JPH05117516A - Colored polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To provide a colored polycarbonate resin composition reduced in the discoloration of dyestuffs and excellent in the thermal stability. CONSTITUTION:The resin composition comprises (A) 100 pts.wt. of a polycarbonate resin. (B) 0.00001-0.3 pt.wt. preferably 0.00005-0.1 pt.wt., of one kind or more of anthraquinone dyestuffs selected from blue, violet and green anthraquinone dyestuffs, (C) 0.0005-0.5 pt.wt., preferably 0.001-0.05 pt.wt., of a polyalkylene glycol derivative of the formula (R<1> is H, lower alkyl; R<2> is 1-30C alkyl; R<3> is H, 1-30C acyl; m is 1-1000) and having a number-average mol.wt. of 500-10000 (e.g. ethylene glycol or propylene glycol), and (D) 0.0001-0.3 pts.wt. of a phosphorous acid or phosphite stabilizer or a phenolic stabilizer as a thermal stabilizer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a colored polycarbonate resin composition having a sharp hue. More specifically, the present invention has good color developability of the dye, and apparent transparency in light color,
The present invention relates to a colored polycarbonate resin composition which is excellent in resistance to discoloration and fading and has a clear color in a dark color and is suitable for producing injection molded products, sheets, films and the like.

[0002]

2. Description of the Related Art Polycarbonate resin has the following properties: transparency, mechanical properties, flame retardancy, dimensional stability, and electrical characteristics.
It is used in a wide range of fields. Further, it is often practiced to color the resin with a dye or pigment for the purpose of changing the market demand or appearance. In that case, the commercial value of the colored polycarbonate is determined by hue, color tone, color vividness, and the like. Therefore, for the coloring, dyes and pigments are used exclusively, which can withstand a molding temperature of about 300 ° C. without adversely affecting the polycarbonate resin and have good dyeability. Examples of such dyes and pigments include anthraquinone dyes, indigoid dyes, perinone dyes, and phthalocyanone pigments. However, the heat resistance of the anthraquinone dyes, which are mostly used for coloring blue, purple and green, is insufficient,
Discoloration and discoloration were likely to occur, and the dyeing of molded products was often insufficient. In order to prevent this discoloration and fading, conventionally, a method of simply using a phosphite stabilizer or a method of using a compound having a hydroxyl group or a polyalkylene glycol together with a phosphite stabilizer (Japanese Patent Publication No. 1-50257) has been proposed. However, even if a heat stabilizer having an effect on a conventional polycarbonate resin is used, it is not possible to improve the color development of the dye, and in general, a molded product that discolors and fades during molding has been obtained.

[0003]

Means for Solving the Problems The present inventors diligently studied in order to reduce discoloration and fading of a colored polycarbonate resin during heating and melting, and to improve the color development of an anthraquinone dye. As a result, an aromatic anthraquinone dye By blending a specific polyalkylene glycol derivative into a polycarbonate resin colored with, a polycarbonate resin having good coloring of the dye without impairing the excellent transparency, mechanical properties, and heat resistance originally possessed by the polycarbonate resin. They have found that a composition is obtained and have reached the present invention.

That is, in the present invention, 0.0100 to 0.3 part by weight of at least one anthraquinone dye per 100 parts by weight of a polycarbonate resin, and 0.0005 to 0.5 part of at least one polyalkylene glycol derivative represented by the following general formula (1) are used. It is a colored polycarbonate resin composition having a clear hue, which is characterized by being mixed by weight, and the composition contains 0.0001 phosphorous acid or a phosphite stabilizer or a phenol stabilizer as a heat stabilizer. ~
0.3 parts by weight, the anthraquinone dye is bluish,
A colored polycarbonate resin composition comprising one or more selected from anthraquinone dyes of purple and green colors. R ² COO- (CH ₂ -CHR ¹ -O) _m -R ³ (1) (wherein R ¹ represents hydrogen or a lower alkyl group, R ² represents an alkyl group having 1 to 30 carbon atoms or 0 to 2 Represents a phenyl group substituted with lower alkyl groups, R ³ is hydrogen or 1 to
30 acyl groups are shown. m is an integer from 1 to 1000. ).

The polycarbonate resin of the present invention is an optionally branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with phosgene or a diester of carbonic acid. It is a polymer. 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-
Tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, etc. Rubis (hydroxyaryl)
Alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxy Diphenyl diaryl ethers exemplified by diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether and the like; 4,4'-dihydroxydiphenyl sulfide, 4,4 '
-Dihydroxydiarylsulfides exemplified by dihydroxy-3,3'-dimethyldiphenylsulfide; 4,4 '
-Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dihydroxydiaryl sulfoxides exemplified by dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-
Dihydroxydiarylsulfones exemplified by 3,3′-dimethyldiphenylsulfone and the like; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like can be mentioned, and bisphenol A is particularly preferable. Further, to obtain a branched aromatic polycarbonate resin, phloroglysin, 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) Polyhydroxy compounds exemplified by -5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,3 Examples thereof include -bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like.

In the case of phosgene-processed polycarbonate,
Usually, a terminator or a molecular weight regulator is used. Examples of the terminal terminator or molecular weight modifier include compounds having a monovalent phenolic hydroxyl group, ordinary phenol, p-
In addition to tert-butylphenol, tribromophenol, etc., long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl acid alkyl ester, alkyl ether phenol, etc. are exemplified.

The anthraquinone-based dye used in the present invention is a dye having an anthraquinone skeleton, and is "New Dyeing and Processing Course 1" 37th Edition edited by the Japan Society for the Promotion of Science, 120th Committee
Such dyes are classified into pages 40 to 40. Specific examples thereof include anthraquinone blue type, anthraquinone violet type, and anthraquinone green type.
It is not necessarily limited to these. These anthraquinone dyes can be used in combination of two or more, and can also be used in combination with other dyes and pigments. The amount of the anthraquinone dye used is appropriately selected according to the purpose from a wide range from light-colored products for masking to general dark products, and at least one anthraquinone is used per 100 parts by weight of the polycarbonate resin. The amount of the system dye is 0.00001 to 0.3 part by weight, preferably 0.00005 to 0.1 part by weight.

The polyalkylene glycol derivative represented by the above general formula (1) of the present invention is ethylene glycol,
Propylene glycol, butylene glycol and other diols, or polyethylene glycol, polypropylene glycol or polybutylene glycol and other polyalkylene glycol alkyl or lower alkyl group-substituted phenyl mono- or di-esters, usually repeating alkylene glycol chain moieties. Those having a number in the range of 1 to 1000 can be used, and the number average molecular weight (Mn) is preferably 500 to 10,000, more preferably 1000 to 5000. Further, the compounding amount thereof may be in the range of 0.0005 to 0.5 part by weight, more preferably 0.001 to 0.05 part by weight, per 100 parts by weight of the polycarbonate resin.

In the present invention, it is preferable to use phosphorous acid or a phosphorous acid ester in combination with the above polyalkylene glycol derivative in order to accelerate color development and prevent thermal discoloration. The amount of phosphorous acid or phosphite used is 0.0001 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin, and may be added as it is or as an aqueous solution. Examples of the phosphite include triphenyl phosphite,
Tricresyl phosphite, tri (nonylphenyl) phosphite, tris (4-tert-butylphenyl)
Phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, diphenyl-monodecyl phosphite, monophenyl-didecyl phosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl diphosphite, bis (nonylphenyl) pentaerythrityl diphosphite, dilauryl pentaerythrityl diphosphite, distearyl pentaerythrityl diphosphite, bis (2,4-di -Tert-butylphenyl) pentaerythrityl diphosphite, bis
(2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, 2,2-methylenebis
(4,6-Di-tert-butyl-phenyl) octyl phosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymer, hydrogenated bisphenol A-phenol phosphite polymer and the like can be preferably used.

Other additives for the purpose of modifying the polycarbonate resin may be added to the composition of the present invention. For example, flame retardants, light stabilizers, heat stabilizers, antistatic agents, plasticizers, release agents, lubricants, compatibilizers, foaming agents, glass fibers, carbon fibers, reinforcing agents such as ceramic whiskers, fillers,
In addition, in combination with dyes and pigments, and in addition to polycarbonate resins, for example, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, polymethylmethacrylate, ABS resin, polyethylene ethene, polyphenylene oxide, and other elastomers. Etc. can also be mixed.

[0011]

EXAMPLES Examples and comparative examples will be described below. The parts in the examples and comparative examples are parts by weight, and the hue stability was evaluated by the following method. Color evaluation method: Pellet each composition using an injection molding machine, injection molding machine (Sumitomo Heavy Industries, Ltd .; Neomat
350/120) resin temperature 320 ℃, mold temperature 80 ℃, holding pressure 1000
5 pieces of 50 mm x 60 mm and 3 mm thick molded pieces are continuously molded in kg / cm ² or after the resin is retained in the cylinder for 30 minutes.
One piece was formed. The color evaluation of the molded product was carried out by superimposing five molded products and visually judging the hue (color type by visual inspection) and the color tone (visual clarity). The judgment result of the color tone is displayed as follows. A: Good (has original hue of dye and clear color) B: Normal C: Poor (hue discoloration or lack of sharpness)

Examples 1-9, Comparative Examples 1-4 Together with triethylamine, sodium hydroxide and p-tert-butylphenol, approximately equimolar amounts of 2,
Polycarbonate homopolymer prepared by reacting 2-bis (4-hydroxyphenyl) propane with phosgene
A predetermined amount of the additive shown in Table 1 was added to 100 parts, mixed with a tumbler type blender, and then pelletized at 300 ° C. with a 50 mmφ extruder. The obtained pellets were molded by the above method, and the color was evaluated. The results are shown in Tables 1-1 and -2. Tables 1-1 and 2 show examples of anthraquinone dyes (hereinafter referred to as "AQ dyes") colored in purple and light purple. From this table, Examples (using polyalkylene glycol derivative) are shown.
It is clear that the above-mentioned method is superior in hue and tone to the comparative example (without using the polyalkylene glycol derivative).

The abbreviations in Tables 1-1 and 2 are as follows. PAGs: Polyalkylene glycols (Mn: number average molecular weight) PPGDS2: Mn = 2 × 10 ³ no polypropylene glycol glycol stearate PPGMA1: Mn = 1 × 10 ³ no poly (polypropylene glycol) monoacetate PEGDS3: Mn = 3 × 10 ³ Polyethyleneglycol stearate PPGMS2: Mn = 2 × 10 ³ no polypropylenglycol monostearate PBGDA2: Mn = 2 × 10 ⁴ nopolyethylenedichloroacetate phosphite: Phosphorous acid or phosphite ester stabilizer TDTBPP: Tris (2,4-di-t-butylphenyl) phosphite HP stabilizer: Sterically hindered phenolic stabilizer Ir1010: pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-human benzyloxyphenyl) ) Propionate

[0014]

[Table 1]Table 1-1 Implementation & Comparative Example Ratio 1 Ratio 2 Ratio 3 Ratio 4 Real 1 Real 2 Real 3 Molding method Continuous continuous continuous retention continuous continuous continuous continuousAQ dye: purple (part ) 0.00008 Same as left Same as left Same as left Same as left Same as left Same as left Same as left PAGs (species) None None None None PPGDS2 PPGDS2 PPGDS2 (Part ) ─ ─ ─ ─ 0.002 0.002 0.002 Phosphite (seed) None Phosphorous acid Phosphorous acid None TDTBPP Phosphorous acid Phosphorous acid (Part ) --0.003 0.003 --0.03 0.003 0.003 HP stabilizer (species) None None None Ir1010 None None None None(Part ) ─ ─ ─ 0.1 ─ ─ ─ Color evaluation Hue Pink Gray Gray Gray Purple Purple PurpleColor C C C C B A B

[0015]

[Table 2] Table 1-2 Implementation & Comparative Examples Real 4 Real 5 Real 6 Real 7 Real 8 Real 9 Molding method Continuous Continuous Continuous Retention Continuous Continuous AQ dye: Purple (part ) 0.00008 Same as left Same as left Same as left Same as left Same as left PAGs (species) PPGDS2 PPGMA1 PEGDS3 PEGDS3 PPGMS2 PBGDA2 (part ) 0.002 0.002 0.002 0.002 0.005 0.003 Phosphite (species) None Phosphorous acid None None TDTBPP TDTBPP (part ) ─ 0.003 ─ ─ 0.03 0.03 HP stabilizer (species) None None Ir1010 Ir10 Ir1010 Ir10 (parts) ─ ─ 0.1 0.1 0.1 ─ color evaluation hue Murasaki Murasaki Murasaki Murasaki Murasaki Murasaki color A B A B A A

Examples 10-15, Comparative Examples 5-8 Example 1 except that the anthraquinone blue dye was used in place of the anthraquinone purple dye and the additives shown in Table 2 were added.
Pelletizing was performed in the same manner as ~ 9, and color evaluation was performed. The results are shown in Tables 2-1 and 2. Examples 10 to 15 are comparative examples 5 to 8.
It is clear that it is superior in color tone to The abbreviations in the table are as follows. AQ Dye: Anthraquinone Dye PAGs: PPGDS2: Mn = 2000 Novopolypropylene glycol Stearate PEGMA3: Mn = 3000 Polyethyleneglycol monoacetate PEGDA3: Mn = 3000 Polyethyleneglycol Acetate PBGDS3: Mn = 3000 Novolene Diesterate phosphites: TDTBPP: tris (2,4-di-t-butylphenyl) phosphite BBPPDP: bis (2,4-ditertiary phenethylphenyl) pentaerythrityl diphosphite HP stabilizer: Ir1010 : Pentaerythrityl tetrakis [3- (3,5-di-t-butyl
-4-Hitoxy) Propione]

[0017]

[Table 3] Table 2-1 Implementation & Comparative Examples Ratio 5 Ratio 6 Ratio 7 Ratio 8 Actual 10 Actual 11 Molding method Continuous Continuous Retention Continuous Continuous Continuous AQ Dye: Blue (part ) 0.005 Same as left Same as left Same as left Same as left PAGs (species) None None None None None PPGDS2 PPGDS2 (part ) ─ ─ ─ ─ 0.003 0.003 Phosphite (seed) None TDTBPP TDTBPP None None BBPPDP (part ) ─ 0.03 0.03 ─ ─ 0.03 HP stabilizer (seed) None Ir1010 Ir1010 Ir1010 None Ir1010 (part) ) ─ 0.1 0.1 0.1 ─ 0.1 color evaluation hue blue blue blue blue blue blue color C C C C B A

[0018]

[Table 4]

Examples 16 to 19 and Comparative Examples 9 to 12 Example 1 except that anthraquinone green dye was used instead of anthraquinone blue dye and the additives shown in Table 3 were added.
Pelletizing was performed in the same manner as ~ 9, and color evaluation was performed. The results are shown in Table 3. From Table 3, it is clear that the examples using the polyalkylene glycol derivative are superior in terms of hue and tone.

[0020]

[Table 5]Table 3 Implementation & Comparative Example Ratio 9 Ratio 10 Ratio 11 Ratio 12 Actual 16 Actual 17 Actual 18 Actual 19 Molding method Continuous retention Continuous retention Continuous continuous Continuous continuousAQ dye: green (part ) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05Titanium oxide (part ) − − − 0.5 − − − 0.5 PAGs (species) No No No No PPGDS2 Same as left PEGDS2 PPGDS2 (Part ) − − − − 0.003 Same as left Same as left Same as left Same as left phosphite (species) No No TDTBPP Same as left No No Phosphorous acid No(Part ) − − 0.05 0.05 ─ ─ 0.002 ─ HP stabilizer (seed) No No Ir1010 Same as left No No Ir1010 No(Part ) − − 0.1 0.1 ─ ─ 0.1 ─ Color evaluation Hue Green Dark Green Green Gray Green Green Green Green GreenColor C C C C A B A A The abbreviations in the table are the same as in Table 1.

[0021]

As is apparent from Tables 1-1 to 3, the composition of the present invention in which the polyalkylene glycol derivative is added to the anthraquinone dye has less discoloration and fading of the dye.
It also has excellent thermal stability. Therefore, the colored polycarbonate resin composition of the present invention is useful for various molding materials due to its good hue.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08K 5/524 KKM 7167-4J C08L 69/00 LPU 8416-4J

Claims (3)

[Claims] 1. At least one anthraquinone type dye 0.00001 to 0.3 per 100 parts by weight of a polycarbonate resin.
Parts by weight, and 0.0005 to 0.5 parts by weight of at least one of the polyalkylene glycol derivatives represented by the following general formula (1) are blended 0.0005 to 0.5 parts by weight of a sharp colored polycarbonate resin composition R ² COO- ( CH ₂ -CHR ¹ -O) _m -R ³ (1) (In the formula, R ¹ represents hydrogen or a lower alkyl group, and R ² represents an alkyl group having 1 to 30 carbon atoms or 0 to 2 lower alkyl groups. Represents a phenyl group substituted by, R ³ is hydrogen or a carbon number 1 ~
30 acyl groups are shown. m is an integer from 1 to 1000. ) 2. As the heat stabilizer, phosphorous acid, a phosphite stabilizer or a phenol stabilizer is added in an amount of 0.0001 to
The composition according to claim 1, comprising 0.3 part by weight. 3. The composition according to claim 1, wherein the anthraquinone dye is one or more selected from blue, purple and green anthraquinone dyes.