JPH11323145A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin compsn. which gives a molded article excellent in antistatic properties and mechanical strengths, esp. impact strength, has a good moldability and esp. hardly exhibits resinous deposit or bleed-out in the molding step. SOLUTION: This compsn. comprises (A) 1-50 pts.wt. modifier comprising (a) a high-mol.-wt. alkylene oxide polymer, (b) a low-mol.-wt. alkylene oxide polymer, and (c) a metal salt, (B) 1-10 pts.wt. ethylene copolymer, and (C) 100 pts.wt. thermoplastic resin, the proportion of ingredient (b) being 5-50 wt.% of ingredient (a) and the proportion of ingredient (c) being 0.3-10 wt.% of the sum of ingredients (a) and (b).

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 having good workability and moldability, and giving a molded article having excellent antistatic properties and mechanical strength, especially excellent impact strength.

[0002]

2. Description of the Related Art Thermoplastic resins are easy to mold and process.
In addition, molded articles have excellent properties and economic advantages, so that they are widely used in various applications. In particular, thermoplastic resins have excellent electrical insulation properties and are often used as electrical insulators in electrical parts.However, this is a problem in that molded products tend to be charged, and dust tends to adhere and become dirty. Is caused. As a means for preventing this problem, there is a method of imparting an antistatic property to a thermoplastic resin.

[0003] As a method for imparting antistatic properties to a thermoplastic resin, a method of applying an antistatic agent to the surface, or adding and kneading an antistatic agent to a resin has conventionally been used. Particularly, in order to provide an antistatic effect for a long period of time, it has been proposed to mix a high molecular weight antistatic agent with a thermoplastic resin. For example, Japanese Patent Application Laid-Open No. 64-26674 proposes a method of blending an ethylene oxide copolymer having a molecular weight of 20,000 or more, and Japanese Patent Application Laid-Open No. 6-200171 discloses a method in which ethylene oxide is used as a component and has a molecular weight of 20,000 or more.
A method of blending an alkylene oxide copolymer of up to 100,000 and a metal salt has been proposed.

However, such an antistatic agent is
Since it has a high molecular weight, it has a high melt viscosity and has a large viscosity difference from a thermoplastic resin, so that it is difficult to be finely dispersed in the resin. In addition, even under high shear molding such as injection molding, since concentration on the surface layer hardly occurs, a relatively large amount of an antistatic agent must be added. As a result, the mechanical properties of the obtained molded product are deteriorated, and due to poor compatibility between the antistatic agent and the thermoplastic resin, so-called scumming (a scum that accumulates around the exit of the die of the extruder) or bleed out during molding. A phenomenon referred to as (blowing out of additives and the like on the surface of the molded product) occurs, and there are problems such as adhesion of the resin composition components to the molding device and impairment of the appearance of the molded product.

[0005] As described above, the conventional high molecular weight antistatic agent has poor compatibility with the thermoplastic resin, so that it is possible to obtain a resin composition having excellent antistatic properties and mechanical properties, particularly excellent moldability. It was difficult.

[0006]

SUMMARY OF THE INVENTION The present invention was conceived under such circumstances, and is a molded article having excellent antistatic properties and mechanical strength, particularly excellent impact strength. It is an object of the present invention to provide a thermoplastic resin composition having good molding processability, particularly less moldability and bleed-out during molding, and excellent moldability.

[0007]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that a high molecular weight alkylene oxide polymer, a low molecular weight alkylene oxide polymer and a specific metal salt are added to a thermoplastic resin. When a modifier consisting of three components is added, and an ethylene copolymer is further added as a compatibilizer, a thermoplastic resin composition having excellent antistatic properties and mechanical strength, and further having excellent moldability can be obtained. That is, the present invention has been completed.

That is, the present invention relates to a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c).
-50 parts by weight, 1-10 parts by weight of ethylene copolymer (B), and 100 parts by weight of thermoplastic resin (C), and the ratio of component (b) in the modifier (A) is (A) is 5 to 50% by weight, and the ratio of the component (c) in the modifier (A) is 0.3 to 10 with respect to the total amount of the component (a) and the component (b). % By weight.

In the present invention, the compatibility between the thermoplastic resin (C) and the modifier (A) is improved by adding the ethylene copolymer (B) as a compatibilizer, A) is finely dispersed in the thermoplastic resin (C). Therefore, a thermoplastic resin having excellent antistatic properties and excellent water resistance and mechanical strength, particularly excellent impact strength and moldability, by adding a relatively small amount of the modifier (A). It is believed that a composition is obtained.

[0010]

Embodiments of the present invention will be described below in detail.

First, the modifier (A) in the present invention comprises a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide (b) and a metal salt (c).

Among them, the high molecular weight alkylene oxide polymer (a) has a weight average molecular weight of 200,000 to 100
A high molecular weight alkylene oxide homopolymer and / or a high molecular weight alkylene oxide copolymer having a molecular weight of 100,000, preferably 500,000 to 6,000,000 are exemplified. Weight average molecular weight 2
If it is less than 10,000, it is difficult to obtain a continuous antistatic effect. When the weight average molecular weight exceeds 10,000,000, the high molecular weight alkylene oxide polymer (a) becomes difficult to knead with other components in the modifier, and the surface condition of the molded article tends to deteriorate.

Examples of the high molecular weight alkylene oxide homopolymer include polyethylene oxide, polypropylene oxide and the like.
Ten million polyethylene oxides are preferably used.

The high molecular weight alkylene oxide copolymer is preferably an alkylene oxide copolymer containing ethylene oxide as one component. Components other than ethylene oxide in the high molecular weight alkylene oxide copolymer include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and the like. Among them, propylene oxide is preferred. The high molecular weight alkylene oxide copolymer can be produced by copolymerizing ethylene oxide with another copolymerizable alkylene oxide in the presence of a suitable alkali, metal catalyst or the like. The production method is not particularly limited, and a known method or a method described in JP-A-5-17566 can be used.

Although there is no particular limitation on the composition ratio of ethylene oxide and other alkylene oxides in the high molecular weight alkylene oxide copolymer, the molar composition ratio of ethylene oxide contained in the high molecular weight alkylene oxide copolymer is as follows. The content is preferably 60 to 99% based on the whole copolymer. When the molar composition ratio is within the above range, the crystallinity of the copolymer can be reduced, and the compatibility with the resin is improved (assuming that low molecular weight alkylene oxide (b) coexists). Thus, a resin composition having excellent antistatic properties can be obtained. If the molar composition ratio of ethylene oxide is less than 60%, an antistatic effect corresponding to the blending amount may not be obtained.

On the other hand, the low molecular weight alkylene oxide polymer (b) has a weight average molecular weight of 5,000 to 2,000.
0, preferably 10,000 to 15000 low molecular weight alkylene oxide homopolymer and / or low molecular weight alkylene oxide copolymer. When the weight average molecular weight is less than 5,000, the low molecular weight alkylene oxide polymer (b) may separate from other components, and the surface condition of the molded product may be deteriorated. Weight average molecular weight of 20
If it is larger than 000, the effect of lowering the melt viscosity of the modifier may not be sufficiently obtained.

The low molecular weight alkylene oxide homopolymer includes polyethylene oxide, polypropylene oxide and the like, and especially has a weight average molecular weight of 5,000.
Polyethylene oxide of ~ 20,000 is preferred.

The low molecular weight alkylene oxide copolymer is preferably an alkylene oxide copolymer containing ethylene oxide as one component. Components other than ethylene oxide of the low molecular weight alkylene oxide copolymer include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and the like. Among them, propylene oxide is preferred. The production method is not particularly limited, and a known method can be used.

The composition ratio of ethylene oxide to the other alkylene oxide in the low molecular weight alkylene oxide copolymer is not particularly limited, but the molar composition ratio of ethylene oxide contained in the alkylene oxide copolymer is 60 to
Preferably it is 99%.

The metal salt (c) used in the present invention is preferably a metal salt having an alkali metal or an alkaline earth metal, and is specifically represented by the following formula (1) MX _n (1) An ion dissociable metal salt or an organic sulfonic acid metal salt represented by the following formula (2) (R—SO ₃ ) _n M (2) is exemplified. Here, M in the formula (1) represents an alkali metal or an alkaline earth metal, and X represents a halogen atom, SCN, C
10 ₄ , BF ₄ , PF ₆ , B [Ph] ₄ (however, Ph
Is a phenyl group), CF ₃ , SO ₃ , or CF ₃ CO ₂
And n represents 1 or 2. R in the formula (2) represents an alkyl group or an alkylphenyl group;
And n are the same as in equation (1).

An ion dissociable metal salt represented by the formula (1):
And alkalis such as lithium, potassium, and sodium
Alkaline metals such as magnesium or calcium
It contains lithium earth metal and has a fluorine ion (F^-),chlorine
Ion (Cl^-), Bromine ions (Br^-), Iodine ion
(I^-), Thiocyanate ion (SCN)^-), Perchlorine
Acid ion (ClO_Four ^-), Tetrafluoroborate ion
(BF_Four ^-), Hexafluorophosphate ion (P
F₆ ^-), Tetraphenylborate ion (B [Ph] _Four
^-) (Where Ph represents a phenyl group), trifluoro
Methanesulfonate ion (CF_ThreeSO_Three ^-), Or
Trifluoroacetate ion (CF_ThreeCO_Two ^-Release)
You.

The metal salt of an organic sulfonic acid represented by the formula (2) is preferably a metal salt of a sulfonic acid having a linear or branched alkyl group or an alkylphenyl group having 1 to 30 carbon atoms. Metal salts of alkylsulfonic acids such as octyl, dodecyl, stearyl, and behenyl; and metal salts of alkylphenylsulfonic acids such as dodecylbenzene. The metal constituting the salt can be arbitrarily selected from alkali metals such as lithium, potassium and sodium, and alkaline earth metals such as magnesium and calcium.

The metal salt (c) represented by the formula (1) or (2) may be added alone, or two or more kinds may be appropriately mixed and added. In addition to the metal salt (c) represented by the formula (1) or (2), a metal carboxylate such as lithium acetate, sodium propionate, and potassium stearate can also be used.

In the modifier (A) comprising the high molecular weight alkylene oxide polymer (a), the low molecular weight alkylene oxide polymer (b) and the metal salt (c), the ratio of the component (b) is as follows. 5 to 50% by weight, preferably 10 to 40% by weight. When the ratio of the component (b) to the component (a) is less than 5% by weight, a sufficient antistatic effect cannot be obtained. If the content exceeds 50% by weight, the processability as a modifier may be deteriorated, or when a thermoplastic resin composition is molded, bleeding to the surface may occur, and the surface condition of the molded product may be deteriorated.

In the modifier (A), the ratio of the component (c) is set to be 0.1 to the total amount of the components (a) and (b).
It is 3 to 10% by weight, preferably 1 to 5% by weight. When the ratio of the component (c) to the total amount of the components (a) and (b) is less than 0.3% by weight, a sufficient antistatic effect cannot be obtained. If the proportion of the component (c) exceeds 10% by weight, the effect of increasing the amount of addition cannot be obtained.

In the present invention, the ethylene copolymer (B) used as a compatibilizer includes a copolymer of ethylene and a carboxyl group-containing monomer, a copolymer of ethylene and a carboxylate ester-containing monomer, and the like. No. The carboxyl group-containing monomer means not only a monomer having a carboxyl group but also a derivative thereof such as a salt and an anhydride thereof. Similarly, the carboxylic acid ester-containing monomer means not only a monomer having a carboxylic acid ester but also a derivative thereof such as a salt and an anhydride thereof.

Specific examples of the ethylene copolymer (B) include, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer and partially neutralized products thereof, ethylene-methyl acrylate copolymer, ethylene -Ethylene-acrylate copolymer, such as ethyl acrylate copolymer, ethylene-methacrylate copolymer,
Examples include an ethylene-ethyl acrylate-maleic anhydride copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-vinyl acetate copolymer. Among them, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer and the like are preferably used, and especially ethylene-ethyl acrylate is used. Copolymers and ethylene-methyl methacrylate copolymers are preferred.

The proportion of the carboxyl group-containing monomer or the proportion of the carboxylate ester-containing monomer contained in the ethylene copolymer (B) is not particularly limited. Is preferably an ethylene copolymer having a content of 1 to 50% by weight.

It is not clear why an excellent effect can be obtained by adding the ethylene copolymer (B). However, the oxygen atom of the polyalkylene oxide polymer as the modifier (A) and the carboxylic acid ester are added. It is presumed that the interaction between the modifying agent (A) and the thermoplastic resin (C) is improved by the interaction with the contained ethylene copolymer (B).

The thermoplastic resin (C) used in the present invention is not particularly limited, and a general thermoplastic resin can be used. For example, polyolefin resins such as polyethylene and polypropylene, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS)
Resins), polymethyl methacrylate, polyethyl methacrylate, and other polymethacrylate resins, vinyl acetate resins, vinyl alcohol resins, vinyl chloride resins, and fluorine-containing resins. Polyester resin such as polybutylene terephthalate, polyethylene terephthalate, ether-ester copolymer, polyurethane resin, polyamide resin,
Examples thereof include a polycarbonate resin and a polyacetal resin. In particular, polyethylene, polypropylene, vinyl chloride, acrylonitrile-styrene-butadiene copolymer and the like are preferable, and among them, polyethylene,
When a polyolefin-based resin such as polypropylene is used, the effect of the blended modifier (A) becomes remarkable. These thermoplastic resins may be used alone, or two or more of them may be used as an appropriate mixture.

In the thermoplastic resin composition of the present invention,
1 to 50 parts by weight of the modifier (A) and 1 part by weight of the ethylene copolymer (B) are added to 100 parts by weight of the thermoplastic resin (C).
10 to 10 parts by weight, preferably 2 to 5 parts by weight. If the amount of the modifier (A) is less than 1 part by weight, a sufficient antistatic effect cannot be obtained. If the amount of the modifying agent (A) exceeds 50 parts by weight, the mechanical strength decreases, the surface condition deteriorates, and the properties of the thermoplastic resin are impaired. If the amount of the ethylene copolymer (B) exceeds 10 parts by weight, the effect of adding a large amount cannot be obtained.
If the amount of the ethylene copolymer (B) is less than 1 part by weight, the effect as a compatibilizer cannot be obtained.

Next, a method for producing the thermoplastic resin composition of the present invention will be described. In addition, what is related to the manufacturing method of a thermoplastic composition, such as a kneading machine, a kneading method, and a timing of adding a compounding component, is not particularly limited. Hereinafter, an example of the manufacturing method will be described.

First, a single screw extruder, a twin screw extruder, a kneader,
High molecular weight alkylene oxide polymer (a) and low molecular weight alkylene oxide polymer (b) by twin-screw kneader etc.
And a metal salt (c) in a predetermined ratio, and these three components are kneaded in a temperature range of 70 to 120 ° C., and pelletized to form a modifier (A). Next, using a single-screw extruder, a twin-screw extruder, a kneader, a twin-screw kneader, or the like, a temperature range of 70 to 2 is used.
The modifier (A), the ethylene copolymer (B) and the thermoplastic resin (C) are kneaded at a predetermined ratio at 70 ° C. to obtain a thermoplastic resin composition.

With respect to the method of adding the ethylene copolymer (B), the three components of the modifier (A), the ethylene copolymer (B) and the thermoplastic resin (C) are dry-blended and then simultaneously melt-mixed. Alternatively, the modifier (A) and the ethylene copolymer (B) or the ethylene copolymer (B) and the thermoplastic resin (C) are mixed and melted in advance, and the remaining components are added and mixed. It shall be.

The thermoplastic resin composition of the present invention can be used alone as a molded article. Alternatively, the thermoplastic resin composition of the present invention can be made into a compound (master batch), blended with another general-purpose resin, and manufactured into a molded product by a usual method such as injection molding, compression molding, blow molding, or extrusion molding.

In addition to the above, the thermoplastic resin composition of the present invention contains plasticizers, antioxidants, heat stabilizers, ultraviolet absorbers, fillers, lubricants, pigments, in an amount not to impair the antistatic property.
Reinforcing agents, vulcanizing agents, vulcanization accelerators and the like can be added. If there are other components to be added, appropriate amounts can be blended according to the purpose of addition.

[0037]

Next, the thermoplastic resin composition of the present invention will be described more specifically with reference to examples and comparative examples. In the Examples and Comparative Examples, the components described below and the methods for obtaining the same and the methods for measuring the physical properties of the obtained resin compositions were employed. The abbreviations (alphabet) described in [] are as described below, and are shown in Table 1 as they are.

1. Components of the modifier (A) Acquisition method: Using an organozinc compound-alcohol catalyst, changing the charged amounts of ethylene oxide and propylene oxide, the following three alkylene oxides having different molar composition ratios of ethylene oxide and propylene oxide A polymer was obtained. The composition ratio of each polymer was analyzed by nuclear magnetic resonance spectrum analysis. (A) High molecular weight alkylene oxide polymer (homopolymer) [A]: ethylene oxide homopolymer weight average molecular weight 2,000,000 (copolymer) [B]: ethylene oxide (90%)-propylene oxide (10%) copolymer Combined Weight average molecular weight 2,000,000 [C]: Ethylene oxide (80%)-propylene oxide (20%) copolymer Weight average molecular weight 2,000,000 [D]: Ethylene oxide (80%)-Propylene oxide (20%) copolymer Weight Average molecular weight 4 million

(B) Low molecular weight alkylene oxide polymer (homopolymer) [L]: ethylene oxide homopolymer Weight average molecular weight 15000 (copolymer) [M]: ethylene oxide (80%)-propylene oxide (20%) Copolymer weight average molecular weight 13000 (Epan U-180: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) [N]: ethylene oxide (75%)-propylene oxide (25%) copolymer weight average molecular weight 15000 (Yukon 75H) : Made by Union Carbide)

(C) Metal salt (ion dissociation metal salt represented by the above formula (1)) [X]: NaSCN (sodium thiocyanate) (metal organic sulfonic acid salt represented by the above formula (2)) [W] : Sodium dodecylbenzenesulfonate

2. Ethylene copolymer (B) [EEA]: Ethylene-ethyl acrylate copolymer EA content 41% (MB870: manufactured by Nippon Unicar Co., Ltd.) [EMMA]: Ethylene-methyl methacrylate copolymer MMA content 38% ( Aclift WM506: Sumitomo Chemical Co., Ltd.)

3. Thermoplastic resin (C) [PP]: polypropylene resin (Noblen H501:
Sumitomo Chemical Co., Ltd.) [PE]: Polyethylene resin (Chemilets HD-121)
0: manufactured by Maruzen Polymer Co., Ltd.) [ABS]: ABS resin (Toyolac 500: manufactured by Toray Industries, Inc.)

4. Method for Measuring Physical Properties of Molded Resin Composition (1) Surface Resistivity (Unit: Ω) A resin composition is injection-molded to have a diameter of 10 cm and a thickness of 0.2 c.
Two m-shaped disc-shaped test pieces were produced. One of them is kept at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours,
The test piece before washing was used. Apart from the test piece, the remaining 1
Each test piece was immersed in pure water for 15 minutes. Thereafter, the surface of the test piece was washed with pure water, and then the temperature was 23 ° C. and the relative humidity was 50.
% In an atmosphere of 24% for use as a test piece after washing. The surface resistivity of both test pieces was measured at a temperature of 23 ° C. and a relative humidity of 50%, and evaluated as antistatic properties before and after washing. The surface resistivity was measured using a super-insulation meter (SM-8)
210: Toa Denpa Kogyo Co., Ltd.) and a measurement voltage of 10
The measurement was performed under the conditions of 0 V and an application time of 1 minute. If the surface resistivity is in the range of 10 ¹² Ω or less, it can be evaluated that the antistatic function is sufficient.

(2) Izod impact strength (unit: kJ /
m ² ) In accordance with JIS K7110, a resin composition is injection-molded and notched, and an impact tester (Toyo Seiki Co., Ltd.)
Was used to measure the impact strength.

(3) Processing State at the Time of Forming A sample having a good processing state was marked with "O", and a sheet with scumming or bleed-out was marked with "X".

Example 1 Ethylene oxide (80%)-propylene oxide (20%) having a weight average molecular weight of 2,000,000
%) Copolymer 10 weight parts, ethylene oxide (80%) having a weight average molecular weight of 13,000-propylene oxide (2%).
0%) 1 part by weight of a copolymer (Epan U-180: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.3 part by weight of sodium thiocyanate, and an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) One part by weight was kneaded at 100 to 120 ° C. for 10 to 20 minutes using an electrically heated two-roll kneader (TM type: manufactured by Yasuda Seiki), and then pelletized to obtain a modifier. Next, an ethylene-ethyl acrylate copolymer (MB
870: 2 parts by weight from Nippon Unicar Co., Ltd.) and a polypropylene resin (Noblen H501: manufactured by Sumitomo Chemical Co., Ltd.)
After mixing 100 parts by weight and 11.4 parts by weight of the modifier, 180 to 24 parts were mixed using a twin-screw extruder (30 mm in diameter).
After melting and kneading at 0 ° C., the mixture was pelletized, and this pellet was used as the thermoplastic resin composition of the present invention. After the obtained pellets were completely dried in a hot air circulating oven at 75 to 80 ° C. for 6 hours or more, an injection molding machine (Nippon Steel Works, Ltd.)
), And molded at a cylinder temperature of 200 to 230 ° C and a mold temperature of 40 ° C to produce test pieces corresponding to each test. Using these test pieces, each physical property was evaluated. Table 1 shows the obtained results.

Example 2 In this example, the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 13000 (Epan U-180: Daiichi Kogyo Seiyaku Co., Ltd.) )), 2 parts by weight of an ethylene oxide (75%)-propylene oxide (25%) copolymer (Yukon 75H: manufactured by Union Carbide) having a weight average molecular weight of 15,000 was used instead of 1 part by weight. The other components were the same as in Example 1 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 3 In this example, the modifier of Example 2 was used, and the amount of the modifier mixed with the polypropylene resin was 24.8 parts by weight, and ethylene-ethyl acrylate copolymer was used. The amount of the coalescence (MB870: manufactured by Nippon Unicar Co., Ltd.) was 3 parts by weight. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 4 In this example, the modifier of Example 2 was used, and the amount of the modifier mixed with the polypropylene resin was 6.2 parts by weight, and ethylene-ethyl acrylate copolymer was used. Combined (MB870: Nippon Unicar Co., Ltd.)
Was 1 part by weight. Other composition was used in Example 2.
And a thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 5 In this example, the ethylene-ethyl acrylate copolymer (MB
870: ethylene-methyl methacrylate copolymer (Aclift WM50) instead of Nippon Unicar Co., Ltd.
6: Sumitomo Chemical Co., Ltd.). Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 6 In this example, sodium dodecylbenzenesulfonate was used in place of sodium thiocyanate in Example 2. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. A test piece was prepared from this thermoplastic resin composition in the same manner as in Example 1,
Each physical property was evaluated. Table 1 shows the obtained results.

Example 7 In this example, instead of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 in Example 2, ethylene oxide having a weight average molecular weight of 4,000,000 was used. (80%)-propylene oxide (20%) copolymer was used. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 8 In this example, instead of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 in Example 2, ethylene oxide having a weight average molecular weight of 2,000,000 was used. (90%)-propylene oxide (10%) copolymer was used. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 9 In this example, instead of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 in Example 2, ethylene oxide having a weight average molecular weight of 2,000,000 was used. Using a homopolymer, ethylene oxide having a weight average molecular weight of 15,000 used in Example 2 (75%)
-Propylene oxide (25%) copolymer (Yukon 7
5H: manufactured by Union Carbide) instead of an ethylene oxide homopolymer having a weight average molecular weight of 15,000. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 10 In this example, the polypropylene resin (Noblen H501:
Instead of Sumitomo Chemical Co., Ltd.), a polyethylene resin (Chemilets HD-1210: manufactured by Maruzen Polymer Co., Ltd.) was used. Other compositions were the same as in Example 2, and the thermoplastic resin composition of the present invention was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 11 In this example, the ethylene-ethyl acrylate copolymer (M
B870: 3 parts by weight of an ethylene methyl methacrylate copolymer (Aclift WM506: manufactured by Sumitomo Chemical Co., Ltd.) instead of 2 parts by weight of Nippon Unicar Co., Ltd. The other compositions were the same as in Example 10, and
The thermoplastic resin composition of the present invention was obtained in the same manner as in the above. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.
Shown in

[Comparative Example 1] In this comparative example, 0.3 parts by weight of sodium thiocyanate in Example 2 was not added at all, and the other composition was the same as that of Example 2, and further the same as Example 1. Thus, a thermoplastic resin composition was obtained.
Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 2 In this comparative example, the ethylene oxide (75%)-propylene oxide (25%) copolymer having a weight average molecular weight of 15,000 in Example 2 (Yukon 75H: manufactured by Union Carbide) was completely added. The other components were the same as in Example 2, and a thermoplastic resin composition was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 3 In this comparative example, no high-molecular-weight alkylene oxide polymer was added, and a low-molecular-weight alkylene oxide polymer having a weight-average molecular weight of 150 was used.
10 parts by weight of ethylene oxide (75%)-propylene oxide (25%) copolymer (Yukon 75H: manufactured by Union Carbide), sodium thiocyanate 0.3
After mixing 0.1 parts by weight of an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) and 100 parts by weight of a polypropylene resin (Noblen H501: manufactured by Sumitomo Chemical Co., Ltd.), the same as in Example 1 was mixed. A test piece is prepared by the method,
Each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 4 In this comparative example, the ethylene-ethyl acrylate copolymer (MB
870: manufactured by Nippon Unicar Co., Ltd.), and the other compositions were the same as in Example 2, and a thermoplastic resin composition was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 5 In this comparative example, the ethylene-ethyl acrylate copolymer (MB
870: Nippon Unicar Co., Ltd.) was changed to 0.5 parts by weight. Other compositions were the same as in Example 2,
Further, a thermoplastic resin composition was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 6 In this comparative example, the ethylene-ethyl acrylate copolymer (MB
870: manufactured by Nippon Unicar Co., Ltd.) was changed to 15 parts by weight. Other compositions were the same as in Example 2, and a thermoplastic resin composition was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

[Comparative Example 7] Polypropylene resin containing no modifier (Nobrene H501: manufactured by Sumitomo Chemical Co., Ltd.)
, Test pieces were prepared in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 8 In this comparative example, the ethylene-ethyl acrylate copolymer (M
B870: manufactured by Nippon Unicar Co., Ltd.) was not added at all. Other compositions were the same as in Example 10, and a thermoplastic resin composition was obtained in the same manner as in Example 1. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

[Comparative Example 9] A test piece was prepared in the same manner as in Example 1 using a polyethylene resin (Chemiretz HD-1210: manufactured by Maruzen Polymer Co., Ltd.) to which no modifier was added, and each physical property was evaluated. went. Table 1 shows the obtained results.

[0066]

[Table 1]

As shown in Table 1, the test pieces of Examples 1 to 11 are excellent in all the characteristics of the surface resistivity, the impact strength, and the processing state. On the other hand, it was confirmed that none of the test pieces of Comparative Examples 1 to 9 had all of the above characteristics. More specifically, the test piece of Comparative Example 1 has a low surface resistivity and impact strength because the modifier (A) contains no metal salt (c) at all, and furthermore has an appearance (processed state). Is also getting worse. The test piece of Comparative Example 2
Since the low molecular weight alkylene oxide polymer (b) is not contained at all in the modifier (A), the modifier (A) is hardly dispersed in the thermoplastic resin (C), and the surface resistivity is lower than that of the embodiment. Is much higher than the one. The test piece of Comparative Example 3 has particularly low impact strength because the modifier (A) does not contain the high-molecular-weight alkylene oxide polymer (a) at all. Since the test piece of Comparative Example 4 did not contain the ethylene copolymer (B) at all, the compatibility between the modifier (A) and the thermoplastic resin (C) was poor, and the appearance (processed state) was poor. It's getting worse.

As described above, when the modifier (A), the ethylene copolymer (B) and the thermoplastic resin (C) are all blended, the test pieces of Examples 1 to 11 (the heat The plastic resin composition) is superior to Comparative Examples 1 to 9 (conventional thermoplastic resin composition) in all of the surface resistivity, impact strength, and processing state.

[0069]

As described above, according to the present invention, the present invention has excellent antistatic properties and mechanical strength, and is also excellent in molding workability. A thermoplastic resin composition having a good surface condition can be obtained. This thermoplastic resin composition comprises a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c), and a thermoplastic resin (C). And an ethylene copolymer (B) as a compatibilizer. The compatibility between the modifier (A) and the thermoplastic resin (C) is improved by the ethylene copolymer (B), so that the mold is less likely to be generated at the time of molding. Adhesion of resin composition components can be reduced. In addition, when performing injection molding or sheet molding, a molded product without surface layer peeling or bleeding out to the surface can be obtained.

The thermoplastic resin composition of the present invention having the above composition has the effect of maintaining good impact resistance and surface condition. Therefore, the thermoplastic resin composition of the present invention can be safely used as a molding material for electronic parts and OA equipment, and a wide range of applications can be expected.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 33/08 C08L 33/08 // (C08L 101/00 71:02 23:08) (72) Inventor Shinji Kato Shima, Himeji-shi, Hyogo No. 1, Irifune-cho, Sumitomo Seika Chemicals Co., Ltd. (72) Inventor Kazuyuki Miura, No. 1, Irifune-cho, Himeji-shi, Hyogo Prefecture, Sumitomo Seika Chemicals Co., Ltd.

Claims (15)

[Claims] 1. An ethylene copolymer (1-50 parts by weight) comprising a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c). B) 1 to 10 parts by weight and 100 parts by weight of the thermoplastic resin (C), and the ratio of the component (b) in the modifier (A) is 5 to 50% by weight based on the component (a). A thermoplastic resin composition wherein the proportion of the component (c) in the modifier (A) is 0.3 to 10% by weight based on the total amount of the components (a) and (b). 2. The thermoplastic resin composition according to claim 1, wherein the high molecular weight alkylene oxide polymer (a) has a weight average molecular weight of 200,000 to 10,000,000. 3. The thermoplastic resin composition according to claim 1, wherein the high molecular weight alkylene oxide polymer (a) is a high molecular weight alkylene oxide homopolymer and / or a high molecular weight alkylene oxide copolymer. 4. The thermoplastic resin composition according to claim 3, wherein the high molecular weight alkylene oxide homopolymer is polyethylene oxide. 5. The high molecular weight alkylene oxide copolymer is a copolymer containing ethylene oxide as one component, and the molar composition ratio of ethylene oxide contained in the copolymer is 60 to 99 relative to the whole copolymer. % Of the thermoplastic resin composition according to claim 3. 6. The thermoplastic resin composition according to claim 1, wherein the low molecular weight alkylene oxide polymer (b) has a weight average molecular weight of 5,000 to 20,000. 7. The heat according to claim 1, wherein the low molecular weight alkylene oxide polymer (b) is a low molecular weight alkylene oxide homopolymer and / or a low molecular weight alkylene oxide copolymer. Plastic resin composition. 8. The thermoplastic resin composition according to claim 7, wherein the low molecular weight alkylene oxide homopolymer is polyethylene oxide. 9. The low-molecular-weight alkylene oxide copolymer is a copolymer containing ethylene oxide as one component, and the molar composition ratio of ethylene oxide contained in the copolymer is 60 to 100 with respect to the whole of the copolymer. The thermoplastic resin composition according to claim 7, which is 99%. 10. The metal salt (c) is a metal salt having an alkali metal or an alkaline earth metal.
The thermoplastic resin composition according to any one of the above. 11. The metal salt (c) is represented by the following formula (1) MX _n (1) (wherein M represents an alkali metal or an alkaline earth metal, and X represents a halogen atom, SCN, ClO ₄ , BF ₄₎ , P
F ₆ , B [Ph] ₄ (where Ph is a phenyl group), C
An ion dissociable metal salt represented by F ₃ , SO ₃ , or CF ₃ CO ₂ , wherein n represents 1 or 2, or the following formula (2) (R—SO ₃ ) _n M (2) (formula Wherein R represents an alkyl group or an alkylphenyl group, M represents an alkali metal or an alkaline earth metal,
11. The thermoplastic resin composition according to claim 10, wherein n is 1 or 2. 12. The method according to claim 1, wherein the ethylene copolymer (B) is a copolymer of ethylene and a carboxyl group-containing monomer or a copolymer of ethylene and a carboxylate ester-containing monomer. The thermoplastic resin composition according to one of the above. 13. The ethylene copolymer (B) is an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid copolymer, or an ethylene-methacrylic acid ester copolymer. The thermoplastic resin composition according to claim 12. 14. The content of the carboxyl group-containing monomer or the content of the carboxylic acid ester-containing monomer contained in the ethylene copolymer (B) is 1 to 50% by weight. Thermoplastic resin composition. 15. The thermoplastic resin (C) is at least one selected from the group consisting of a polyolefin-based resin, a polyvinyl chloride-based resin, a polymethacrylate-based resin, and a polystyrene-based resin. The thermoplastic resin composition according to any one of the above.