JPH0797525A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] 100 parts by weight of thermoplastic resin (A), 2.0 to 40 parts by weight of bromine-containing organic flame retardant (B), 0 to 15 parts by weight of inorganic flame retardant aid (C). Part, and polyolefin structural unit (I) 58 to 98.9 mol%, carboxylic acid structural unit (I
I) 0.1 to 2 mol% and amide structural unit (III) 1 to
The weight average molecular weight of linearly arranged 40 mol% is 1,
000-50,000 cation-modified copolymer (D)
A thermoplastic resin composition containing 1.0 to 30 parts by weight. [Effect] It was possible to obtain a thermoplastic resin composition having both excellent flame retardancy and permanent antistatic property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in antistatic property and its durability and excellent in flame retardancy.

[0002]

2. Description of the Related Art Conventionally, in order to make a thermoplastic resin exhibit an excellent antistatic ability with durability, for example, JP-A-60-23435 has been proposed.
The amide or ester condensate of polyether diol found in JP-A-4-5691 and JP-A-3-258850, and the polyether-based copolymer found in JP-A-63-314261 are heated. It was included in the plastic resin. Attempts have also been made to add a bromine-containing compound to a thermoplastic resin to make it flame-retardant, and to add a surfactant to the composition to impart antistatic properties.

However, in the former method of adding an ester (amide) condensate of a polyether or a polyether copolymer obtained from ethylene oxide, epichlorohydrin, etc., the method itself has a large amount of ether oxygen. Very easy to burn, even in the case of a composition with a commonly used brominated flame retardant,
Compositions that meet satisfactory flame retardancy, and more specifically test standards such as UL standards, cannot be obtained.

Further, in the latter method of using a bromine-containing compound and a surfactant together, flame retardancy is obtained to some extent, but since the antistatic ability is manifested by the migration of the surfactant to the surface, it can be used for a long period of time. It is difficult to maintain its effect. Further, in many cases, the effect does not appear due to the interaction with the bromine-containing compound used as the flame retardant, and a satisfactory composition has not been obtained.

[0005]

The present invention has been made in view of such conventional problems. That is, the thermoplastic resin composition of the present invention having excellent antistatic properties for a long period of time and having flame retardancy is (A) 100 parts by weight of the thermoplastic resin (hereinafter, simply referred to as “part”). ), (B) bromine-containing organic flame retardant 2.0-
40 parts, 0 to 15 parts of (C) inorganic flame retardant aid, and (D)
Thermoplastic resin composition containing 1.0 to 30 parts of a cation-modified copolymer having a weight average molecular weight of 1,000 to 50,000, in which the following structural units (I) to (III) are linearly arranged Is.

Polyolefin structural unit (I) represented by the chemical formula 4 (58 to 98.9 mol%), carboxylic acid structural unit (II) represented by the general formula (5) 0.1 to 2 mol% and the general formula A cation-modified copolymer represented by 1 to 40 mol% of an amide structural unit (III) represented by 6.

[0007]

[Chemical 4]

[0008]

[Chemical 5]

[0009]

[Chemical 6]

(However, in Chemical formula 4, Chemical formula 5 and Chemical formula 6, R is a methyl group or a hydrogen atom, and in Chemical formula 6, R ² has 2 to 2 carbon atoms.
8 alkylene group, R ³ and R ⁴ each independently have 1 carbon atom
To 4 alkyl group, R ⁵ is an alkyl group or an arylalkyl group of C 6-8 having 1 to 18 carbon atoms, X ^- a halogen ion, ClO _3, CH ₃ OSO ₃ is ^- or C ₂ H ₅ OS
O ₃ ^- represents a. ) The structural units may be arranged regularly or irregularly.

Component (A) The thermoplastic resin used in the present invention includes polyolefin resin, polyvinyl chloride, polystyrene resin, ABS.
Resin, polyamide resin, polyester resin, polycarbonate resin, modified polyphenylene ether, etc. can be exemplified. Among them, it is preferable to use polyolefin resin, ABS resin, polystyrene resin, polyamide resin, polyester resin, polycarbonate resin. This is preferable because it has the advantage that it can be carried out more effectively.

Here, the polyolefin resin includes polyolefins, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, and the like, and blends of these various polyolefins and copolymers are also included. Among them, the use of polyolefins is preferable because it has the advantage that the compatibility with the component (D) is excellent in the present invention.

More specifically, the above polyolefins are
High density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, a copolymer of ethylene and α-olefin, and the like. Among such polyolefin resins,
High-density polyethylene, medium-density polyethylene, low-density polyethylene, and polypropylene are preferable, and the number average molecular weight thereof is usually 5,000 to 500,000, preferably 10,000 to 200,000.
Those that match.

The type of ABS resin is not particularly limited, and those obtained by a grafting method or a polymer blending method can be used. In addition, AS resin (acrylonitrile-
Styrene resin), AES resin (acrylonitrile-EP
(DM-styrene resin) and the like can be used, but ABS resin is preferable. As a polystyrene resin,
Polystyrene, (meth) acrylic acid ester-styrene copolymer, and styrene-α-methylstyrene copolymer having a number average molecular weight of 10,000 to 200,000 are suitable.

The polyamide resin is not particularly limited, and various kinds can be used, and either aliphatic or aromatic polyamide resin may be used. The molecular weight is not particularly limited, but in consideration of the moldability and physical properties of the obtained composition, the number average molecular weight is 4,000 to 5
10,000, preferably 5,000 to 30,000 are suitable. Such a polyamide resin can be manufactured by various known methods. For example, it can be produced by ring-opening (co) polymerization or (co) polycondensation of a lactam having three or more members, a polymerizable ω-amino acid, a dibasic acid and a diamine.

Various types of polyamide resin can be used as the above-mentioned polyamide resin.
Nylon 6; Nylon 6-6; Nylon 6-10; Nylon 11; Nylon 12; Nylon 6-12; Aliphatic polyamides such as Nylon 4-6, Nylon 6/6 (Copolymer of Nylon 6, Nylon 6-6 ) And; Nylon 6 /
6,10; Nylon 6/6, 12 and other aliphatic copolyamides, polyhexamethylenediamine terephthalamide; polyhexamethylenediamine isophthalamide; aromatic polyamides such as xylene group-containing polyamide. Furthermore, polyester amide, polyester ether amide, etc. can be mentioned. Of these, the preferred polyamide resin is nylon 6; nylon 6-6.

The polyester resin is a resin having a bond unit of ester such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). The polycarbonate resin is a resin obtained by polycondensing bisphenols such as bisphenol A with phosgene or carbonic acid ester. The component (A) may be used alone or in a system in which two or more kinds are blended at an arbitrary ratio.

Component (B) The bromine-containing organic flame retardant used in the present invention is an aromatic bromine substitution product, an aliphatic bromine substitution product, an alicyclic bromine substitution product, etc. Etc. may exist at the same time. Examples include bromide of diphenyl ether such as tetrabromodiphenyl ether, octabromodiphenyl ether, and decabromodiphenyl ether, bromide of triphenylene oxide, tetrabromobisphenol A, tribromophenol, tris (tribromophenyl) phosphite, hexabromocyclododecane. , Tetrabromocyclooctane, tetrabromophthalic anhydride and diamine imide condensate, pentabromotoluene, hexabromobenzene, tris (tribromophenoxy) cyanurate, 1,2-bis (pentabromophenoxy) ethane, etc. Bromobisphenol A, diglycidyl ether polymer, tribromophenol adduct, tetrabromobisphenol A polycarbonate, bromination Polystyrene,
Also included are brominated polymers such as brominated polyphenylene oxide.

Component (C) The inorganic flame retardant aid used here is one that increases the flame retardancy by interaction with the bromine-containing organic flame retardant,
For example, red phosphorus, boron trichloride, antimony trioxide,
Examples thereof include antimony pentoxide and zinc borate. Among them, antimony compounds such as antimony trioxide and antimony pentoxide are particularly preferable in terms of effects.

Component (D) As described above, the cation-modified copolymer used as the component (D) of the present invention has three structural units, a polyolefin structural unit (I), a carboxylic acid structural unit (II) and an amide structural unit ( III) are linearly arranged (may be regularly arranged or may be irregularly arranged) weight average molecular weight 10
It is a copolymer of 00-50000.

In the present invention, the proportion of the polyolefin structural unit (I) is preferably 58 to 98.9 mol%, and when the proportion of the polyolefin structural unit (I) is less than 58 mol%, Since the proportion of the carboxylic acid structural unit (II) and the amide structural unit (III) in this copolymer is relatively increased, the compatibility of this copolymer with a thermoplastic resin, particularly polyolefin, becomes Getting worse,
This causes deterioration of the mechanical properties of the resin. Also, 98.9 mol%
If it exceeds, the antistatic ability of the cation-modified copolymer of the present invention becomes small. The proportion of the polyolefin structural unit (I) is particularly preferably 75 to 97 mol% from the viewpoint of the balance of softening point, mechanical properties and antistatic ability.

The cation-modified copolymer of the present invention has the chemical formula
The carboxylic acid structural unit (II), that is, acrylic acid or methacrylic acid is contained in an amount of 0.1 to 2 mol%.
When the content of the carboxylic acid structural unit (II) exceeds 2 mol%, the thermoplastic resin in which the copolymer of the present invention is internally added becomes hard and the amide structural unit (III) that ionically bonds increases. Antistatic performance is insufficient. When the content of the carboxylic acid structural unit (II) is less than 0.1 mol%, the impact resistance and flex resistance of the internally added thermoplastic resin are not improved. The content ratio of the carboxylic acid structural unit (II) is from 0.2 to 10 from the viewpoints of antistatic performance, impact resistance, bending resistance and coating film adhesion.
1.5 mol% is more preferable, 0.3 to 0.8 mol%
Is particularly preferable.

In the present invention, the proportion of the amide structural unit (III) represented by the general formula 6 in the cation-modified copolymer is 1 to 40 mol%. When the proportion of the amide structural unit (III) is less than 1 mol%, the cation-modified copolymer obtained has insufficient antistatic ability. When the proportion of the amide structural unit (III) exceeds 40 mol%, hygroscopicity occurs when blended with the thermoplastic resin. Further, the mechanical properties of the resin deteriorate due to the deterioration of the compatibility with the thermoplastic resin. The content of the amide structural unit (III) is particularly preferably 2 to 25 mol% in view of the balance between antistatic ability, hygroscopicity and compatibility.

Here, R in the amide structural unit (III)
² is an alkylene group having 2 to 8 carbon atoms, specifically an ethylene group, a propylene group, a hexamethylene group and a neopentylene group, and these may be mixed in one molecule. From the viewpoint of ease of production and economy, ethylene group and propylene group are preferable, and propylene group is particularly preferable.

R ³ and R in the amide structural unit (III)
Each of ⁴ is independently an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, or a butyl group. These alkyl groups may be mixed in one molecule.
From the viewpoint of imparting antistatic properties, a methyl group and an ethyl group are preferred.

R ^{5 in the} amide structural unit (III) is an alkyl group having 1 to 18 carbon atoms or an arylalkyl group having 6 to 8 carbon atoms. Specifically, methyl group, ethyl group, n
-Propyl group, i-propyl group, benzyl group and the like,
These groups may be mixed in one molecule. A lower alkyl group is preferable from the viewpoint of imparting antistatic ability, and a lower alkyl group or a benzyl group is preferable from the viewpoint of heat resistance. Of these, a methyl group and an ethyl group are particularly preferable.

The X ⁻ ion in the amide structural unit (III) is a halogen ion such as Cl ⁻ , Br ⁻ , I ⁻ , or Cl.
O ₃ , CH ₃ OSO ₃ ⁻ or C ₂ H ₅ OSO ₃ ⁻ . These ions may be mixed in one molecule. From the viewpoint of imparting antistatic ability, Cl ⁻ , C ₂ H ₅ OSO ₃ ⁻ , CH ₃ OS
O ₃ ⁻ is preferred.

The cation-modified copolymer of the present invention has a weight average molecular weight of 1,000 to 50,000. When the weight average molecular weight is less than 1,000, physical properties such as antistatic property deteriorate when compounded with other substances, which is not preferable. When the weight average molecular weight exceeds 50,000, workability is deteriorated when compounding with other substances. The preferred weight average molecular weight range is 3,000 to 35,000. The weight average molecular weight was measured based on the ultrahigh temperature GPC method (Kinukawa, Kogaku Kobunshi, Vol. 44, No. 2, 139-141 (1987)).

The method for producing a cation-modified copolymer according to the present invention comprises a polyolefin structural unit (I) represented by Chemical Formula 4
58 to 98.9 mol% and a carboxylic acid structural unit (II) represented by the general formula 5 in a copolymer consisting of 1.1 to 42 mol%, the carboxyl group of the carboxylic acid structural unit (II) On the other hand, diamine (IV) 0.7 represented by the general formula 7
After reacting ~ 0.99 times mol to amidate,

[0030]

[Chemical 7]

By quaternizing the tertiary amino group introduced by the amidation reaction with a 1-fold mole of the quaternizing agent (V) represented by the general formula 8,

[0032]

[Chemical 8]

It is characterized in that a copolymer having a polyolefin structural unit (I), a carboxylic acid structural unit (II) and an amide structural unit (III) is obtained. Here, in Chemical formulas 7 and 8, R ² , R ³ , R ⁴ and R ⁵ are the same as above.

In the method for producing a cation-modified copolymer of the present invention, as a raw material copolymer comprising a polyolefin structural unit (I) and a carboxylic acid structural unit (II), for example, ethylene and acrylic acid are contained at 150 ° C to 240 ° C. ℃, 1,50
Directly copolymerized by a high pressure method under conditions of 0 to 2,400 kg / cm ² , ethylene-acrylic acid copolymer obtained by copolymerizing by a low pressure solvent method using tert-butanol or benzene as a solvent, and the like. Can be used. As other raw material copolymers that can be used,
A partially esterified polyethylene oxide wax may be mentioned. In addition, the carboxylic acid structural unit (I
In I), R is a methyl group or a hydrogen atom. Therefore, in the present invention, the carboxylic acid structural unit (II) is a structural unit composed of acrylic acid and methacrylic acid as described above.

The proportion of each structural unit of the raw material copolymer is 98.9 to 58 mol% for the polyolefin structural unit (I) and 1.1 to 4 for the carboxylic acid structural unit (II).
It is 1 mol%.

In the method for producing a cation-modified copolymer of the present invention, first, the carboxylic acid structural unit (II) of the raw material copolymer is used.
Is partially converted to an intermediate amide structural unit (VI) represented by the general formula 9 by an amidation reaction.

[0037]

[Chemical 9]

Aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as ligroin and kerosene, chlorinated hydrocarbons such as chlorobenzene, and raw material resins such as ketones are dissolved as reaction solvents for the amidation reaction. A possible inert solvent or the like is used.

In the production method of the present invention, the amidation reaction is carried out using the diamine (IV) represented by the general formula (7). In R ^2, R ³ and R ⁴ in the general formalized 7 are the same as in R ^2, R ³ and R ⁴ in the above amide structural unit (III). Specific examples of the diamine (IV) that can be used in the amidation reaction in the present invention include, for example, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine, N, N.
-Diethylaminopropylamine, N, N-dipropylaminoethylamine, N, N-dipropylaminopropylamine, N, N-dibutylaminoethylamine, N,
N-dibutylaminopropylamine, N, N-dimethylaminobutylamine, N, N-diethylaminobutylamine, N, N-dimethylaminoneopentylamine,
Examples thereof include N, N-dimethylaminohexylamine and N, N-dimethylaminooctylamine.

These diamines (IV) may be used alone or in admixture of two or more. The amount of the diamine (IV) used is 0.7 to 0.99 times mol, preferably 0.85 times, of the carboxyl group of the raw material copolymer composed of the polyolefin structural unit (I) and the carboxylic acid structural unit (II). ~
It is 0.99 times mol. The amount of diamine (IV) used is 0.
When the amount is less than 7 times the molar amount, it takes a long time for the reaction to reach 0.9.
If the amount is more than 9 times the molar amount, the result of the amidation reaction is
The carboxylic acid structural unit (II) does not remain in the copolymer containing a primary amino group, and the carboxylic acid structural unit (II) cannot remain in the finally obtained cation-modified copolymer. Therefore, the impact resistance and flex resistance of the resin containing the cation-modified copolymer of the present invention are lowered, and an excellent antistatic effect cannot be exhibited.

The reaction mixture thus obtained after completion of the amidation reaction can be added to a large amount of an immiscible solvent such as methanol for purification, if necessary, but it is usually used as it is for the following quaternary compound. Can lead to a chemical reaction.

In the production method of the present invention, the amino group 4
The quaternizing agent (V) used in the quaternization reaction has the general formula 8
It is an alkylating agent represented by. In the general formula 8,
R ⁵ is the same as in R ⁵ in the aforementioned amide structural unit (III).

R ⁵ is preferably a linear alkyl group or an arylalkyl group from the viewpoint of heat resistance of the resulting cation-modified copolymer, and is preferably a lower alkyl group from the viewpoint of antistatic property. Particularly preferred R ⁵ is a methyl group or an ethyl group.

X in the quaternizing agent (V) is the same as described above, for example, halogen such as Cl, Br, I, or ClO.
₃ , CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ . These may be mixed in one molecule, and among these, Cl, CH ₃ OSO ₃ and C may be included from the viewpoint of antistatic property.
₂ H ₅ OSO ₃ is also preferable as in the above.

Specific examples of the quaternizing agent (V) include alkylsulfuric acid such as dimethylsulfate and diethylsulfate,
Alkylbenzyl chloride, benzyl chloride, methyl chloride, ethyl chloride, butyl chloride, propyl chloride, ethyl bromide, butyl bromide, methyl iodide, ethyl iodide,
Butyl iodide, α-chloroparaxylene and the like can be mentioned, and these quaternizing agents are usually used alone or in combination of two or more kinds.

The amount of the quaternizing agent (V) used is equimolar to the tertiary amino group introduced into the raw material copolymer by the amidation reaction. When the amount of the quaternizing agent (V) used is less than 1 mol, the tertiary amide remains, which is not preferable. On the other hand, when the amount is more than 1 time, the carboxylic acid structural unit (II) is esterified and the content of the carboxylic acid structural unit (II) is decreased, which is not preferable.

The quaternization reaction is preferably carried out at a reaction temperature of 70 to 140 ° C. under a nitrogen atmosphere from the viewpoint of preventing coloration of the reaction product. The quaternization reaction is completed by aging at 70 to 140 ° C. for about 1 to 6 hours after addition of the quaternization agent. After completion of the reaction, by distilling off the solvent and then pulverizing, or by throwing in an immiscible solvent such as methanol, ethanol, isopropanol, n-hexane, etc. to precipitate and isolate the product, and then drying. Thus, a cation-modified copolymer as a product can be obtained.

The composition of the components (A), (B), (C) and (D)
Combining method Components (A), (B), (C) and (D) are kneaded under heating and melting using a single-screw or twin-screw extruder, a pressure kneader or the like to obtain a composition. Alternatively, a small amount of the component (A) and the total amount of the components (B), (C), and (D) are mixed in advance to form a masterbatch, and then the remaining component (A) is mixed, and further kneaded or It may be directly subjected to a molding machine such as an injection molding machine or an extruder.

The composition of the components (A), (B), (C) and (D)
The mixing ratio of the bromine-Motokei compound is in the mix ratio (B) of the present invention, a 2.0 to 40 parts per 100 parts of component (A). If it is less than 2.0 parts, the desired flame retardancy cannot be obtained, and 4
Addition of more than 0 parts is not only uneconomical, but also extremely deteriorates the physical properties (impact resistance, weather resistance, etc.) of the obtained composition.

Further, the component (C) has a composition ratio with the component (B) which gives good flame retardancy, and in the present invention, it is 0 to 15 parts relative to 100 parts of the component (A), but in particular, In order to obtain a high degree of flame retardancy, it is desirable to add 2.0 to 15 parts.

Further, the amount of the cation-modified copolymer of the component (D) contained in the present invention is 1.0 to 30 parts. If it is less than 1.0 part, good antistatic property cannot be obtained. When an amount exceeding the above range is added, the impact resistance of the resulting thermoplastic resin is significantly reduced. From the balance of antistatic properties and physical properties, it is particularly desirable to add 3.0 to 25 parts.

The cation-modified copolymer used as the component (D) of the present invention has ionic conductivity by itself, forms a leakage layer of electrostatic charge in the molded body during molding, and thereafter melts and the like. It keeps its form unless it happens. Therefore, as with the commonly used surfactant-based antistatic agents, there is no inhibition of surface migration due to adsorption of fillers or additives, desorption by external factors on the surface, and so on. The durability of prevention performance is extremely good. In addition, since a large amount of ether oxygen atoms is not contained in the molecule unlike the conventionally used polyether modified products, when the component (D) is used in the flame retardant resin, its flame retardancy is not lowered. A high antistatic ability can be imparted.

[0053]

【Example】

A. Synthesis of Cation-Modified Copolymer <Production Example 1 [Da]> 400 mL of xylene was added to a 4-neck flask with an internal volume of 1 L equipped with a thermometer, a stirrer, a dropping funnel and a Dean-Stark water diverter, and Table 1 was used. 150 g (containing 0.463 mol of carboxyl groups) of ethylene- (meth) acrylic acid copolymer (raw material copolymer) having the composition shown in was charged and heated to 100 ° C. to be uniformly dissolved.
Next, N, N-dimethylaminopropylamine 42.5
g (0.416 mol) was charged, the mixture was heated to 140 ° C., and the produced water was continuously removed by azeotropic distillation with xylene.
Further, the reaction was carried out at 140 ° C. for 20 hours, and the amidation reaction was continued until the azeotropic distillation of the produced water was not observed. The reaction mixture was cooled to 80 ° C., and the reaction mixture was put into methanol which was 5 times the amount of the reaction mixture. The precipitate was further washed with methanol and dried under reduced pressure to obtain a resin containing the intermediate amide structural unit (VI). When the amount of the tertiary amine introduced into the obtained copolymer was determined by neutralization titration, it was 2.24 meq / g.

150 g of the intermediate amide structural unit (VI) was again dissolved in xylene, and 47.7 g of methyl iodide was added dropwise from the dropping funnel over 1 hour. While heat generation was observed during this period, the reaction temperature was kept at 110 ° C. by cooling, and after completion of dropping, aging reaction was carried out at 120 ° C. for 3 hours. This converted the tertiary amino group into a quaternary ammonium base. The obtained reaction mixture was put into methanol, and the precipitate was further washed with methanol and dried under reduced pressure to obtain 178 g of the cation-modified copolymer [D-a] of this example.

[0055]

[Table 1]

<Production Examples 2 to 5, Copolymer [Db] to
[D-e]> A cation-modified copolymer was obtained in the same manner as in Production Example 1 using the raw material copolymer, diamine and quaternizing agent shown in Table 1. The infrared absorption spectrum, ¹³ C-NMR spectrum, weight average molecular weight and color tone of the cation-modified copolymers obtained in Production Examples 1 to 5 were examined. The measurement results and the substituents of the amide structural unit (III) are shown in Tables 2 and 1.

[0057]

[Table 2]

The methods for measuring infrared absorption spectrum, ¹³ C-NMR spectrum and weight average molecular weight are shown below. <Measurement of weight average molecular weight> Polymers, 44, 2
No. 139-141 (1987). Waters, GPC-244 (column; Showa Denko KK, Shodex, A-80M /
S (2), 1-chloronaphthalene as a solvent, a flow rate of 0.7 mL / min, a column temperature of 210
It was measured at ° C.

<Measurement of infrared absorption spectrum> FT-200 manufactured by Horiba Ltd. was used to measure KBr tablets. <Measurement of ¹³ C-NMR spectrum> manufactured by JEOL Ltd.,
Measured by JMN-GSX270 at 100 ° C. using heavy DMSO as solvent.

Examples 1 to 14 and Comparative Examples 1 to 21 The components (A) to (D) shown in [Table 3] and [Table 4] were
The twin-screw extruder (made by Kurimoto Iron Works Co., Ltd.)
The mixture was kneaded with a KRC kneader and cold cut to obtain thermoplastic resin composition pellets (B in the table).
For the components, see [Chemical Formula 10] to [Chemical Formula 18] below. The obtained pellets were molded by an injection molding machine (Hyper Shot 3000 manufactured by Niigata Iron Works Co., Ltd.) to prepare test pieces, which were subjected to a surface resistivity test, a durability test, and a flame retardancy test. Each test method is as follows, and the results are shown in [Table 3] and [Table 5].

Surface Specific Resistance Test Using a test piece of 60 × 60 × 3 mm, the surface specific resistance value was measured under the conditions of 20 ° C. × 65% RH with a super insulation resistance meter manufactured by Advantest.

Durability Test The surface of the above test piece was wiped 80 times with water-soaked gauze, air-dried and then conditioned under conditions of 24 hr or more and 20 ° C. × 65% RH to measure the surface resistivity value.

Flame Retardancy Test According to UL-94 test method, the grade was judged by a 1/16 inch thick test piece.

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Chemical 10]

[0067]

[Chemical 11]

[0068]

[Chemical 12]

[0069]

[Chemical 13]

[0070]

[Chemical 14]

[0071]

[Chemical 15]

[0072]

[Chemical 16]

[0073]

[Chemical 17]

[0074]

[Chemical 18]

[0075]

EFFECTS OF THE INVENTION A thermoplastic resin composition having both flame retardancy and permanent antistatic property, which have hitherto been considered difficult, can be obtained.

Claims (1)

[Claims] 1. (A) thermoplastic resin 100 parts by weight (B) bromine-containing organic flame retardant 2.0 to 40 parts by weight (C) inorganic flame retardant aid 0 to 15 parts by weight, and (D) A thermoplastic resin composition comprising 1.0 to 30 parts by weight of a cation-modified copolymer having a weight average molecular weight of 1,000 to 50,000 and linearly arranging the following structural units (I) to (III). Polyolefin structural unit (I) represented by Chemical formula 1 from 58 to 98.9 mol% and carboxylic acid structural unit (II) represented by General formula 2 from 0.1 to 0.1
2 mol% and the amide structural unit (I
II) A cation-modified copolymer represented by 1 to 40 mol%. [Chemical 1] [Chemical 2] [Chemical 3] (However, in Chemical formula 1, Chemical formula 2 and Chemical formula 3, R is a methyl group or a hydrogen atom, R ^{2 in} Chemical formula 3 is an alkylene group having 2 to 8 carbon atoms, and R ³ and R ⁴ are independently carbon atoms. 1 to 4 alkyl group, R ⁵ is an alkyl group having 1 to 18 carbon atoms or 6 carbon atoms
~ 8 arylalkyl group, X ^- is a halogen ion, C
Represents 10 ₃ , CH ₃ OSO ₃ ⁻ or C ₂ H ₅ OSO ₃ ⁻ . )