JPH0220588A - Antistatic agent for thermoplastic resin, production thereof and resin composition having permanent antistatic property - Google Patents

Abstract

PURPOSE:To provide an antistatic agent which is free from bleed out and a loss of the antistatic effect with the lapse of time and exhibits improved dispersibility and compatibility when being blended in a thermoplastic resin by using a comb-type copolymer having a particular compsn. and contg. an ammonium salt. CONSTITUTION:This antistatic agent for a thermoplastic resin is composed of a comb-type copolymer comprising a terminal-polymerizable polyalkylene oxide (a) having acryloyl or methacryloyl groups at molecule terminals thereof, an acrylate or methacrylate (b) contg. an ammonium salt and a terminal- polymerizable copolymer of acrylonitrile and styrene (c) having acryloyl or methacryloyl groups or vinyl arom. groups at molecule terminals thereof. If desired, in addn. to the comonomers (a)-(c), vinyl monomers (d) copolymerizable with the comonomers may be added.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention relates to an antistatic agent, and more specifically, an antistatic agent that is blended into a thermoplastic resin as a base material and improves the antistatic properties of a thermoplastic resin molded product. This invention relates to an antistatic agent, a method for producing the same, and a permanent antistatic resin composition containing the antistatic agent.

[Prior Art] Thermoplastic resins have excellent moldability and electrical insulation properties, so they are used to manufacture various molded products such as housings and parts for electrical products and office equipment. . However, thermoplastic resin molded products are easily charged with electricity, and as a result, not only does dirt and dust adhere to the surface of the molded product, damaging the appearance of the product, but the molded product can also be used as a housing or component of electrical products or electronic devices. If this happens, it may cause poor insulation of electrical parts, short circuits, deterioration of electronic parts, malfunctions, etc.

Conventionally, methods of applying an antistatic agent to the surface of a molded article and methods of kneading an antistatic agent into a thermoplastic resin for molding have been carried out to address the electrostatic properties of these thermoplastic resins.

[Problems to be Solved by the Invention] In the method of applying an antistatic agent to the surface of a molded product, the coating film of the antistatic agent peels off due to changes over time or washing, and the antistatic effect is lost over time. It is necessary to add an antistatic agent coating process in addition to the molding process, which increases the manufacturing cost of the molded product and reduces productivity.

In contrast to the above method of coating, a method of kneading an antistatic agent into a thermoplastic resin yields a permanently antistatic resin composition.
This prevents deterioration over time due to peeling of the antistatic agent film, reduces the number of steps, and improves productivity. Decreases the durability of the preventive effect.

In addition to the above-mentioned conventional technology, vinyl monomers having ionic residues can be used as polymerizable seven polymers constituting thermoplastic resins.
It is known that antistatic properties can be imparted to thermoplastic resins by copolymerizing them with ionic structural units and introducing ionic structural units into the copolymer.

However, since the ionic structural units introduced as copolymer components are uniformly dispersed inside the resin in the order of molecular size, the surface of molded products obtained from thermoplastic resins containing this copolymer is prevented from becoming static. The effect is small, and in order to exhibit a sufficient antistatic effect, a large amount of the above-mentioned copolymer must be blended, and as a result, the performance of the thermoplastic resin containing the above-mentioned copolymer may be deteriorated.

This invention was made based on the above-mentioned background, and its purpose is to prevent bleed-out and prevent loss of antistatic effect over time even when kneaded into a base thermoplastic resin, and to maintain dispersibility and The object of the present invention is to provide an antistatic agent with excellent compatibility, a method for producing the same, and a permanently antistatic resin composition containing the antistatic agent.

[Means for Solving the Problems] As a result of conducting various tests and studies to solve the above-mentioned problems, the present inventors have developed a comb-shaped copolymer with a specific composition containing an ammonium salt as an antistatic agent. It has been found that when used, the antistatic effect does not bleed out and the antistatic effect is not lost over time even when kneaded into a thermoplastic resin, and the dispersibility and compatibility are excellent. As a result of further development based on this knowledge, we found that when producing an ammonium salt-containing comb-shaped copolymer, a good solvent is required for both the raw material ammonium salt-containing monomer and the polymer monomer that develops the branched structure (comb). However, first, an amine group-containing comb-shaped copolymer was prepared, and then the amine group was converted into an ammonium salt. It was found that the desired product could be effectively obtained by converting the above-described method into a compound, leading to the completion of this invention.

That is, the antistatic agent for thermoplastic resins of the present invention is composed of a comb-shaped copolymer composed of the following comonomers.

(a) A terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end, preferably a terminally polymerizable copolymer with a repeating unit of ethylene oxide or/and a repeating unit of propylene oxide (b) Ammonium salt-containing acrylate or methacrylate (c) A terminally polymerizable copolymer of acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end. If necessary, a vinyl copolymerizable with comonomers (a) to (c). system monomer (d
) can be used.

The production method of the present invention is a method for producing the antistatic agent, comprising: (a) a terminal polymerizable polyalkylene oxide 10 having an acryloyl group or a methacryloyl group at the molecular terminal;
~80ffi parts, (b') 0.5ff1m part or more of amino group-containing acrylate or methacrylate, and (c) terminal polymerizability of styrene and acrylonitrile having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end. 10 to 90 parts by weight of copolymer (however, 7 months (a) to
The total amount of (c) is 100 parts by weight. ), and (d) if necessary, the comonomers (a) to (c
) and 100 parts or less of vinyl heptamer copolymerizable with 100 parts or less of vinyl heptamer to produce a comb-shaped copolymer. Polymerization step A of producing a comb-shaped copolymer; This method is characterized in that it includes an ammonium forming step B.

A preferred permanent antistatic resin composition containing the antistatic agent according to the present invention is the antistatic agent 1 to 2 specified above.
0 parts by weight, and 99 to 80 parts of a thermoplastic resin compatible with the antistatic agent.

This invention will be explained in more detail below.

Method for producing an antistatic agent In the polymerization step A of the method for producing an antistatic agent of the present invention, comonomers (a), (b'), and (c), or comonomers (a), (b'), and ( c) and (d),
Copolymerization produces a comb-shaped copolymer.

The comonomer (a) used in this invention is a terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end. More specifically,
For example, a terminal polymerizable polymer represented by the following structural formula (I) can be mentioned.

(In the formula, R1 and R2 are hydrogen or a methyl group, R3 is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and n is an integer of 2 to 500.) Alkylene oxide The bonding unit n is selected in the range of 2 to 500. The larger n is, the more pronounced the effect as an antistatic agent is, but the copolymerization reactivity becomes smaller.

Preferred comonomers (a) include terminally polymerizable polyalkylene oxides which are copolymers of repeating units of ethylene oxide and/or repeating units of propylene oxide.

The amount of comonomer (a) used in the copolymerization is 10 to 80 parts by weight. If it is less than 10 parts by weight, antistatic effects such as antistatic effects cannot be imparted, and the antistatic effect cannot be obtained. If it exceeds 80 parts by weight, the comonomer (c)
When the amount of the copolymer used is relatively reduced, the antistatic effect of the obtained copolymer decreases, and the antistatic effect is no longer obtained.

The comonomer (b') used in this invention is an acrylate or methacrylate containing an amino group. More specifically, examples include acrylate or methacrylate derivatives represented by the following structural formula (II).

R40 (wherein, R is hydrogen or a methyl group, R5 has 1 to 1 carbon atoms)
6, preferably a divalent hydrocarbon group such as 1 to 4 alkylene groups, R6 and R7 represent hydrogen or an alkyl group such as a methyl group or an ethyl group, or an aralkyl group such as a phenyl group or a benzyl group) The amount of comonomer (b') used in the polymerization is 0.5 part by weight, preferably 1 part by weight or more. If it is less than 1 part by weight, a sufficient antistatic effect cannot be imparted, and if it is less than 0.5 part by weight, this tendency becomes noticeable and an antistatic effect cannot be obtained.

The comonomer (c) used in this invention is an end-polymerizable copolymer of acrylonitrile and styrene, which has a polymerizable functional group such as an acryloyl group, a methacryloyl group, or a vinyl aromatic group at one end of the molecule. Comonomer (c
The number average molecular weight of ) is preferably 200 to 20,000, and 200 to 20,000.
If it is less than 20,000, the effect of improving compatibility will be small, and if it exceeds 20,000, copolymerization reactivity will decrease, which is not preferable. The vinyl aromatic group at the end of the molecule in comonomer (c) is
It is an aromatic group having a polymerizable vinyl group, such as vinyl-p-phenylene group and isopropenyl m-phenylene group.

The amount of comonomer (e) used in the copolymerization is 10 to 90 parts by weight, preferably 20 to 80 parts by weight. If it is less than 20 parts by weight, the compatibility between the antistatic agent and the base thermoplastic resin will be reduced, resulting in poor antistatic effect sustainability; if it is less than 10 parts by weight, this tendency will be noticeable, and if it exceeds 80 parts by weight, the antistatic effect will be poor. This is because although the compatibility is good, the antistatic effect decreases, and this tendency becomes even more pronounced when the amount exceeds 90 parts by weight.

The total amount of comonomers (a), (b'), and (c) used is 1
00 parts by weight.

The comonomer (d) used as necessary in the present invention is a vinyl monomer copolymerizable with the comonomers (a) to (c) and the comonomers described above.

Examples of such vinyl monomers include alkyl esters of acrylic acid or methacrylic acid having 1 to 10 carbon atoms, acrylonitrile, styrene, α-methylstyrene, o-lm- or p-vinyltoluene, or mixtures thereof; Examples include nuclear halogenated styrene, α- or β-vinylnaphthalene, and the like. These may be used alone or in combination of two or more. Among these, alkyl esters of acrylic acid or methacrylic acid, particularly methyl methacrylate, are preferred; as a copolymerization method in copolymerization step A, solution polymerization is most suitable.

During copolymerization in copolymerization step A, a normal radical polymerization initiator and, if necessary, a chain transfer agent can be used to adjust the molecular ffi.

When copolymerizing by a solution polymerization method, an azo compound such as azobisisobutyronitrile or a peroxide such as benzoperoxide can be used as a polymerization initiator.

The solvent used in the solution polymerization method is preferably one that can dissolve each comonomer, and specific examples include acetone, methyl ethyl ketone, diethyl ketone, t-butyl ketone, tetrahydrofuran,
Examples include dimethylformamide, benzene, toluene, methanol, and ethanol. The solvent used here is preferably selected depending on the type of reagent used in the step of converting the produced amino group-containing copolymer into an ammonium salt, and is easily resistant to ammonium-forming reagents (e.g., acidic substances). Choose a solvent that is soluble or soluble. for example,
As the acidic substance, when using hydrochloric acid, acetone, tetrahydrofuran, ethanol, methanol, etc. are preferable.

In step B of the method for producing an antistatic agent of this invention,
The amino group-containing comb-shaped copolymer obtained in the above step A,
An ammonium-forming reagent and, if necessary, an auxiliary agent such as an ammonium-forming catalyst are added to convert it into an ammonium salt-containing comb-shaped copolymer, and then unnecessary solvents and the like are removed.

The ammonium-forming reagent is a reagent that converts an amino group into the corresponding ammonium salt, such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfite, phosphoric acid, boric acid, monosodium sulfate, monosodium phosphate, Carboxylic acids such as formic acid, acetic acid, propionic acid, and oxalic acid, acidic substances such as p-toluenesulfonic acid and alkylphosphonic acid, alkyl halides such as ethyl chloride and methyl bromide, or aralkyl halides such as benzyl chloride, etc. There is. These may be one type or a mixture of 211 or more.

The amount of ammoniumation reagent used is preferably in a range corresponding to 30 to 100% of the number of moles based on the amino group.

The method for producing the antistatic agent comprising the ammonium salt-containing comb copolymer of the present invention is not limited to the example described above, and can be produced by various methods.

For example, in solution polymerization, a mixed solvent can be used for polymerization, and in addition to solution polymerization, either a suspension polymerization method or an emulsion polymerization method can be used. In suspension polymerization, the same polymerization initiators as azo compounds and peroxides can be used in solution polymerization, and in emulsion polymerization,
In addition to water-soluble peroxides such as potassium persulfate, redox polymerization initiators can also be used.

Antistatic agent The antistatic agent of the present invention is a comb-shaped copolymer containing an ammonium salt, (a) a terminally polymerizable polyalkylene oxide having an acryloyl group or a methacryloyl group at the molecular end, preferably a repeating unit of ethylene oxide; or/and a terminally polymerizable copolymer of propylene oxide repeating unit; (b) acrylate or methacrylate containing an ammonium salt; (c) acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end; and (d) a vinyl seventh polymer copolymerizable with the comonomers (a) to (c), which is used as necessary.

The molecular weight of the comb-shaped copolymer can be appropriately selected depending on the use, processing method, etc.

Permanent Antistatic Resin Composition The permanent antistatic resin composition according to the present invention contains 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, of the antistatic agent of the present invention detailed above, and an antistatic agent. It consists of 99.5 to 70 parts by weight, preferably 99 to 80 parts by weight of a thermoplastic resin that is compatible with the agent.

This means that if it is less than 1 part by weight, the antistatic properties of the permanent antistatic resin composition will be poor, and if it is less than 0.5 part by weight, this tendency will be marked.
This is because if the amount exceeds 20 parts by weight, the manufacturing cost increases and becomes uneconomical, and at the same time, the physical properties of the thermoplastic resin composition change, making it impossible to obtain the desired physical properties.

The thermoplastic resin that can be used in the permanent antistatic resin composition according to the present invention is one that is compatible with the antistatic agent, and includes, for example, polystyrene, rubber-reinforced polystyrene,
Polymer alloys of polystyrene/polyphenylene ether, styrene-acrylonitrile copolymer, ABS resin, MBS resin, AES resin, polymethyl methacrylate, polymethyl acrylate, polyvinyl acetate, polyphenylene oxide, polycarbonate, polyamide, etc. In the invention, a mixture of two or more of these may be used.

When blending thermoplastic resins such as styrene-acrylonitrile copolymers and ABS resins in consideration of compatibility and dispersibility, it is important to consider It is preferable to maintain antistatic properties by combining the styrene-acrylonitrile composition of the polymer with the composition of the styrene-acrylonitrile copolymer or the like in the thermoplastic resin base.

In addition to the above-mentioned components, the permanent antistatic resin composition of the present invention includes a plasticizer, a lubricant, an antioxidant, a filler, a reinforcing agent, a reinforcing agent, a modifier, a flame retardant, a colorant, and a heat stabilizer. , foaming agents, softeners, anti-blocking agents, surface treatment agents, and other additives may be added.

In order to blend the above-mentioned components and additives into the permanent antistatic resin composition of the present invention, conventional equipment such as a tumbler, mixer, kneader 1 extruder, etc. can be used.

[Function] In this invention, an ammonium salt-containing comb-shaped copolymer obtained from a terminal polymerizable polyalkylene oxide, an ammonium base, a (meth)acrylate, and an AS (acrylonitrile and styrene) terminal polymerizable copolymer is A branched chain whose chain portion corresponds to polyalkylene oxide, and AS
It is mainly composed of branched chains corresponding to the copolymer and electrically conductive chains containing ammonium salts that have a synergistic effect with these branched chains.

Although it is not necessarily theoretically clear, the ammonium salt in the molecule imparts ionicity to the comb copolymer, and the branched chain corresponding to the polyalkylene oxide contributes to ionic conduction, resulting in the formation of a comb copolymer. into an electrically conductive polymer. In a molded article of a thermoplastic resin composition containing this comb-shaped copolymer, the ionic ammonium salt chain and the ion-conductive polyalkylene oxide chain migrate or orient to the surface of the molded article, and are concentrated on the surface of the molded article. The ionic conductivity (electrical conductivity) concentrated on the surface allows the charges on the surface to escape to the outside, thereby suppressing and preventing electrification.

[Effects of the Invention] This invention having the above-described structure and operation has the following effects.

(b) The antistatic effect having the composition according to claim 1, claim 2, or claim 3 is obtained by blending with the thermoplastic resin for molding of the base body and providing it for molding, and the surface resistance of the obtained molded product is 10 to 10. It can be made to a low level of about 1010Ω. Therefore, the molded product can exhibit an antistatic effect.

(b) In the method for producing an antistatic agent according to claim 4, an ammonium salt-containing comb copolymer is not directly produced, but an amine group-containing comb copolymer is first prepared, and then this amine group is replaced with an ammonium salt. Since ammonium is converted into a salt, it is possible to select a solvent that dissolves both of the raw material comonomer components of the comb-shaped copolymer, and there is no need to make the polymerization system heterogeneous or to perform difficult solvent recovery.

(c) In the molding resin composition according to claim 5, the branched chain corresponding to the AS-terminated polymerizable copolymer increases the compatibility and dispersibility with the molding thermoplastic resin serving as the base, and the thermoplastic resin Because the antistatic agent is entangled with the molecular chains of the antistatic agent, it does not grade out or peel off from the molded product, greatly improving the ability to maintain antistatic properties such as antistatic effects. be able to.

[Examples] This invention will be specifically explained below based on Examples and Comparative Examples, but the present invention will not exceed its gist.
The present invention is not limited to the following examples.

Example A-1 (1) Preparation of antistatic agent Tetrahydrofuran was added to 3001 in a Ja 500 ml flask equipped with a stirrer, and then, under stirring, an end-polymerizable copolymer of acrylonitrile having a methacryloyl group at one end and styrene was added. Polymer (hereinafter abbreviated as SANml, containing acrylonitrile ff 123% by weight, number average molecular weight 55
00) 30 g, polyethylene oxide having an acryloyl group at one end (hereinafter abbreviated as PE0m1, R3-ethyl of structural formula (I), nn-3) 61, and 9 g of dimethylaminoethyl acrylate (hereinafter abbreviated as DMA). ,
was added and dissolved.

The inside of the flask was replaced with nitrogen, 0.1 g of azobisisobutyronitrile as a polymerization initiator was further added, and the polymerization was continued at 70°C for 60 minutes.
Time went. After the polymerization was completed, 5.7% of 36% by weight hydrochloric acid was added.
5g (90% for dimethylaminoethyl acrylate)
mol %) was added under stirring, and 30 minutes later, the solution was transferred to a Teflon container, and the solvent was removed under reduced pressure to obtain a polymer.

(11) Evaluation of antistatic effect 5 g of the above polymer and a copolymer of acrylonitrile and styrene (hereinafter abbreviated as SAN, acrylonitrile content 2
9. 5ffi weight%, number average molecular weight 110,000) was kneaded with a Brabender blastograph at 200°C for 5 minutes, and after further pulverization, an injection molding machine with a cylinder temperature of 235°C and a mold temperature of 40°C was used to form a 75+ om x 130 mm x
A flat sample of 25 m+w was molded.

The surface resistance of the obtained sample was measured using the following measurement method and measurement conditions.

Surface Resistance Measuring Method Using a flat plate sample of 75 m x 130 m x 25 m
l) A method of measuring with the old ghResistance Meter (manufactured by Huyuret φPatsu Card Co., Ltd.).

It is evaluated that the smaller this measured value (surface resistance (Ω)) is, the better the antistatic effect is.

7I-1 Conditions (1) Measure the sample after keeping it in a constant temperature and humidity chamber at 23°C and 50% relative humidity for 24 hours (unwashed measurement) (2) Wash the sample with detergent (Mama Royal, Lion Co., Ltd.) Wash thoroughly with gauze impregnated with an aqueous solution (manufactured by Mikuni), then thoroughly rinse with distilled water, remove water from the surface, and hold in a constant temperature and humidity chamber at 23°C and 50% relative humidity for 24 hours. Repeat the cycle 10 times. Table 1 shows the results of ΔP1 constant (measured after 10 washing-drying cycles).

Examples A-2 to A-23 In the example described in Example A-1, the type and weight ratio of the comonomer, the ammonium forming reagent, and the weight ratio of antistatic agent/base resin were changed as shown in Table 1. Other than that, an antistatic agent was produced in the same manner as in the same example, and the antistatic effect of the obtained antistatic agent was evaluated in the same manner as in the same example.

The results are shown in Table 1.

Comparative Examples 1 to 7 In the example described in Example A-1, the type and weight ratio of the comonomer, the type of ammonium-forming reagent, the antistatic agent/
An antistatic agent was produced in the same manner as in the same example except that the weight ratio with the base resin was changed as shown in Table 1.

The antistatic effect of the obtained antistatic agent was evaluated in the same manner as in the same example.

The results are shown in Table 1.

1st Example Example A1 Example A2 Example A3 Example A4 Comparative Example A1 Comparative Example A2 Example A5 Example A6 Example A7 Example A8 Example A9 Example ALO Comparative Example A3 Comparative Example A3 Comparative Example A5 Antistatic Type and weight ratio of comonomers, etc. for agent production Comonomers (a) Comonomer (bo) Comonomer (c) Comonomer (d) PEOml 61 DMA 9
5ANIIl 30PEK2 61 DMA
9 5ANIIl 30PE~3 61
DMA 9 SAllJml 30PEOI
3 61 DMA 9 5ANII 30
DMA 9 5ANn+1 300A 6
1 DMA 9 5ANsl 30PEO
1261DMA I 5ANI11 30P
EOm2 61 D14A 9 SANm
l 30PE 2 57 DMA15
SANml 28PEOm2 78 DMA
2 5ANIIl 20PEOm2 69
D) 4A 9 5ANal 22PEOm2
11 DMA 9 SANml 80
PE 2 81 DMA 9 5ANa+1
10PEOn+2 1 D)tA Q
5ANa+1 90PR)+112 67 −
5ANi1 33 Ammoniumation reagent Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 0.23 Hydrochloric acid 2.07 Hydrochloric acid 3.44 Hydrochloric acid 0.46 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Hydrochloric acid 2.07 Resin composition antistatic agent/base resin 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (SAN) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (ABS) 10/90 (SAN) 10/ 90 (SAN) 10/90 (SAN) Surface resistance (Ω) Uncleaned 10 times washed lX1O129xlO" 7X10116x1011 6X10117xlO"6X10114X10" 5X10135X1014 7X10115x1014 5x10127x1012 3 ×10112×1011 6×1093×1010 5X10124X1. 012 2X10■14X1011 4X10125×1012 4xlO” 3X10”’ 2×10142×1014 1 0131X1013 Examples B-1 to B-17 In the example described in Example A-1, a mixed solvent of tetrahydrofuran and ethanol was used as the polymerization solvent. (Mixing ratio 15
Further, an antistatic agent was produced in the same manner as in the same example except that the comonomer 111m ratio and the weight ratio of antistatic agent/base resin shown in Table 2 were used to obtain an antistatic effect. evaluated.

The results are shown in Table 2.

Comparative Examples B-1 to B-6 In the example described in Example A-1, a mixed solvent of tetrahydrofuran and ethanol (mixing ratio 15
Further, the antistatic effect was produced in the same manner as in the same example except that the comonomer weight ratio and the antistatic agent/base resin weight ratio shown in Table 2 were used. was evaluated.

The results are shown in Table 2.

Examples Example B1 Example B2 Example B3 Example B4 Comparative Example B1 Comparative Example B2 Example B5 Example B6 Example B7 Example B8 Example B9 Example BIO Comparative Example B3 Comparative Example B4 Comparative Example B5 Example Bll Implementation Example B12 Example B13 Example B14 Example BL5 Example BIG Comparative Example B6 Example B17 Second table Antistatic agent production Types and weight ratios of comonomers etc. Comonomer (a) Comonomer (b) Comonomer (c) Comonomer (d) PIEOml 61 TMA 9
SANml 30P [EOm2 61T
MA 9 SANml 30PEOm3 6
1 TMA 9 SANml 30PE
Om3 61 TMA 9 SANml
30- TKA 9
SANml 300A 61T
MA 9 SANml 30PEO1i2
66 TMA I SANml 33
PIEOm2 61 TKA 9 SAN
ml 30PEOm2 57 TMA15
SANml 28PrEOm2 78T)
4A 2 SANml 20PEOm2 6
9 TMA 9 SANml 22PEO
m2 11 TMA 9 SANml
80PEOm2 81 TMA
9 SANml 1010PE0
1 TMA 9 SAN+++1
90PEOm2 67-SANml
3BPEOm5 61 T14A 9
SANm2 30PPOm 61 TMA
9 SAtJml 30PAOm 6
1 TMA 9 SANml
30PEOm2 61 DMBA
9 SANml 30P[EO
m2 61 T)tA 9 SANml
30PEOm2 61 TMA
9 5ANIIll 30PEOm2 6
1 TMA 9 SAN+nl 30
MMA 40 resin composition DMBA; methacryloyloxypropyldimethylbenzyl ammonium chloride As is clear from the above results, thermoplastic resin molded articles containing an antistatic agent selected from the composition range of this invention were compared to the resin molded products of the comparative example. It can be seen that the antistatic effect is superior to that of other products, and it also has excellent sustainability, that is, excellent antistatic properties.

Claims (1)

[Scope of Claims] 1. An antistatic agent for thermoplastic resins comprising a comb-shaped copolymer composed of the following comonomers (a) to (c). (a) Terminal polymerizable polyalkylene oxide having an acryloyl group or methacryloyl group at the molecular end (b) Acrylate or methacrylate containing an ammonium salt (c) Acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the molecular end The antistatic agent according to claim 1, wherein the terminal polymerizable copolymer 2 and the comb-shaped copolymer are composed of comonomers (a) to (c) and a vinyl monomer (d) copolymerizable with the comonomers. . 3. Claim 1 or Claim 2, wherein the terminally polymerizable polyalkylene oxide is a copolymer of a repeating unit of ethylene oxide and/or a repeating unit of propylene oxide.
Antistatic agent as described. 4. (a) 10 to 80 parts by weight of a terminally polymerizable polyalkylene oxide having an acryloyl or methacryloyl group at the end of the molecule, (b) 0.5 parts by weight or more of an acrylate or methacrylate containing an amino group, and (c) the molecule 10 to 90 parts by weight of a terminally polymerizable copolymer of acrylonitrile and styrene having an acryloyl group, methacryloyl group, or vinyl aromatic group at the end (however,
The total amount of comonomers (a) to (c) is 100 parts by weight. ), and (d) if necessary, 100 parts by weight or less of a vinyl monomer copolymerizable with the comonomers (a) to (c), to produce a comb-shaped copolymer; A method for producing an antistatic agent, which comprises converting an amino group of a type copolymer into an ammonium salt. 5. From 1 to 20 parts by weight of the antistatic agent according to any one of claims 1, 2, or 3, and 99 to 80 parts by weight of a thermoplastic resin that is compatible with this antistatic agent. A permanent antistatic resin composition characterized by: