JP2002080707A - Thermoplastic resin composition and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate-based thermoplastic resin composition having excellent antistatic characteristics without damaging the transparency, and further to provide a polycarbonate-based thermoplastic resin composition capable of providing a molded product having improved resistance to becoming dirt by dust without damaging the flame retardancy and the mechanical strengths. SOLUTION: This thermoplastic resin composition comprises (A) 100 pts.wt. polycarbonate resin, (B) 0.0001-10 pts.wt. phosphonium salt of a sulfonic acid, and (C) 0.0001-1 pt.wt. metal salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate-based thermoplastic resin composition and a molded product thereof, and more particularly to a lighting device such as a headlight for an automobile, a headlight for a motorcycle, an indoor light or an outdoor light. Various lenses such as used lenses, spectacle lenses, optical lenses,
The above-mentioned resin composition and its molded product, or a copy thereof, which can be suitably used for applications requiring transparency and easily adhering to dust, such as optical discs, transport cases and storage cases, windows, various sheets or films, etc. Suitable for applications that require flame retardancy and are easily contaminated by dust, such as exterior plastic parts such as electrical equipment such as machines, fax machines, printers, televisions, and monitors for computers, and housing materials for electronic equipment and office equipment. The present invention relates to the usable resin composition and a molded product thereof.

[0002]

2. Description of the Related Art Polycarbonate resins and their alloy resins are used in various fields because of their excellent moldability, heat resistance and mechanical strength. For example, applications such as covers and lenses of various lighting equipment, films or sheets, OA equipment, office equipment, various parts of home appliances, storage and transport case materials, and the like can be mentioned. In particular, in applications such as exterior plastic parts, there is a problem that poor surface appearance impairs commercial value. One of the causes of the poor surface appearance is the occurrence of a stain pattern due to dust adhesion, which has become a major problem. This means that as the molded product is used, the molded product becomes contaminated by external fine dust. The method of soiling is that the whole surface is not evenly soiled, but that there are places where dirt is likely to adhere and places where dirt is difficult to adhere, and which forms non-uniform amorphous patterns (such as round patterns and lightning bolts). However, the soiled portion becomes conspicuous over time, deteriorating the commercial value. Therefore, there has been a demand for a polycarbonate-based resin material having an excellent anti-dust property, that is, an anti-static property. Various antistatic agents have been proposed in order to improve the anti-dust property of polycarbonate resins. However, most antistatic agents have the problem that their addition impairs transparency and flame retardancy. For example,
Since the addition of a metal salt impairs the transparency of the polycarbonate resin, it cannot be used for applications requiring both transparency and antistatic properties, such as covers and lenses of various lighting equipment. Further, the addition of a general antistatic agent such as a polyether-based compound deteriorates the flame retardancy when used together with a flame retardant such as a phosphate ester. As a method of imparting flame retardancy to a polycarbonate resin, a method of adding a phosphate ester flame retardant and a metal salt is known (Japanese Patent Application Laid-Open No. Hei 6 (1994) -176).
-299060, JP-A-10-306208). However, it has not been possible to satisfy both the properties of flame retardancy and antistatic properties.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a polycarbonate-based thermoplastic resin composition having excellent antistatic properties without impairing transparency, and a method for producing molded articles without impairing flame retardancy and mechanical strength. It is intended to provide a polycarbonate-based thermoplastic resin composition having improved stain resistance due to the above.

[0004]

Means for Solving the Problems The present inventors have made various studies to improve the antistatic properties of polycarbonate resins. As a result, conventionally, since the transparency of the polycarbonate resin is impaired, even in the case of a metal salt that could not be used as an antistatic agent in applications where transparency is required, a predetermined amount of the following metal salt and a phosphonium sulfonate salt are combined. When blended with a polycarbonate resin, it is possible to impart a high antistatic property to the polycarbonate resin without impairing the transparency of the polycarbonate resin, and especially when using sodium sulfonate or potassium sulfonate as a metal salt. Then, they have found that more excellent effects can be obtained, and have completed the present invention.

That is, the first embodiment of the present invention comprises:
(A) 100 parts by weight of a polycarbonate resin, (B) 0.0001 to 10 parts by weight of a phosphonium sulfonate,
And (C) 0.0001 to 1 part by weight of a metal salt. As a preferred embodiment, (2) the thermoplastic resin composition according to the above (1), which contains 0.001 to 5 parts by weight of the phosphonium sulfonate (B), and (3) the phosphonium salt (B) of 0.1 to 0.1% by weight. The thermoplastic resin composition according to the above (1) containing 4 parts by weight, (4) the thermoplastic resin composition according to the above (1) containing 0.5 to 3 parts by weight of a phosphonium sulfonate (B), (5) Metal salt (C)
The thermoplastic resin composition according to any one of the above (1) to (4), wherein the metal salt (C) is 0.005 to 0.1 parts by weight. Above (1) to
(4) the thermoplastic resin composition according to any one of the above,
(7) The thermoplastic resin composition according to any one of the above (1) to (4), which contains 0.01 to 0.08 parts by weight of the metal salt (C); The thermoplastic resin composition according to any one of the above (1) to (7), which is selected from the group consisting of a sulfonic acid metal salt, a sulfonamide metal salt, a sulfimide metal salt and a carboxylic acid metal salt, (9) metal (1) wherein the salt (C) is a metal sulfonate;
-The thermoplastic resin composition according to any one of (7),
(10) The metal salt (C) according to any one of the above (1) to (7), which is selected from the group consisting of a metal salt of an aromatic sulfonic acid, a metal salt of a verfluoroalkanesulfonic acid, and a metal salt of an aliphatic sulfonic acid. The thermoplastic resin composition according to any one of (8) to (10), wherein (11) the metal of the metal salt (C) is selected from the group consisting of alkali metals and alkaline earth metals. The thermoplastic resin composition according to any one of the above (1) to (7), wherein the metal salt (C) is a sodium sulfonic acid salt or a potassium sulfonic acid salt, (13) Metal salt (C)
Is a potassium sulfonate (1) to
(7) the thermoplastic resin composition according to any one of the above,
(14) The heat as described in any one of (1) to (7) above, wherein the metal salt (C) is a potassium salt of diphenylsulfon-3-sulfonic acid or a potassium salt of perfluorobutanesulfonic acid. A thermoplastic resin composition; (15) a molded article comprising the thermoplastic resin composition according to any one of the above (1) to (14); (16) a lens for a headlight for an automobile and a headlight for a motorcycle. (17) The molded article according to the above (15) which is a lens for a room light or an outdoor light, (17) the molded article according to the above (15) which is a sheet or a film, (18) a 3 mm or less thick part. (15) -where the total light transmittance is 85% or more
The molded article according to any one of (17), (19) 3 m
The molded article according to any one of the above (15) to (17), wherein the total light transmittance of the thick part of m or less is 86% or more, (20) the thickness of 3 mm or less (15) wherein the total light transmittance of the portion is 87% or more.
To (17).

[0006] Further, the present inventors have found that the addition of a phosphate ester-based flame retardant and a metal salt to a polycarbonate-based resin, as in the above-mentioned prior art, provides both flame retardancy and dust adhesion-preventing properties. Although it could not be satisfied, if a phosphate ester compound, a phosphonium sulfonate and a metal salt are added to the polycarbonate resin in the following predetermined amounts,
It has been found that the antistatic property is improved without impairing the flame retardancy, and the present invention has been completed.

That is, the second embodiment of the present invention provides (2)
1) (A) 100 parts by weight of a polycarbonate resin,
(B) phosphonium sulfonate 0.0001-10
It is a flame-retardant thermoplastic resin composition containing 0.001 to 5 parts by weight of (C) a metal salt and 0.5 to 30 parts by weight of (D) a phosphate compound.

In a preferred embodiment, (22) the metal salt (C) is 5 to 5 parts by weight of the phosphonium sulfonate (B).
The flame-retardant thermoplastic resin composition according to the above (21), which is contained in an amount of 0% by weight or less, (23) an amount of the metal salt (C) of 30% by weight or less based on the phosphonium sulfonate (B). (21) wherein the metal salt (C) is contained in an amount of 10% by weight or less based on the phosphonium sulfonate (B). The above (21), wherein the metal salt (C) is selected from the group consisting of a metal sulfonic acid salt, a metal sulfonamide salt and a metal carboxylate.
Any one of the above (21) to (24), wherein the flame-retardant thermoplastic resin composition according to any one of the above (24) to (26), wherein the metal salt (C) is a metal sulfonic acid salt. The flame-retardant thermoplastic resin composition according to one of the above, (27) the metal salt (C) is selected from the group consisting of a metal salt of an aromatic sulfonic acid, a metal salt of a perfluoroalkanesulfonic acid, and a metal salt of an aliphatic sulfonic acid. (21) The flame-retardant thermoplastic resin composition according to any one of (21) to (24), wherein (28) the metal of the metal salt (C) is selected from the group consisting of alkali metals and alkaline earth metals. (25) The flame-retardant thermoplastic resin composition according to any one of (25) to (27), wherein (29) the metal salt (C) is a sodium sulfonate or a potassium sulfonate. 21) The flame retardancy according to any one of (24) to (24). Thermoplastic resin composition, (3
0) The flame-retardant thermoplastic resin composition according to any one of the above (21) to (24), wherein the metal salt (C) is a potassium sulfonate, (31) a metal salt (C) Is a potassium salt of diphenylsulfon-3-sulfonic acid or a potassium salt of perfluorobutanesulfonic acid, wherein the flame-retardant thermoplastic resin composition according to any one of the above (21) to (24), (32) The flame-retardant thermoplastic resin composition according to any one of the above (21) to (31), further comprising not more than 200 parts by weight of a thermoplastic resin (E) other than a polycarbonate resin, (33) The thermoplastic resin (E) other than the polycarbonate resin may be a styrene resin, an aromatic vinyl / diene / vinyl cyanide copolymer, an acrylic resin, a polyester resin, a polyolefin resin, or a polyphenylene resin. Oxide-based resin, polyester mosquito -
(3) at least one resin selected from the group consisting of a carbonate resin, a polyetherimide resin, and a methyl methacrylate / butadiene / styrene copolymer;
2) The flame-retardant thermoplastic resin composition according to (2), wherein the phosphonium sulfonate (B) is a tetraalkylphosphonium salt of dodecylbenzenesulfonic acid, and the phosphate compound (D) is aromatic. The flame-retardant thermoplastic resin composition according to any one of the above (21) to (33), which is a polyphosphate;
(34) A molded article comprising the flame-retardant thermoplastic resin composition according to any one of (34) and (36) a molded article according to the above (35), which is an external plastic part for equipment.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is produced by a known production method. For example, a method of synthesizing a polycarbonate by subjecting an aromatic dihydroxy compound and a carbonate precursor (eg, carbonic acid diester) to transesterification in a molten state (melting method), a method in which an aromatic dihydroxy compound and a carbonate precursor (eg, phosgene ) (Interface method).

These production methods are described in, for example, JP-A-63-215763, JP-A-2-124934, JP-A-2-175723, and US Pat. No. 4,001,184.
No. 4,238,569, 4,238,597, and 4,474,999.

The polycarbonate resin comprises a carbonate component and a diphenol component. Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate. Suitable diphenols include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A);
Bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl)
Propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) decane; 1,4 -Bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl)
Cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5
-Dihydroxydiphenyl ether and the like. These can be used alone or in combination. In addition, it is also possible to use a compound having three or more phenolic hydroxyl groups.

Alternatively, component (A) may be an aromatic copolyestercarbonate. It has ester units derived from aromatic diols and aliphatic dicarboxylic acids having 6 to 18 carbon atoms in addition to carbonate units derived from known aromatic diols. For the production thereof, a phosgene method and a melting method known as a method for producing an aromatic polycarbonate can be used (US Pat. No. 4,238,5).
Nos. 96, 4,238,597 and 3,169,121).

The phosphonium sulfonate (B) used in the present invention is, for example, a compound represented by the following formula (I):

Embedded image (In the above formula, ^Ra is an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms, and R ^b , R ^c , R ^d and R
^e is independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms). However, it is not limited to this.

Here, the alkyl group includes a linear, branched or cyclic alkyl group. The aryl group includes an alkylaryl group and an arylalkyl group. In addition, the alkyl group and the aryl group can be substituted with an arbitrary substituent.

[0015] In R ^a, as the alkyl group, such as dodecyl group, decyl group, butyl group, ethyl group and the like. Examples of the aryl group include a dodecylphenyl group, a phenyl group, a benzyl group, a benzyl group, a phenethyl group, a tolyl group, and a xylyl group. ^Ra is preferably an aryl group.

In R ^{b to} R ^e , examples of the alkyl group include groups such as methyl, ethyl, propyl, and butyl. Examples of the aryl group include a phenyl group,
Examples include a benzyl group, a phenethyl group, a tolyl group, and a xylyl group.

Further, phosphonium salts of perfluoroalkanesulfonic acid can also be used. Preferably 1 to 19 carbon atoms
And more preferably a phosphonium salt of a sulfonic acid having a perfluoroalkane group having 4 to 8 carbon atoms, such as a phosphonium salt of perfluorobutanesulfonic acid.

Preferred phosphonium salts of sulfonic acid include, for example, tetraalkylphosphonium salts of dodecylsulfonic acid and tetraalkylphosphonium salts of dodecylbenzenesulfonic acid.

Component (B) is used in an amount of at least 0.0001 part by weight, preferably 0.001 part by weight, per 100 parts by weight of component (A).
Parts by weight or more, more preferably 0.01 parts by weight or more, still more preferably 0.1 parts by weight or more, particularly preferably 0.5 parts by weight or more, and 10 parts by weight or less, preferably 5 parts by weight or less, more preferably Is 4 parts by weight or less, more preferably 3 parts by weight.
Used below parts by weight. When the amount of the component (B) is less than the above lower limit, the dust adhesion preventing effect and the antistatic effect cannot be sufficiently exhibited, and when the amount exceeds the above upper limit, discoloration, decrease in heat resistance, decrease in mechanical properties, Causes poor appearance of molded products.

The metal salt (C) of the present invention preferably includes a metal salt of sulfonic acid, a metal salt of sulfonamide, and a metal salt of carboxylic acid. Of these, metal sulfonic acid salts are more preferably used, and particularly preferred are metal aromatic sulfonic acid salts, metal metal perfluoroalkanesulfonic acids, and metal aliphatic sulfonic acid salts.

The metal of the metal salt preferably includes an alkali metal, an alkaline earth metal and the like. here,
As alkali metals and alkaline earth metals, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium,
Examples include barium and the like, preferably sodium or potassium, and particularly preferably potassium.

The metal salt of aromatic sulfonic acid used in the present invention is preferably diphenyl sulfone-3.
Sodium salt of sulfonic acid, diphenyl sulfone-3
Potassium salt of sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid,
Potassium salt of 4′-dibromodiphenyl-sulfon-3-sulfonic acid, calcium salt of 4-chloro-4′-nitrodiphenylsulfon-3-sulfonic acid, disodium salt of diphenylsulfone-3 / 3′-disulfonic acid, Dipotassium salt of diphenylsulfone-3 / 3'-disulfonic acid, sodium salt of dodecylbenzenesulfonic acid, potassium salt of paratoluenesulfonic acid, sodium salt of paratoluenesulfonic acid, sodium salt of dichlorobenzenesulfonic acid, sodium salt of benzenesulfonic acid Examples thereof include a potassium salt and a sodium salt of benzenesulfonic acid.

The perfluoroalkane sulfonic acid metal salt is preferably a sulfonic acid metal salt having a perfluoroalkane group having 1 to 19 carbon atoms, more preferably having 4 to 8 carbon atoms, and more preferably perfluorobutane sulfonic acid. Sodium acid salt, potassium perfluorobutanesulfonic acid, sodium salt of perfluoromethylbutanesulfonic acid, potassium salt of perfluoromethylbutanesulfonic acid, sodium salt of perfluorooctanesulfonic acid, potassium of perfluorooctanesulfonic acid And the like.

Of the above, potassium salts of diphenylsulfone-3-sulfonic acid and potassium salts of perfluorobutanesulfonic acid are particularly preferably used.

In the first embodiment, the amount of component (C) is 0.000 parts by weight based on 100 parts by weight of component (A).
1 part by weight or more, preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, still more preferably 0.1 part by weight or more.
Not less than 01 part by weight and not more than 1 part by weight, preferably 0.1 part by weight.
It is used in an amount of 5 parts by weight or less, more preferably 0.1 part by weight or less, further preferably 0.08 part by weight or less. If the use amount of the component (C) is less than the above lower limit, the effect of preventing dust adhesion cannot be sufficiently exhibited, and if it exceeds the above upper limit, the transparency of the polycarbonate resin is undesirably lost. In the second embodiment, 0.0001 parts by weight or more, preferably 0.001 parts by weight, per 100 parts by weight of component (A).
005 parts by weight or more, more preferably 0.001 parts by weight or more, and 5 parts by weight or less, preferably 2.5 parts by weight or less, more preferably 1 part by weight or less, and still more preferably 0.1 part by weight or less.
Used at 5 parts by weight or less. If the amount of the component (C) is less than the above lower limit, the effect of preventing dust adhesion cannot be sufficiently exhibited.

Further, from the viewpoint of improving flame retardancy and dust adhesion, the amount of the component (C) is preferably 50% by weight or less, more preferably 30% by weight or less, based on the amount of the component (B). Particularly preferably, it is at most 10% by weight. Thereby, flame retardancy and improvement of dust adhesion can be satisfied in a well-balanced manner with a smaller addition amount.

Next, as the component (D) phosphate compound used in the present invention, the following formula (II):

Embedded image (Where R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but R ¹ = R ² = R ³
= R ⁴ = H is excluded. X represents a divalent or higher valent organic group, p represents 0 or 1, q represents an integer of 1 or more, for example, 30 or less, and r represents an integer of 0 or more. )). However, it is not limited to these.

In the above formula (II), examples of the organic group include an alkyl group which may or may not be substituted, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group,
An aryloxy group, an arylthio group, a halogenated aryl group, or the like; a group obtained by combining these substituents (for example, an arylalkoxyalkyl group); or these substituents are bonded by an oxygen atom, a sulfur atom, a nitrogen atom, or the like. (For example, an arylsulfonylaryl group) may be used as a substituent. Also, 2
The organic group having a valency of 2 or more means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the organic group described above. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols, such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are bisphenol A, hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.

Examples of the phosphoric ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) ) Phosphates and bis (chloropropyl) monooctyl phosphate, OR1, OR2, OR3 and OR4 are alkoxy, such as methoxy, ethoxy And polyphosphates such as propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate, and the like. Triphenyl phosphate and various aromatic polyphosphates (especially, resorcinol polyphosphate or bisphenol A polyphosphate).

When the component (D) is liquid, the component (D) can be added in the middle of the extruder by a method such as liquid injection.

The component (D) is used in an amount of 0.5 parts by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and 30 parts by weight or less, based on 100 parts by weight of the component (A). Is used in an amount of 25 parts by weight or less, more preferably 20 parts by weight or less. If the amount of the component (D) is less than the above lower limit, desired flame retardancy cannot be obtained, and if it is more than the above upper limit, heat resistance is impaired.

A preferred combination of the above components (B) and (D) is that (B) the phosphonium sulfonate is a tetraalkylphosphonium salt of dodecylsulfonic acid or a tetraalkylphosphonium salt of dodecylbenzenesulfonic acid,
In particular, the tetraalkylphosphonium salt of dodecylbenzenesulfonic acid and the (D) phosphate compound are aromatic polyphosphates.

The resin composition of the present invention may further contain (E) a thermoplastic resin other than polycarbonate in addition to the above components. The thermoplastic resin other than polycarbonate is not particularly limited as long as it is a thermoplastic resin. Preferably, a styrene resin, an aromatic vinyl / diene / vinyl cyanide copolymer, an acrylic resin, a polyester resin, a polyolefin resin, a polyphenylene oxide (PPO) resin, a polyester carbonate resin, It is selected from the group consisting of polyetherimide resins and methyl methacrylate / butadiene / styrene copolymer (MBS resin). These resins can be used alone or in combination of two or more.

Examples of the styrene-based resin include polystyrene, poly-α-methylstyrene, styrene-acrylonitrile copolymer (SAN resin) and the like.

Examples of the aromatic vinyl-diene-vinyl cyanide copolymer include a styrene-butadiene-acrylonitrile copolymer (ABS resin).

Examples of the acrylic resin include polymethyl methacrylate.

Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, and ethylene-propylene resin.
Propylene-diene copolymer and the like.

Examples of the polyphenylene oxide (PPO) resin include polyphenylene oxide resins, in which the benzene nucleus-bonded hydrogen may be substituted (for example, with alkyl, halogen, etc.).

The optional component (E) can be blended in an amount of preferably 200 parts by weight or less, more preferably 100 parts by weight or less based on 100 parts by weight of the component (A).
If the amount exceeds 200 parts by weight, the characteristics of the polycarbonate resin cannot be utilized.

The resin composition of the present invention may further contain the following components in addition to the above components.

UV absorbers : UV absorbers include P
Any conventional ultraviolet absorber can be used in the C resin composition. For example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylate-based ultraviolet absorber, and the like can be given. Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-t-octylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-amylphenyl) benzotriazole, 2- (2'- Hydroxy
-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1, 3,3-
Tetramethylbutyl) -6- (2H-benzotriazole-2
-Yl) phenol]. Examples of the benzotriazole-based ultraviolet absorber include UV5411 manufactured by American Cyanamid Co. and Tinuvin 234 manufactured by Ciba Geigy. Benzophenone UV absorbers are commercially available from Synamid as UV531. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, pt-butylphenyl salicylate,
p-octylphenyl salicylate and the like. The ultraviolet absorber is preferably at least 0.01 part by weight, more preferably at least 0.05 part by weight, and preferably at most 10 parts by weight, based on 100 parts by weight of the polycarbonate resin,
More preferably, 5 parts by weight or less is used.

Phosphorus stabilizer : As the phosphorus stabilizer, for example, any of those commercially available from various stabilizer manufacturers as antioxidants can be used. For example, phosphorous acid, triphenylphosphine, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, triphenylphosphite, diphenylnonylphosphite, tris (2,4-diphenyl -t-butylphenyl) phosphite, trisnonylphenylphosphite, diphenylisooctylphosphite, 2,2′-methylenebis (4,
6-di-t-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono (tridecyl) phosphite, 2,2′-ethylidenebis (4,6-di
-t-butylphenol) fluorophosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutylhydrogen phosphite, tributylhydrogen phosphite Lauryl trithiophosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropylidene diphenolalkyl (C12-C15) phosphite, 4,4 '-Butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite, phenyl-busphenol A pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite Phosphite, 1,1,3-tris
(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide and the like can be used. it can. Examples of available products include ADK STAB PEP-36, P
EP-24, PEP-4C, PEP-8 (all trademarks, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgafos168 (trademark, Ciba
Geigy), Sandstab P-EPQ (trademark, Sands (Sa
ndoz), Chelex L (trademark, Sakai Chemical Industry Co., Ltd.)
3P2S (trademark, manufactured by Ihara Chemical Industry Co., Ltd.), Ma
rk 329K, Mark P (both trademarks, Asahi Denka Kogyo Co., Ltd.)
And Weston 618 (trademark, manufactured by Sanko Chemical Co., Ltd.). The phosphorus stabilizer is preferably added in an amount of 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin.

Hindered phenolic antioxidants : for example, n-octadecyl-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Hydroxymethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-
And tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. Such a hindered phenolic antioxidant is preferably added in an amount of 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin.

Epoxy stabilizers : For example, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and the like. Such an epoxy-based stabilizer is preferably used in an amount of 0.0001 to 5 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin.
Parts by weight, more preferably 0.005 to 0.5 parts by weight.

Sulfur stabilizer . Release agent : Preferred release agents include silicone release agents such as methylphenyl silicone oil, pentaerythritol tetrastearate, glycerin monostearate,
Ester release agents such as montanic acid wax and polyalphaolefin, and olefin release agents. The release agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polycarbonate resin.
Parts by weight, more preferably 0.1 to 1 part by weight.

The resin composition of the present invention may further contain a conventional additive such as a colorant (eg, a pigment such as titanium oxide or carbon black) according to the purpose, as long as the physical properties are not impaired. , Dyes such as bluing agents), inorganic fillers (glass fiber, carbon fiber, talc, clay, mica, glass flake, milled glass,
Glass beads, silica, alumina, etc.), heat resistant agents, antioxidant inhibitors, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, flame retardants (other than phosphate ester compounds), fluidity improvers Etc. can be added.

Further, polytetrafluoroethylene (Teflon (registered trademark)) or the like can be blended as an anti-drip agent.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, generally the melt mixing method is preferred. The use of small amounts of solvents is possible but generally unnecessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

The present invention also provides a molded article of the above resin composition. As the molding method, any molding method commonly used for polycarbonate resins, for example, extrusion molding, injection molding, compression molding and the like can be used.

The resin composition of the present invention and a molded article thereof can be used as a lens used for lighting equipment such as a headlight for an automobile, a headlight for a motorcycle, an indoor light or an outdoor light, a lens for spectacles, and an optical lens. Various lenses, optical disks,
It can be suitably used for applications that require transparency and are easily contaminated with dust, such as transport cases, storage cases, windows, various sheets or films, or copiers, fax machines, printers, televisions, and computers. It can be suitably used for applications where dust adheres and is easily stained, and furthermore flame retardancy is required, such as exterior plastic parts, such as housing materials for electric, electronic equipment, and office equipment, such as monitors for office use. Of course, the application is not limited to the above, and it can be used widely in the field where various problems due to dust (for example, poor appearance, defective during painting, etc.) are involved. In a molded article requiring transparency, the total light transmittance of a thick portion of 3 mm or less is preferably 85% or more, more preferably 86% or more, and particularly preferably, but is not limited thereto. Is 87% or more.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0053]

EXAMPLES In the following examples and comparative examples, the following substances were used. <(A) Polycarbonate resin> Polycarbonate (P
C) [Lexane, trademark, manufactured by Nippon GE Plastics Co., Ltd. (intrinsic viscosity 0.50 dl / g measured at 25 ° C. in methylene chloride)] <(B) Phosphonium sulfonate> Tetrabutylphosphonium dodecylbenzenesulfonate (EPA20
(2, trademark, manufactured by Takemoto Yushi Co., Ltd.) <(C) Metal salt> (c-1) Potassium salt of diphenylsulfone-3-sulfonic acid (KSS, trademark, Seal Sands Chem)
icals Ltd.) (c-2) potassium perfluorobutane sulfonate _{(C 4 F 9 SO 3 K} , Bayowet C4, trademark, Bay
(c-3) Dodecylbenzenesulfonic acid sodium salt (EPA219, trademark, manufactured by Takemoto Yushi Co., Ltd.) <(D) Phosphate ester compound> Resorcinol polyphosphate (RDP) (CR733S, trademark, Daihachi Chemical Co., Ltd.) <(E) Thermoplastic resin other than polycarbonate resin>-Acrylonitrile / butadiene / styrene copolymer (ABS) (UX050, trademark, manufactured by Ube Sicon Co., Ltd.)-Silicon-acrylic rubber (Si-A) ( S200
1. Trade mark, manufactured by Mitsubishi Rayon Co., Ltd.)-Styrene / acrylonitrile copolymer (SAN) (7
89A, trademark, manufactured by Asahi Kasei Corporation) <Other optional components>-Polytetrafluoroethylene (Teflon) (PTF
E) (Anti-drip agent, polyflon D2C, trademark, manufactured by Daikin Chemical Industry Co., Ltd.) Tris (2,4-di-t-butylphenyl) phosphite (MK2112) (Mark 2112, trademark, manufactured by Asahi Denka Co., Ltd.) Octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (MKAO50) (Mar
k AO50, trademark, hindered phenol-based antioxidant, manufactured by Asahi Denka Co., Ltd.) Further, various tests and evaluations performed in Examples and Comparative Examples are as follows.
It carried out as follows. (1) Antistatic properties (half value) An injection molded plate having a thickness of 3 mm (5 cm × 5 cm square plate) was molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
Using onestmeter (S-5109, manufactured by Shishido Shokai Co., Ltd.)
The time until the charge of the charged body was reduced by half was measured as a half value (time unit: second). The smaller the half value, the better the antistatic effect. (2) Presence or absence of dust Box type (length 85 mm x width 200 mm x depth 15 mm,
After leaving the molded product (thickness: 3 mm) indoors for one month (30 days), dirt on the surface was visually observed. (3) Transparency (total light transmittance) 3 mm thick (5 cm × 5 c) according to ASTM D1003
Injection molded plate (m square plate) is molded at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C, and a spectrophotometer (Minolta CM-3700)
The total light transmittance was measured using d). (4) Transparency (Visual Evaluation) An injection-molded 6.4 mm thick test piece was molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and the degree of cloudiness of the molded product was visually evaluated in three stages. The smaller the value below, the better the visual transparency. 0: good transparency without white turbidity 1: slight white turbidity inside the molded article (core part) 2: clear white turbidity inside the molded article (core part) (5) Yellowness [YI] 3 mm A thick (5 cm × 5 cm square) injection molded plate is molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and the yellowness (YI-A) is measured using a spectrophotometer (Minolta CM-3700d).
Was measured. Next, the formed plate was heat-aged at 120 ° C. for 1000 hours, and the yellowness after aging (YI-B)
Was measured. (6) Flame retardancy Measured according to Underwriters Laboratories Inc. (Underwriters Laboratories Inc.), Bulletin 94 "flammability test for material classification" (referred to as UL-94 test). The thickness of the test piece is 1.6 mm
Tested. Using five test pieces, the burning time after flame contact was measured twice in total, ten times in total, and the total burning time and the presence or absence of drip were shown in Table 2. (7) Izod impact strength Izod impact strength with 1/8 inch notch was measured according to ASTM D256. (8) Melt index (MI) Measured at 300 ° C. and 1.2 kg load based on ASTM D1238. In Table 1, MI-A is the initial (pellet is M
I-measurement index 4 minutes after filling in the cylinder of the I-measuring device), and MI-B was retained in the cylinder of the MI-measuring device for 15 minutes longer than the time of the initial measurement (the pellet was subjected to MI measurement). (Measured 19 minutes after filling in the cylinder of the vessel).

[0054]

Examples 1 to 3 and Comparative Examples 1 to 5 Each component was mixed at the ratio (weight ratio) shown in Table 1 and extruded with a twin screw extruder set at 280 ° C. and 270 rpm to produce pellets. Next, injection molding was performed using the obtained pellets under the conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C. Various tests were performed on the obtained molded product. Table 1 shows the results.

[0055]

[Table 1]

Examples 1 to 3 are based on the first embodiment of the present invention, in which the type of the metal salt (C) is changed within the scope of the present invention. Both the antistatic property (half value) and the transparency (total light transmittance of a 3 mm thick molded plate) are good, and the resin composition is suitable for applications where transparency is required and dust easily adheres and is easily stained. It turns out that it can be used for. Transparency (visual evaluation of 6.4 mm thick test specimen), difference in yellowness (YI) before and after aging, and difference in melt index (MI) before and after residence all use potassium salt as metal salt (C). Examples 1 and 2 were
A better result was shown as compared with Example 3 using a sodium salt as the metal salt (C). This is because molded products using potassium salts have better transparency even if they are thicker,
Therefore, it is possible to partially have a thick portion, thereby increasing the degree of freedom in designing a molded product,
Even when used in a high-temperature environment, less yellowing and little loss in transparency, and resin deterioration during molding,
It is superior to a molded product using a sodium salt in that a decrease in viscosity is smaller, and therefore a reduction in productivity such as a decrease in mechanical strength and interruption of continuous molding due to a burr trouble is hardly caused. Therefore, materials having high transparency, less yellowing and excellent moldability are particularly required.For applications such as lenses for lighting, sheets and films, molded articles using potassium salts are more preferable. . In particular, the potassium salt of diphenylsulfone-3-sulfonic acid used in Example 1 was found to be good. On the other hand, in Comparative Example 1, the phosphonium phosphonium salt (B) and the metal salt (C) were not blended.
No antistatic properties were obtained with only the polycarbonate resin (A). Comparative Example 2 did not contain the metal salt (C). The half value was remarkably large and the antistatic property was very small. In Comparative Examples 3 to 5, the phosphonium phosphonium salt (B) was not blended. No antistatic property was obtained by adding any of the metal salts. Further, as is apparent from Comparative Example 5, the transparency of the polycarbonate resin was impaired by the addition of the sodium salt of dodecylbenzenesulfonic acid.

[0057]

Example 4 and Comparative Examples 6 and 7 Each component was mixed in the ratio (weight ratio) shown in Table 2 and extruded with a twin-screw extruder set at 240 ° C. and 250 rpm to form pellets. Next, using the obtained pellets, a set temperature of 240 ° C. and a mold temperature of 60 ° C.
Injection molding was performed under the condition of ° C. Various tests were performed on the obtained molded product. Table 2 shows the results.

[0058]

[Table 2]

Example 4 is based on the second embodiment of the present invention, and comprises a phosphonium sulfonate (B) and a metal salt (C) as antistatic agents and a phosphate compound as a flame retardant. It is a polycarbonate resin composition containing (D). On the other hand, Comparative Examples 6 and 7 show that the metal salt (C)
And a phosphate-based compound (D). Unlike the conventional polycarbonate resin composition, the polycarbonate resin composition of the present invention sufficiently satisfies both the flame retardancy and antistatic properties of the molded article without impairing the mechanical strength. Was.

[0060]

Industrial Applicability The present invention provides a polycarbonate-based thermoplastic resin composition having excellent antistatic properties without impairing transparency, and a molded article having improved dust resistance without impairing the flame retardancy and mechanical strength. An object of the present invention is to provide an improved polycarbonate-based thermoplastic resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/435 C08K 5/435 5/50 5/50 5/521 5/521 C08L 101/00 C08L 101 / 00 G02B 1/04 G02B 1/04 (72) Inventor Alex Skorten The Netherlands, 4600 AC Bergen Op Zum, Plastic Slane 1F Term (Reference) 4F071 AA15 AA20 AA22 AA33 AA45 AA46 AA50 AA51 AA77 AC09 AC14 AC15 AE07 AH07 AH07 AH07 AH07 AH07 AH07 AH07 AH17 BC01 BC07 4J002 BB032 BB122 BB152 BB172 BC032 BC062 BC092 BG062 BN152 BN162 CF062 CF072 CG011 CG031 CG042 CH072 CM042 EG007 EV257 EV287 EW048 EW176 FD010 FD030 FD050 FD070 FD090 FD137

Claims (15)

[Claims] (A) 100 parts by weight of a polycarbonate resin, (B) phosphonium sulfonate 0.0001 to
A thermoplastic resin composition containing 10 parts by weight and (C) 0.0001 to 1 part by weight of a metal salt. 2. The thermoplastic resin composition according to claim 1, wherein the metal salt (C) is an alkali metal salt of sulfonic acid or an alkaline earth metal salt of sulfonic acid. 3. The thermoplastic resin composition according to claim 1, wherein the metal salt (C) is a potassium sulfonate. 4. A shaped article comprising the thermoplastic resin composition according to claim 1. 5. The molded article according to claim 4, which is a lens for an automobile headlight, a motorcycle headlight, an interior light or an outdoor light. 6. The molded article according to claim 4, which is a sheet or a film. 7. The molded article according to claim 4, wherein a total light transmittance of a thick portion of 3 mm or less is 85% or more. 8. (A) 100 parts by weight of a polycarbonate resin, (B) phosphonium sulfonate 0.0001 to
10 parts by weight, (C) metal salt 0.0001 to 5 parts by weight,
And (D) a flame-retardant thermoplastic resin composition containing 0.5 to 30 parts by weight of a phosphate compound. 9. The flame-retardant thermoplastic resin composition according to claim 8, wherein the metal salt (C) is contained in an amount of 50% by weight or less based on the phosphonium sulfonate (B). 10. The flame-retardant thermoplastic resin composition according to claim 8, further comprising a thermoplastic resin (E) other than the polycarbonate resin in an amount of 200 parts by weight or less. 11. The thermoplastic resin (E) other than the polycarbonate resin may be a styrene resin, an aromatic vinyl / diene / vinyl cyanide copolymer, an acrylic resin, a polyester resin, a polyolefin resin, or a polyphenylene oxide resin. The flame-retardant thermoplastic resin composition according to claim 10, which is at least one resin selected from the group consisting of a resin, a polyester carbonate-based resin, a polyetherimide-based resin, and a methyl methacrylate / butadiene / styrene copolymer. object. 12. The flame-retardant thermoplastic resin composition according to claim 8, wherein the metal salt (C) is an alkali metal salt of sulfonic acid or an alkaline earth metal salt of sulfonic acid. 13. The phosphonium sulfonate (B)
A tetraalkylphosphonium salt of dodecylbenzenesulfonic acid, and a phosphate compound (D),
The flame-retardant thermoplastic resin composition according to any one of claims 8 to 12, which is an aromatic polyphosphate. 14. A molded article comprising the flame-retardant thermoplastic resin composition according to any one of claims 8 to 13. 15. The molded article according to claim 14, which is a plastic part for equipment exterior.