method: injection molding machine for pellets of each composition (Sumitomo Heavy Industries, Ltd .; Neomat 350 /
120 ； Resin temperature 320 ℃, Mold temperature 80 ℃, Holding pressure 1000Kg / c
Five molded articles each having a size of 50 × 60 mm and a thickness of 3 mm in m ² were continuously molded, and the resin was retained in the cylinder for 20 minutes and then molded into five. This molded product was visually inspected by the color evaluation method described below.

Weather resistance evaluation method: For weather resistance, the pellets of each composition are injection molded by an injection molding machine (Sumitomo Heavy Industries, Ltd .; Neomat 350/120; resin temperature 290 ° C, mold temperature 80 ° C, holding pressure).
A molded product having a size of 50 × 60 mm and a thickness of 3 mm was continuously molded at 1000 kg / cm ² ) and a weather resistance accelerated test was performed on this molded product.

Weather resistance accelerated test: Initial transparency: The transparency of an untreated molded article was measured with a head meter (HM-100 type, manufactured by Murakami Color Research Laboratory Co., Ltd.). It was measured. Aging resistance: Hot air circulating dryer PH-2 manufactured by Tabai Co., Ltd.
After aging with a 00 type at 120 ° C. for 720 hours, the molded product was visually inspected by the color evaluation method described later. Moisture and heat resistance: The haze was measured by treating with steam at 121 ° C for 100 hours.

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

Examples 1-6, Comparative Examples 1-6 With triethylamine, caustic soda, and phenol in an organic solvent in approximately equimolar amounts of 2,2-bis (4-hydroxyphenyl) propane and phosgene. A predetermined amount of the additive shown in Table 1 was added to 100 parts by weight of the polycarbonate homopolymer prepared by the reaction of the above, mixed with a V type blender, and then pelletized at 290 ° C. by a 50 mmφ extruder. The obtained pellets were molded and evaluated by the above method. 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 Bull-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]

[Chemical 2] Compound B: tetrakis (2,4-di-t-butylphenyl) -4,
4'- Biphenylenediphosphonite (Sand Co.,
(Product name Sand Star P-EPQ)

[0031]

[Chemical 3]

Other Stabilizers AO-1: Pentaerythrityl [3- (3,5-di-t-butyl-4]
-Hydroxyphenyl) propionate] (Asahi Denka Co., Ltd., trade name Adeka Stab AO-60) AO-2: Tris (nonylphenyl) phosphite (Asahi Denka Co., Ltd., trade name Adeka Stab 1178) AO-3: Tris (2 , 4-Di-t-butylphenyl) phosphite (Asahi Denka Co., Ltd., trade name ADEKA STAB 2112) UV: 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole (Chempro Kasei Co., Ltd. , Product name Chemisorb 78)

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

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

INDUSTRIAL APPLICABILITY As described above, the molded article according to the present invention containing the specific phosphonite compound has a good color tone, little discoloration of the dye at the time of molding and use, heat resistance, weather resistance and transparency. It has excellent properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Daisuke Sanada 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (6)

[Claims] 1. 0.001 to 5 parts by weight of tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite is added to 100 parts by weight of a polycarbonate resin. Weather resistant polycarbonate resin molded product. 2. Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite 0.001 to 5 parts by weight and at least one of 100 parts by weight of a polycarbonate resin. Anthraquinone dye 0.0000
A weather-resistant polycarbonate resin molded product containing 01 to 0.1 part by weight. 3. Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonite of 0.01 to
The polycarbonate resin molded product according to claim 1 or 2, which is 5 parts by weight. 4. The polycarbonate according to claim 2, which is an aliphatic or aromatic carboxylic acid ester having 8 or more carbon atoms, and 0.001 to 5 parts by weight of an organic carboxylic acid ester-based releasing agent having an iodine value of 15 or less. Resin molded product. 5. The molded article according to claim 4, wherein the release agent is 0.01 to 1 part by weight. 6. An anthraquinone dye is 0.00001 to 0.001.
The polycarbonate resin molded article according to claim 2, which is parts by weight.