JPH06322250A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To prevent the decrease in mol.wt. of a polycarbonate resin caused by an inorg. pigment compounded and thereby give a polycarbonate resin compsn. which gives a molded article excellent in hue and mechanical properties by using a specific reactive silicone. CONSTITUTION:A polycarbonate resin compsn. is prepd. by compounding 100 pts.wt. polycarbonate resin with 0.001-20 pts.wt. inorg. pigment (except a white pigment) and 0.001-5 pts.wt. organopolysiloxane having an organoxysilyl group bonded to a silicon atom through a divalent hydrocarbon group. An example of the organopolysiloxane is represented by formula I [wherein R<1> is a monovalent hydrocarbon group; A is a monovalent hydrocarbon group or an organoxysilylated monovalent hydrocarbon group of formula II (wherein R<2> is a divalent hydrocarbon group; R<3> and R<4> are each a monovalent hydrocarbon group; and X is 0-2) provided at least one of A's is an organoxysilylated monovalent hydrocarbon group; and m is 1-300 and n is 0-300 provided m+n is 1-300].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate resin composition. More specifically, the decrease in the molecular weight of the polycarbonate due to the incorporation of the inorganic pigment is suppressed, and the yellowing is small and the change in the color tone is suppressed, and a molded article having excellent mechanical properties such as appearance and impact resistance can be obtained. The present invention relates to a polycarbonate resin composition.

[0002]

2. Description of the Related Art Polycarbonate resins have mechanical strength (particularly impact resistance),
It has excellent electrical properties and transparency, and is widely used as an engineering plastic in various fields such as electric and electronic equipment and automobiles. When a polycarbonate resin having such characteristics is used for colored molded parts in various fields, the polycarbonate resin has a carbonic acid ester bond. Particularly, when it becomes alkaline, there is a problem that hydrolysis occurs, which causes a decrease in molecular weight.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have conducted intensive studies to develop a polycarbonate resin composition in which a decrease in the molecular weight of the polycarbonate is suppressed, a yellowing is small, and a change in the color tone is suppressed in a system containing various inorganic pigments. As a result, they have found that by using a special reactive silicone, a decrease in the molecular weight of the polycarbonate resin is small and a polycarbonate resin composition having the desired properties can be obtained. The present invention has been completed based on such findings. That is, the present invention comprises (A) 100 parts by weight of a polycarbonate resin, (B) an inorganic pigment (excluding a white pigment) 0.00
1 to 20 parts by weight and (C) 0.001 to 5 parts by weight of organopolysiloxane containing an organooxysilyl group bonded to a silicon atom via a divalent hydrocarbon group, 0.001 to 5 parts by weight Is provided.

There are various kinds of polycarbonate resin (PC) as the component (A) which constitutes the resin composition of the present invention. Preferably the general formula (III)

[0005]

[Chemical 2]

[In the formula, X is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and when there are plural Xs, they are the same. May or may not be a
And b are integers of 1 to 4, respectively. And Y
Is a single bond, an alkylene group having 1 to 8 carbon atoms, or 2 to carbon atoms.
An alkylidene group having 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or-
S -, - SO -, - SO 2 -, - O -, - CO- bond or formula (IV) or (IV ')

[0007]

[Chemical 3]

The bond represented by ] It can be easily produced by reacting a dihydric phenol represented by the above with phosgene or a carbonic acid diester compound. That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor. Here, there are various dihydric phenols represented by the general formula (III), but 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. As dihydric phenols other than bisphenol A, bis (4-hydroxyphenyl) alkanes other than bisphenol A are 1,1- (4-hydroxyphenyl) methane; 1,1- (4-hydroxyphenyl) ethane; hydroquinone; 4 , 4'-Dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4
-Hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; compounds such as bis (4-hydroxyphenyl) ketone or bis (3,3 5-dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane and the like can be mentioned. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonic acid diester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. Further, the molecular weight regulator may be any one commonly used, for example, aromatic phenol such as phenol, p-tert-butylphenol, p-cumylphenol, p-tert-octylphenol, tribromophenol, or the like. In addition to aliphatic alcohols such as methanol and butanol, mercaptan, phthalimide and the like can be mentioned.

The polycarbonate resin used in the present invention may be a homopolymer using one kind of the dihydric phenol or a copolymer using a combination of two or more kinds. Further, it may be a thermoplastic random branched polycarbonate resin obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. Further, it may be a polycarbonate-polyorganosiloxane copolymer composed of a siloxane block having a number average degree of polymerization of n = 5 or more. From the viewpoint of mechanical strength and molding processability, the polycarbonate resin in the present invention preferably has a viscosity average molecular weight of 10,000 to 100,000, and particularly preferably 20,000 to 40,000. .

Next, the inorganic pigment as the component (B) constituting the resin composition of the present invention may be one that is generally used, and there are various ones. Specifically, for example, iron oxide, ultramarine blue, pearl mica, carbon black, conductive carbon black, calcium carbonate, molybdenum red,
At least one selected from yellow lead, alumina, zinc chromate, chromium oxide, copper phthalocyanine (phthalocyanine blue), mineral violet, cobalt blue, cobalt violet and the like is used. Among these, iron oxide, ultramarine blue, pearl mica, carbon black and calcium carbonate are preferably used. Here, iron oxide is a reddish-brown pigment containing ferric oxide as a main component and is commonly called red iron oxide. This iron oxide is
Depending on the size of the particles, the color tone varies widely from orange red to purple and can be selected arbitrarily. Also, ultramarine is
A vivid blue pigment consisting of silica, alumina, sodium oxide and sulfur. It is mainly produced by the synthetic method, and depending on the size of the particles, there are blue-margin and red-margin. As the pearl mica, there is a pearl pigment that artificially expresses pearl luster. That is, the pearl pigment is obtained by treating and coating the surface of natural mica with titanium oxide, iron oxide, which is a metal oxide having a high refractive index, or a mixture of titanium oxide and iron oxide. By changing the film thickness of the metal oxide to be coated, it is possible to enhance a specific color of the iris color. Examples of such a pearl pigment include, for example, Irio manufactured by Merck & Co., Inc.
You can get din easily. Further, as the black pigment, there is carbon black. The quality of this carbon black depends on the size of the particles (particle diameter, specific surface area), structure, surface chemistry, and the like. Various grades of carbon black have been put on the market from varieties having a small particle size, a large specific surface area, and excellent coloring power. Further, calcium carbonate is roughly classified into natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (precipitable calcium carbonate), and any of them may be used. As the pigment, finely divided calcium carbonate having a particle diameter of 10 μm or less is used. When such calcium carbonate is used, particle size, aggregation and dispersion are important factors.

Then, an organopolysiloxane containing an organooxysilyl group bonded to a silicon atom through a divalent hydrocarbon group of the component (C) constituting the resin composition of the present invention (hereinafter referred to as "organopolysiloxane"). Abbreviated.)
Has a function of suppressing a decrease in the molecular weight of the polycarbonate resin of the component (A) constituting the polycarbonate resin composition of the present invention, and maintaining impact resistance and thermal stability. Therefore, it is an essential component in the polycarbonate resin composition of the present invention. There are various kinds of organopolysiloxanes as the component (C), and specifically, they contain a straight-chain, cyclic, reticulated structure containing an organooxysilyl group bonded to a silicon atom through a divalent hydrocarbon group. And linear organopolysiloxanes having some branches. In particular, a straight-chain organopolysiloxane containing an organooxysilyl group bonded to a silicon atom via a divalent hydrocarbon group is preferable. Examples of the organopolysiloxane containing an organooxysilyl group bonded to a silicon atom through such a divalent hydrocarbon group include linear organopolysiloxanes represented by the general formula (I).

[0012]

[Chemical 4]

[Wherein R ¹ represents a monovalent hydrocarbon group, and A 1
Monovalent hydrocarbon radical or formula _{^{(II) -R 2 SiR 3 x}} (OR 4) (3-x) ··· (II) ( wherein, R ² is a divalent hydrocarbon radical, R ³ And R
⁴ represents a monovalent hydrocarbon group. Further, x is an integer of 0 to 2. ) Represents an organooxysilyl group-containing monovalent hydrocarbon group. However, at least one of A represents an organooxysilyl group-containing monovalent hydrocarbon group. Also, m
Is an integer of 1 to 300, n is an integer of 0 to 300, and m + n is an integer of 0 to 300. ] It is an organopolysiloxane represented by this.

Here, in the general formula (I), the monovalent hydrocarbon group represented by R ¹ is specifically a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like. Alkenyl group, vinyl group, allyl group, butenyl group, pentenyl group, alkenyl group such as hexenyl group,
Examples include aryl groups such as phenyl, tolyl, and xylyl groups, aralkyl groups such as benzyl and phenethyl groups, and substituted alkyl groups such as chloromethyl group, chloropropyl group, and 3,3,3-trifluoropropyl group. It And
The monovalent hydrocarbon group represented by A is the same as above. On the other hand, in the general formula (II), the divalent hydrocarbon group represented by R ² is specifically exemplified by alkylene groups such as methylmethylene group, ethylene group, methylethylene group, propylene group and butylene group. It The monovalent hydrocarbon group represented by R ³ and R ⁴ is the same as above, and specific examples of the organooxysilyl group-containing monovalent hydrocarbon group include:
Trimethoxysilylethylene group, triethoxysilylethylene group, dimethoxyphenoxysilylpropylene group,
Examples thereof include a trimethoxysilylpropylene group, a trimethoxysilylbutylene group, a methyldimethoxysilylpropylene group and a dimethylmethoxysilylpropylene group. The molecular weight of the component (C) is not particularly limited, and it is possible to suppress a decrease in the molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention. Therefore, in the general formula (II), m and n are respectively , M is 1 to 300
, N is an integer from 0 to 300, and m +
It is desirable that n is an integer of 1 to 300.

The organopolysiloxane as the component (C) can be obtained by various methods. For example, it can be produced by subjecting an organopolysiloxane having a silicon atom-bonded hydrogen atom and an organooxysilyl group to a hydrocarbon compound having an aliphatic unsaturated hydrocarbon bond in the presence of a platinum-based catalyst. Also,
It can be produced by subjecting a hydrocarbon group-containing organopolysiloxane having an aliphatic unsaturated hydrocarbon bond and an organooxysilane having a silicon atom-bonded hydrogen atom to an addition reaction in the presence of a platinum-based catalyst.

The resin composition of the present invention comprises the above-mentioned components (A), (B) and (C), and the mixing ratio thereof is 100 parts by weight of the polycarbonate resin which is the component (A). On the other hand, the inorganic pigment which is the component (B) 0.
001 to 20 parts by weight, preferably 0.005 to 15 parts by weight, and (C) the organopolysiloxane 0.00
1 to 5 parts by weight, preferably 0.01 to 3 parts by weight is blended. Here, if the amount of the component (B) is less than 0.001 part by weight, it is difficult to obtain the desired color tone. Further, when it exceeds 20 parts by weight, it is excessive to obtain a desired color tone,
It is not preferable because mechanical properties are deteriorated. When the amount of the component (C) is less than 0.001 part by weight, the effect of suppressing the decrease in the molecular weight of the polycarbonate is small. Further, when it exceeds 5 parts by weight,
During kneading of the polycarbonate resin composition, the feed becomes unstable by sliding on the screw. Furthermore, there is a concern that the mechanical strength such as strength and rigidity may decrease, which is not preferable.

In addition to the components (A), (B) and (C), the resin composition of the present invention may optionally contain
As the component (D), as long as the object of the present invention is not impaired,
Various inorganic fillers, additives or other synthetic resins, elastomers, etc. can be blended. First, examples of the above-mentioned inorganic filler that is blended for the purpose of mechanical strength, durability or amount increase of the polycarbonate resin composition include calcium sulfate, calcium silicate, titanium oxide,
Examples thereof include silica, asbestos, talc, clay, mica, carbon fiber, potassium titanate whiskers, mineral fiber, and quartz powder. Examples of the above-mentioned additives include hindered phenol-based, phosphite-based, phosphate-based, amine-based antioxidants, benzotriazole-based, benzophenone-based UV absorbers, hindered amine-based antioxidants, and the like. Examples thereof include light stabilizers, aliphatic carboxylic acid ester-based, paraffin-based, internal lubricants such as silicone oil and polyethylene wax, release agents, commonly used flame retardants, flame retardant aids, antistatic agents, and colorants.

Here, as the hindered phenolic antioxidant, BHT (2,6-di-tert-butyl-p) is used.
-Cresol), "Irganox 1076" (trade name) and "Irganox 1010" manufactured by Ciba-Geigy
(Trade name), "Ethyl 330" (trade name) manufactured by Ethyl Co., and "Sumilyzer GM" (trade name) manufactured by Sumitomo Chemical Co., Ltd. are preferably used. Examples of other synthetic resins include polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polyarylate, polyethylene, polypropylene,
Examples of the resin include polymethyl methacrylate, polystyrene, ABS resin, AS resin, and polycarbonate other than the polycarbonate as the component (A). Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, core-shell type elastomer MBS, MAS and the like.

The resin composition of the present invention can be obtained by blending the above-mentioned components (A), (B) and (C) with (D) if necessary and kneading. Then, for the compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be done using. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained is
Various known molding methods, such as injection molding, blow molding,
Extrusion molding, compression molding, calender molding, rotational molding, etc. can be applied and can be used for manufacturing various molded products.

[0020]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1 [Production of Polydimethylsiloxane Having Alkoxysilyl Group in Side Chain of Molecule] Hexamethyldisiloxane 151 g and octamethylcyclotetrasiloxane 482 were placed in a 1 liter round bottom flask equipped with a stirrer, a reflux machine and a thermometer.
g, 167 g of tetramethylcyclotetrasiloxane and 3.0 g of activated clay were charged and the temperature was 60 ° C with a mantle heater.
It was heated and stirred for 8 hours. After cooling, the mixture was filtered to obtain 760 g of a colorless transparent oily substance. The structure of the obtained oily substance is NM
It was determined by the R measurement as follows.

[0021]

[Chemical 5]

Then, in a 500 ml round-bottomed flask equipped with a stirrer, a reflux condenser and a thermometer, the above oily product 24 was added.
7 g, 153 g of vinyltrimethoxysilane and 0.15 g of a 3% alcohol solution of chloroplatinic acid were charged, and the mixture was heated with a mantle heater at 80 ° C. for 4 hours and stirred. 120 ° C,
After distilling under reduced pressure at 30 mmHg to remove excess vinyltrimethoxysilane, it was filtered to give a pale brown transparent oily substance 36.
3 g was obtained. The structure of the obtained oily substance was determined by NMR measurement as follows (type I).

[0023]

[Chemical 6]

Production Example 2 [Production of Polydimethylsiloxane Having Alkoxysilyl Group in Side Chain of Molecule] In a 1 liter round bottom flask equipped with a stirrer, a reflux machine and a thermometer, 28 g of hexamethyldisiloxane and octamethylcyclotetra were prepared. Siloxane 700
g, 72 g of tetramethylcyclotetrasiloxane and 3.0 g of activated clay were charged, and the mixture was heated with a mantle heater at 60 ° C. for 8 hours and stirred. After cooling, the mixture was filtered to obtain 744 g of a colorless transparent oily substance. The structure of the obtained oily substance is NMR
The measurement was determined as follows.

[0025]

[Chemical 7]

Then, in a 500 ml round bottom flask equipped with a stirrer, a reflux condenser and a thermometer, the above oily substance 31
6 g, 84 g of vinyltrimethoxysilane and 0.15 g of a 3% alcohol solution of chloroplatinic acid were charged, and the mixture was heated with a mantle heater at 80 ° C. for 4 hours and stirred. 120 ° C, 3
After distilling under reduced pressure at 0 mmHg to remove excess vinyltrimethoxysilane, it was filtered to give a light brown transparent oil 367.
g was obtained. The structure of the obtained oily substance was determined by NMR measurement as follows (type II).

[0027]

[Chemical 8]

Production Example 3 [Production of polydimethylsiloxane having alkoxysilyl groups at both ends of the molecule] In a 1-liter round bottom flask equipped with a stirrer, a reflux machine and a thermometer, 92 g of tetramethyldisiloxane and octamethylcyclotetra were prepared. Siloxane 708
g and activated clay 3.0 g were charged, and the mixture was heated with a mantle heater at 60 ° C. for 8 hours and stirred. After cooling, the mixture was filtered to obtain 760 g of a colorless transparent oily substance. The structure of the obtained oily substance was determined by NMR measurement as follows.

[0029]

[Chemical 9]

Then, the above oily product 30 was placed in a 500 ml round bottom flask equipped with a stirrer, a reflux machine and a thermometer.
7 g, 73 g of vinyltrimethoxysilane and 0.15 g of a 3% alcohol solution of chloroplatinic acid were charged, and the mixture was heated with a mantle heater at 80 ° C. for 4 hours and stirred. 120 ° C, 3
After distilling under reduced pressure at 0 mmHg to remove excess vinyltrimethoxysilane, it was filtered to give a pale brown transparent oil 365.
g was obtained. The structure of the obtained oily substance was determined by NMR measurement as follows (type III).

[0031]

[Chemical 10]

Examples 1 to 8 Polycarbonates (PC), various inorganic pigments, and various silicones having a methoxy group in the side chain obtained in the above Production Example were dry-blended according to the blending amounts shown in Table 1. Then, using a 40φ single-screw extruder with a vent (manufactured by Tanabe Plastic Machinery Co., Ltd.), the mixture was kneaded at 280 to 300 ° C. to prepare pellets. The resulting pellets are 120
After being dried at 8 ° C. for 8 hours, injection molding was performed at a molding temperature of 280 ° C. [molding machine: Toshiba Machine Co., Ltd. IS45P, mold: three-stage plate for color matching] to prepare a test piece.

Comparative Examples 1 to 6 Comparative Examples 1 to 6 were carried out in the same manner as in Examples except that polycarbonate (PC) and various inorganic pigments were used according to the blending amounts shown in Table 1. Comparative Example 7 The same procedure as in Example was carried out except that polycarbonate (PC), ultramarine and dimethyl silicone were used according to the blending amounts shown in Table 1.

For the test pieces obtained in the examples and comparative examples, the hue of the molded product was checked as a quality evaluation. Further, the pellet and the test piece were crushed to measure the viscosity average molecular weight (Mv). The results are shown in Table 2.

[0035]

[Table 1]

[0036]

[Table 2]

The raw materials used in the examples and comparative examples are as follows. (A) PC: Toughlon A2500 (Mv = 24,20
0) [Polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd.] (B) Inorganic pigment A: Iron oxide Bayfferox 140M [manufactured by Bayer] B: Ultramarine Ultramarin Blue # 1500 [Daiichi Kasei Co., Ltd.]
Made] C: Pearl mica Iriodine 100 Silver Pear-1 [Merck] D: Carbon black # 850 [Mitsubishi Kasei Co.] E: Calcium carbonate Cypron A [Cipron Kasei Co., Ltd.]
(C) Silicone type I: Silicone methoxy group content produced in Production Example 1 21.4 wt% kinematic viscosity 20 cSt Type II: Silicone methoxy group content produced in Production Example 2 11.4 wt% kinematic viscosity 85 cSt Type III: Silicone produced in Production Example 3 Methoxy group content 12.7 wt% Kinematic viscosity 15 cSt Type IV: Dimethyl silicone SH200 [Toray Dow Corning Silicone Co., Ltd.]

Further, each measurement in the quality evaluation was as follows. 1) Viscosity average molecular weight (Mv) Pulverized pellets and molded products are dissolved in a methylene chloride solution, insoluble matter is removed by a filter, evaporated to produce a film, and the film is dissolved again in methylene chloride. Measure the viscosity with a Ubbelohde viscosity tube at ℃,
After determining the intrinsic viscosity [η] from this, it was calculated by the following formula. [Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 2) Hue of molded product Based on JIS-K-7105. CIE1976 L ^* a ^* b ^* (D light source) L ^* is an index showing brightness, and a ^* and b ^* are color quality indexes. Here, when a ^* becomes positive, it becomes reddish.
When a ^* becomes negative, it becomes greenish. When b ^* becomes positive, it becomes yellowish. When b ^* becomes negative, it becomes bluish. YI (yellow index)

[0039]

As described above, according to the polycarbonate resin composition of the present invention, the decrease in the molecular weight of the polycarbonate due to the incorporation of the inorganic pigment is suppressed, the hue corresponding to the original color material is obtained, and the appearance and appearance are improved. A molded article having excellent mechanical properties such as impact resistance can be obtained. Therefore, the polycarbonate resin composition of the present invention can be effectively used for various colored molded articles.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Sato 1 Anezaki coast, Ichihara city, Chiba prefecture 1 Idemitsu Petrochemical Co., Ltd. (72) Haruhiko Furukawa 2 Chizen coast beach, Ichihara city, Chiba prefecture 2 Toray Dow Corning・ Research and development headquarters of Silicone Co., Ltd.

Claims (3)

[Claims] 1. (A) 100 parts by weight of polycarbonate resin, (B) inorganic pigment (excluding white pigment) 0.001
To 20 parts by weight and (C) 0.001 to 5 parts by weight of organopolysiloxane containing an organooxysilyl group bonded to a silicon atom via a divalent hydrocarbon group (0.001 to 5 parts by weight). 2. The polycarbonate resin composition according to claim 1, wherein the inorganic pigment as the component (B) is at least one selected from iron oxide, ultramarine blue, pearl mica, carbon black and calcium carbonate. 3. The organopolysiloxane having an organooxysilyl group as the component (C) has the general formula (I): [In the formula, R ¹ represents a monovalent hydrocarbon group, A represents a monovalent hydrocarbon group or the general formula (II) -R ² SiR ³ _x (OR ⁴ ) _(3-x) ... (II) ( In the formula, R ² represents a divalent hydrocarbon group, R ³ and R ⁴ each represent a monovalent hydrocarbon group, and x is an integer of 0 to 2). Indicates a monovalent hydrocarbon group. However, at least one of A represents an organooxysilyl group-containing monovalent hydrocarbon group. Also, m
Is an integer of 1 to 300, n is an integer of 0 to 300, and m + n is an integer of 1 to 300. ] It is organopolysiloxane represented by these, The polycarbonate resin composition of Claim 1 characterized by the above-mentioned.