JP2000144114A - Resin modifier for antistatic use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin modifier capable of imparting antistatic properties sustaining over a long period to a thermoplastic resin, especially a styrene-based resin without deteriorating thermal and mechanical characteristics thereof. SOLUTION: This resin modifier for antistatic use contains a reactional product of (A) a styrene-maleimide-maleic anhydride copolymer with (B) at least one polyalkylene oxide monoether selected from a polyalkylene oxide monoalkyl ether, a polyalkylene oxide monophenyl ether and a polyalkylene oxide monoalkylphenyl ether or its metal salt as an active component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic modifier for a thermoplastic resin, and more particularly, to an antistatic modifier which lasts for a long time without impairing the thermal and mechanical properties of a styrene resin. The present invention relates to a resin modifier capable of imparting properties.

[0002]

2. Description of the Related Art Impact resistant polystyrene (HIPS) and A
Styrene resins such as BS resin have impact resistance,
It is excellent in moldability, heat resistance, mechanical properties, etc., and is therefore widely used in various fields in addition to automobile parts, electric equipment parts, information and communication equipment, and those parts.

[0003] As described above, styrene resins are excellent in various properties, however, like other resins,
Because the resin itself is an insulator, the molded product is easily charged, dust and the like adhere to it, not only impairing the appearance, but also causing an explosion or fire due to an electric shock or spark caused by the discharge of accumulated static electricity. In addition, there are various problems in electrical equipment such as malfunction.

Conventionally, as one method of imparting antistatic properties to a synthetic resin molded article, generally, polyethylene oxide monoalkyl ether, which itself has antistatic properties, is kneaded and compounded with a resin before molding. After molding, a method of applying the polyethylene oxide monoalkyl ether to the surface of the molded article is known. However, according to such a method, the antistatic effect is reduced or eliminated by washing the molded product with water or wiping the surface. On the other hand, when a large amount of polyethylene oxide monoalkyl ether is kneaded into a resin, the resin lacks compatibility, so it bleeds on the surface of the molded product, sticks, and on the contrary, dust easily adheres to the resin. There is also a problem that the moldability and mechanical properties of a molded product are deteriorated.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned various problems in the conventional antistatic agent, and it is intended to provide a thermoplastic resin, in particular, a styrene resin. It is an object of the present invention to provide a resin modifier capable of imparting a long-lasting antistatic property without impairing thermal and mechanical properties, and the present invention further provides such a modifier. It is an object of the present invention to provide a blended thermoplastic resin composition, particularly a styrene resin composition, and a molded article obtained therefrom.

[0006]

The antistatic resin modifier according to the present invention comprises (A) a styrene / maleimide / maleic anhydride copolymer, (B) a polyalkylene oxide monoalkyl ether and a polyalkylene oxide monoalkyl ether. It is characterized by using a reaction product with at least one kind of polyalkylene oxide monoether selected from phenyl ether and polyalkylene oxide monoalkylphenyl ether, or a metal salt thereof as an active ingredient.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A styrene / maleimide / maleic anhydride copolymer as a first raw material of an antistatic resin modifier according to the present invention has a number average molecular weight in the range of 5,000 to 300,000 and has It is preferable that the ratio of the styrene component to 1 mol part of the maleic acid component is in the range of 1 to 50 mol parts, and that the ratio of the maleimide component is in the range of 1 to 20 mol parts.
Number average molecular weight in the range of 000, especially 50,000 to 15
000 and a ratio of styrene to 1 mol part of the maleic anhydride component of 1 to 4
0 mole parts, and the ratio of the maleimide component is 1 to 1
Those in the range of 5 mole parts are preferred. Various such styrene / maleimide / maleic anhydride copolymers can be obtained as commercial products.

In the styrene / maleimide / maleic anhydride copolymer, when the ratio of the maleimide component to 1 mol part of the maleic anhydride component is less than 1 mol part,
When the obtained resin modifier is blended with a thermoplastic resin, the heat resistance of the obtained resin composition is significantly reduced.
When the amount is more than the molar part, the reactivity with the polyalkylene oxide monoalkyl ether is poor, and the desired resin modifier cannot be obtained.

In the styrene / maleimide / maleic anhydride copolymer, when the ratio of the styrene component to 1 mol part of the maleic anhydride component is less than 1 mol part, the obtained resin modifier is a thermoplastic resin, particularly, On the other hand, it is not preferable because of poor compatibility with the styrenic resin.
When the amount exceeds 0 mole parts, even if the obtained resin modifier is blended with the thermoplastic resin, the surface specific resistance of the resin does not decrease,
It is not preferable because the antistatic effect is poor.

The polyalkylene oxide monoether, which is the second raw material of the antistatic resin modifier according to the present invention, comprises:
General formula (I)

[0011]

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(Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, a phenyl group or a phenyl group having an alkyl group having 1 to 10 carbon atoms, and R ² represents hydrogen or an alkyl group having 1 or 2 carbon atoms. Represents an alkyl group, and n is an integer of 5 to 100.), and the number average molecular weight is preferably in the range of 400 to 5,000.

In the polyalkylene oxide monoether, when the number of carbon atoms of the alkyl group in the alkyl alcohol residue or the alkylphenol residue forming the monoether is larger than 10, styrene / maleimide.
The compatibility of the modifier obtained as a reaction product with the maleic anhydride copolymer with the resin becomes poor. Further, when the number average molecular weight of the polyalkylene oxide monoether is smaller than 400, as described later, a modifier obtained as a reaction product with a styrene / maleimide / maleic anhydride copolymer is added to the resin. However, a sufficient antistatic effect cannot be imparted to the resin, while the number average molecular weight is 50%.
When it is larger than 00, the reactivity with the styrene / maleimide / maleic anhydride copolymer is poor, and the desired modifier cannot be obtained. In particular, in the present invention,
The polyalkylene oxide monoether is 500 to 40
It preferably has a number average molecular weight in the range of 00.

Such a polyalkylene oxide monoether can usually be obtained by reacting the corresponding polyalkylene oxide with an alkyl alcohol, phenol or alkylphenol. here,
In general, the polyalkylene oxide can be obtained by ring-opening polymerization of the alkylene oxide. In the present invention, the polyalkylene oxide may be a homopolymer or a copolymer. That is, the polyalkylene oxide may be any of polyethylene oxide, polypropylene oxide, and polyethylene polypropylene oxide.

However, in the present invention, among these various polyalkylene oxide monoethers, the reactivity with the styrene / maleimide / maleic anhydride copolymer and the charge as a modifier of the obtained reaction product are improved. In particular, polyethylene oxide monoalkyl phenyl ethers, especially polyethylene oxide monononyl phenyl ether, polypropylene oxide monoalkyl ethers, and especially polypropylene oxide Monobutyl ether is preferred.

First, the production of a reaction product of the styrene / maleimide / maleic anhydride copolymer and the polyalkylene oxide monoether will be described. This reaction product can be produced by any of a batch method and a continuous method. In the batch method, for example, a styrene / maleimide / maleic anhydride copolymer and a polyalkylene oxide monoether are heated and melted in a reaction vessel equipped with a stirrer, and reacted under stirring. The two raw materials are heated in a single-screw, twin-screw or multi-screw extruder, melted, and reacted under stirring.

In either method, the styrene / maleimide / maleic anhydride copolymer and the polyalkylene oxide monoether are used in an amount of 1 part by weight of the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer. The alkylene oxide monoether (that is, the hydroxyl group component) is added in an amount of 0.05 to 1.5 mol parts, preferably 0.08 to 1.5 mol parts.
To 1.2 parts by mole, most preferably 0.1 to 1.0 parts by mole. This styrene / maleimide /
When the polyalkylene oxide monoether (that is, hydroxyl group) is used in an amount of more than 1.5 mole parts per 1 mole part of the maleic anhydride component of the maleic anhydride copolymer, unreacted polyalkylene oxide monoether after the reaction is used. If the amount of ether increases and the reaction product is used as a resin modifier, the moldability of the resin composition is reduced, the molded product is sticky, and the thermal properties are reduced. When the polyalkylene oxide monoether (that is, hydroxyl group) is used in an amount of less than 0.05 mol part to 1 mol part of the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer, the obtained reaction product Have no sufficient antistatic effect.

According to a preferred embodiment, when the modifier is produced by a batch method, a styrene / maleimide / maleic anhydride copolymer and a predetermined amount of half of a polyalkylene oxide monoether are charged into a reaction vessel, and nitrogen is added. 1 in the atmosphere
After heating to a temperature of 70 to 300 ° C., preferably 190 to 280 ° C. to melt, and after melting, the other half of the polyalkylene oxide monoether is charged, and further, 170 to 260 ° C., preferably 190 to 260 ° C. ° C to 230
React at a temperature of ° C. The reaction time is generally about 10 minutes to 6 hours, preferably about 15 minutes to 4 hours.

When the reaction temperature is lower than 170 ° C., the reactivity of the styrene / maleimide / maleic anhydride copolymer is poor. On the other hand, when the reaction temperature is higher than 300 ° C., depending on the polyalkylene oxide monoether used, decomposition may occur. When the reaction occurs, the reaction may not be uniform because of lack of compatibility with styrene, maleimide and maleic anhydride.

In a continuous system using a single-screw or multi-screw extruder, a styrene / maleimide / maleic anhydride copolymer and a half of a predetermined amount of polyalkylene oxide monoether are charged into an extruder, and a temperature of 190 to 280 ° C. After melt-kneading the mixture and cooling to obtain a target precursor as a solid, this was pulverized, and this was again charged into an extruder together with the other half of the polyalkylene oxide monoether, and the mixture was mixed with the extruder.
The desired product is obtained by melting and kneading at a temperature of from 250C to 250C.

Thus, styrene / maleimide /
The antistatic resin according to the present invention as a reaction product of a maleic anhydride copolymer and a polyalkylene oxide monoether, that is, a graft type polymer of a polyalkylene oxide monoether onto a styrene / maleimide / maleic anhydride copolymer A modifier can be obtained. According to the present invention, if such a graft polymer itself is blended with a thermoplastic resin, an antistatic effect can be imparted, but a metal salt of the graft polymer can also be used as an effective antistatic agent. .

That is, according to the present invention, in the reaction of a styrene / maleimide / maleic anhydride copolymer with a polyalkylene oxide monoether, a carboxyl group formed secondarily from an acid anhydride group and an unreacted group By utilizing the acid anhydride group of the above, the obtained graft polymer can be made into various metal salt structures, or the graft polymer can be made into an ionomer structure. As described above, when the graft polymer has a metal salt structure or an ionomer structure, not only the rubber elasticity of the graft polymer can be enhanced, but also the antistatic effect can be enhanced.

As described above, in order for the graft type polymer to have a metal salt structure or an ionomer structure, styrene.
When a maleimide / maleic anhydride copolymer and a polyalkylene oxide monoether are melt-kneaded and reacted, various metal oxides and hydroxides, or carbonates, acetates, and organic acid salts (for example, Metal salts such as stearate) may be allowed to coexist. Here, according to the present invention, the metal oxide, hydroxide, metal salt and the like are usually based on a reaction product of a styrene / maleimide / maleic anhydride copolymer and the polyalkylene oxide monoether. , 0.0
It is used in an amount of 1 to 10% by weight, preferably 0.05 to 5% by weight.

The metal ions forming the metal salts include lithium, sodium, potassium, aluminum,
Although metal ions such as magnesium and zinc can be mentioned, according to the present invention, lithium or sodium ions are particularly preferable.

The antistatic resin modifier according to the present invention can have a long lasting antistatic property by being blended with a thermoplastic resin. The modifier can be suitably used for a styrene resin. Here, the styrene-based resin includes a homopolymer of a styrene-based monomer, a copolymer of a styrene-based monomer and a monomer copolymerizable with the styrene-based monomer, and a rubber of these homopolymer or copolymer. It includes a mixture with a homopolymer and a homopolymer or a copolymer modified with a rubbery polymer.

Here, as the styrene monomer,
For example, styrene, halogenated styrene (chlorostyrene, bromostyrene, etc.), alkylated styrene (α-methylstyrene, vinyltoluene, etc.), divinylbenzene and the like can be mentioned.

Examples of monomers copolymerizable with these styrene monomers include 1-alkenes (ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
Octene), conjugated dienes (isobrene, butadiene, etc.), vinyl esters of monobasic fatty acids (vinyl acetate, vinyl propionate, etc.), unsaturated carboxylic acids ((meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid) , Itaconic acid, etc.) and their esters, one or more of vinyl cyanide (acrylonitrile, methacrylonitrile), alkylene glycol di (meth) acrylate (1,3-butylene glycol dimethacrylate, etc.) and the like. be able to.

Typical styrene resins include, for example, polystyrene, styrene-maleic anhydride copolymer, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), and a blend with butadiene rubber. And high impact polystyrene.

The modifier according to the present invention is used in an amount of usually 0.1 to 30% by weight, preferably 0.2 to 2% by weight, based on the thermoplastic resin.
It is blended in the range of 0% by weight.

The resin modifier according to the present invention thus comprises:
By bonding a polyalkylene oxide monoether and a styrene / maleimide / maleic anhydride copolymer by an esterification reaction between the former terminal hydroxyl group and the latter maleic anhydride site, styrene / maleimide / maleic anhydride is obtained. The present invention solves the above-mentioned problems of the conventional antistatic agent as a graft polymer having an appropriate molecular weight and having a copolymer as a main chain and a polyalkylene oxide monoether as a side chain. That is, according to the modifier of the present invention, styrene / maleimide /
The maleic anhydride copolymer improves the compatibility with the thermoplastic resin while suppressing a decrease in the heat resistance of the thermoplastic resin composition containing the same, and further improves the side chain polyalkylene oxide monoether. And the effect of maintaining the mechanical properties of the modifier due to the elastic properties of the graft structure by the side chains of the modifier, which is not seen in conventional antistatic agents.

Further, the modifier according to the present invention has a high affinity with many additives and fillers having various polar groups to be blended in the thermoplastic resin due to its polar structure. Dispersibility in resin can be improved, and it is also effective in reducing problems such as adhesion to a mold during molding by bleed and poor appearance of a molded product.

The modifier according to the present invention includes various heat stabilizers, antioxidants, antioxidants, light stabilizers, lubricants, release agents, antifogging agents, depending on the required properties and applications of the molded article. Processing aids, plasticizers, coloring agents, pigments, fillers, reinforcing materials, in combination with additives such as flame retardants, and, if necessary, in combination with conventionally known antistatic agents, You may mix | blend with a thermoplastic resin.

The modifier according to the present invention, if necessary, is blended with a thermoplastic resin by an appropriate means together with the above-mentioned additives and the like, melted and kneaded to form a resin composition. Can be processed into various molded products. For blending the modifier with the thermoplastic resin and melt-kneading, for example, a conventionally known one such as a Henschel mixer, a Banbury mixer, a mixing roll, a kneader, or a single-screw or twin-screw extruder is used. Used as appropriate. In order to process the resin composition thus obtained into a required molded product, any conventionally known appropriate means such as injection molding, extrusion molding, hollow molding, compression molding and the like can be used.

By applying the antistatic resin modifier according to the present invention to various resins, it is possible to provide a long lasting antistatic effect and also to improve the moldability of the resin. In particular, the modifier according to the present invention can impart long-lasting antistatic properties and excellent moldability to a styrenic resin without impairing thermal and mechanical properties.

Thermoplastics incorporating the modifier according to the invention,
In particular, styrene resins have high antistatic properties over a long period of time, and in addition to electrical equipment parts, information and communication equipment, and those parts, automotive parts, packaging materials, industrial materials,
It can be suitably used in a wide range of fields such as indoor / outdoor parts and miscellaneous goods.

[0036]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the following, the reaction rate of polyethylene oxide monoether is determined from a method in which a reaction product is sampled, dissolved in dioxane or tetrahydrofuran, and titrated with a methanol solution of potassium hydroxide to measure the disappearance of the acid value. Was.

(Production of Antistatic Resin Modifier) Example 1 A 500 mL separable flask equipped with a magnetic stirrer was charged with a styrene / maleimide / maleic anhydride copolymer (number average molecular weight: 140,000, styrene / maleimide / maleic anhydride). Molar ratio = 7.25 / 4.25 / 1, acid value 88.73m
gKOH / g), 100 g of an antioxidant (Irganox 1076 manufactured by Ciba-Geigy, hereinafter the same), and 50 g of polyethylene oxide monononyl phenyl ether (a 70 mol adduct of nonylphenol ethylene oxide, number average molecular weight 3300) (0.015) ) And heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to melt, and then reacted for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 9
8%. Next, 50 g of the above-mentioned polyethylene oxide monononylphenyl ether (0.015
Mol), heated to a temperature of 200 ° C. to 230 ° C., and reacted for 1 hour to obtain a reaction product of a styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether, which is a target substance. Obtained. The reaction rate of the target product is 98%, and styrene / maleimide /
The molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SA-1.

Example 2 In a 500 mL separable flask equipped with a magnetic stirrer, 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.1 g of an antioxidant, and polyethylene oxide monononylphenyl as in Example 1 were used. Ether 50
g (0.015 mol) and sodium acetate
0.6 g was added, and the mixture was heated and melted at a temperature of 250 to 270 ° C. under a nitrogen atmosphere, and then reacted for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Next, 50 g (0.015 mol) of the above-mentioned polyethylene oxide monononylphenyl ether and 0.2 g of sodium acetate are added to the precursor, and the mixture is heated to a temperature of 200 to 230 ° C., and reacted for 1 hour to obtain the desired product. A reaction product of a styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononylphenyl ether was obtained. The reaction rate of the target product is 9
The molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SA-1A.

Example 3 In a separable flask with a magnetic stirrer having a capacity of 500 mL, 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.1 g of an antioxidant, and polyethylene oxide monononyl phenyl ether (nonylphenol ethylene oxide 40) were used. Molar adduct, number average molecular weight 194
0) 29.1 g (0.015 mol) were charged and heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to be melted, and then reacted for 1.5 hours to obtain a precursor of the target substance as a solid. As obtained. The reaction rate determined from the acid value of this precursor was 98%. Then, 29.1 g of the same polyethylene oxide monononyl phenyl ether as in Example 1 (0.0
15 mol), heated to a temperature of 200 ° C. to 230 ° C., and allowed to react for 1 hour to obtain a reaction product of styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether, which is a target substance. Obtained. The reaction rate of the target product is 98%, and styrene / maleimide /
The molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SA-2.

Example 4 In a 500 mL separable flask equipped with a magnetic stirrer, 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.1 g of an antioxidant, and polyethylene oxide monononyl phenyl ether (nonylphenol ethylene oxide 10 Molar adduct, number average molecular weight 64
0) 9.6 g (0.015 mol) was charged, and heated to 250 to 270 ° C. under a nitrogen atmosphere to be melted.
The reaction was carried out for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Then, 9.6 g (0.015 g) of the same polyethylene oxide monononyl phenyl ether as in Example 1 was added to this precursor.
Mol) and heated to a temperature of 200 ° C to 230 ° C,
After reacting for a time, the desired product styrene / maleimide /
A reaction product of the maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether was obtained. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononylphenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was
0.38. Hereinafter, this is referred to as SA-3.

Example 5 Twin screw extruder (BT-3 manufactured by Plastic Engineering Laboratory Co., Ltd.)
0-S2-42-L) with 1000 g of a styrene / maleimide / maleic anhydride copolymer as in Example 1, 1 g of an antioxidant, and 500 g (0.15 mol) of polyethylene oxide monononyl phenyl ether as in Example 1. And heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere,
The mixture was melted and kneaded for 30 minutes to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 99%. Then, 500 g of the same polyethylene oxide monononyl phenyl ether as in Example 1 (0.15
Mol), and the mixture was heated to a temperature of 200 ° C to 230 ° C and melt-kneaded to obtain a reaction product of a styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether, which was the target substance. . The conversion of the target product was 99%, and the molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.3.
It was 8. Hereinafter, this is referred to as SA-11.

Example 6 A 500 mL separable flask equipped with a magnetic stirrer was charged in a separable flask with a magnetic stirrer with 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.1 g of an antioxidant, and polyethylene oxide monononylphenyl as in Example 1. Ether 50
g (0.015 mol) and 0.8 g of lithium chloride,
The mixture was heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to be melted, and then reacted for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Then, the same polyethylene oxide monononyl phenyl ether 50 as in Example 1 was added to this precursor.
g (0.015 mol) and 0.2 g of lithium chloride, and 2
Heated to a temperature of 00 ° C to 230 ° C and reacted for 1 hour,
A reaction product of the desired product, styrene / maleimide / maleic anhydride copolymer, and polyethylene oxide monononylphenyl ether was obtained. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononylphenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.38.
Hereinafter, this is referred to as SA-1B.

Example 7 In a separable flask with a magnetic stirrer having a capacity of 500 mL, 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.025 g of an antioxidant, and polyethylene oxide monononylphenyl as in Example 1 were used. 12.5 g (0.004 mol) of ether was charged and heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to be melted.
The reaction was carried out for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Then, 12.5 g (0.000) of the same polyethylene oxide monononyl phenyl ether as in Example 1 was added to this precursor.
4 mol) and heated to a temperature of 200 ° C to 230 ° C,
The reaction was carried out for 1 hour to obtain a reaction product of a target product of styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononylphenyl ether. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.10. Hereinafter, this is referred to as SA-1-1.

Example 8 In a separable flask with a magnetic stirrer having a capacity of 500 mL, 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.25 g of an antioxidant, and polyethylene oxide monononylphenyl as in Example 1 were used. Ether 1
00g (0.03 mol), and 25 g under a nitrogen atmosphere.
The mixture was heated to 0 to 270 ° C. to be melted, and then reacted for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Next, 100 g (0.03 mol) of the same polyethylene oxide monononyl phenyl ether as in Example 1 was added to this precursor,
The mixture was heated to a temperature of 200 ° C. to 230 ° C. and reacted for 1 hour to obtain a reaction product of a target product of styrene / maleimide / maleic anhydride copolymer and polyethylene oxide monononylphenyl ether. Reaction rate of target substance is 98
%, And the molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.76. Hereinafter, this is referred to as SA-1-2.

Comparative Example 1 In a separable flask having a magnetic stirrer having a capacity of 500 mL, 100 g of a styrene / maleimide / maleic anhydride copolymer, 0.004 g of an antioxidant and polyethylene oxide monononyl phenyl ether (nonylphenol ethylene oxide 20) were used. Molar adduct, number average molecular weight 3
00) 4.5 g (0.015 mol), and heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to be melted. Thereafter, the mixture was reacted for 1.5 hours to obtain the target precursor as a solid. As obtained. The reaction rate determined from the acid value of this precursor was 98%. Next, 4.5 g (0.015 mol) of the above polyethylene oxide monononylphenyl ether was further added to the precursor, and the mixture was heated to a temperature of 200 ° C. to 230 ° C. and reacted for 1 hour to obtain the desired styrene / maleimide. A reaction product of a maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether was obtained. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononyl phenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.3.
It was 8. Hereinafter, this is referred to as SA-4.

Example 9 A 500 mL separable flask equipped with a magnetic stirrer was charged into a separable flask having a magnetic stirrer with 100 g of the same styrene / maleimide / maleic anhydride copolymer as in Example 1, 0.06 g of an antioxidant, and polyoxyethylene lauryl ether (number-average molecular weight: 2,000). ) 30
g (0.015 mol) and 250 g under a nitrogen atmosphere.
The mixture was heated to a temperature of about 270 ° C. to be melted, and then reacted for 1.5 hours to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 98%. Next, 30 g (0.015 mol) of the above polyoxyethylene lauryl ether was further added to this precursor,
The mixture was heated to a temperature of 30 ° C. and reacted for 1 hour to obtain a reaction product of a styrene / maleimide / maleic anhydride copolymer and polyoxyethylene lauryl ether. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononylphenyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SA-5.

Comparative Example 2 A 500 mL separable flask equipped with a magnetic stirrer was placed in a separable flask equipped with a magnetic stirrer.
0000, styrene / maleic anhydride molar ratio = 1/1,
100 g of acid value 500 mg KOH / g) and 0.1 of antioxidant
g and polyethylene oxide monononyl phenyl ether (nonylphenol ethylene oxide 70 mol adduct,
50 g (0.015 mol) of a number average molecular weight of 3300, and heated and melted at a temperature of 250 to 270 ° C. under a nitrogen atmosphere, followed by a reaction for 1.5 hours to obtain a precursor of the target substance. Obtained as a solid. The reaction rate determined from the acid value of this precursor was 98%. Then, 50 g of the above polyethylene oxide monononyl phenyl ether was added to this precursor.
(0.015 mol), heated to a temperature of 200 ° C. to 230 ° C., and reacted for 1 hour to form a reaction product of styrene / maleic anhydride copolymer and polyethylene oxide monononyl phenyl ether, which are the desired products. I got something. The conversion of the target product was 98%, and the molar ratio of polyethylene oxide monononylphenyl ether to the maleic anhydride component of the styrene / maleic anhydride copolymer was 0.067. Hereinafter, this is referred to as SA-6.

(Preparation of Test Piece and Evaluation of Antistatic Resin Modifier) Extruder (UE manufactured by Union Plastics Co., Ltd.)
Using a V-type extruder), the antistatic resin modifier produced in Examples 1 to 9 and Comparative Examples 1 and 2 was added to ABS resin (Modifier Resin B300N (registered trademark) manufactured by Ube Sycon Co., Ltd.). Compounded at the ratio shown in Table 1,
After kneading and compounding at a temperature of ~ 240 ° C, an injection molding machine (TOSH
8c using IBA MACHINE Battenfeld PLUS 250)
It was molded into a test piece of mx 5 cm x 3 mm. Each test piece had a good appearance and had no sticky surface.
For these test pieces, the electrostatic characteristics (surface resistivity),
The heat distortion temperature and Izod impact strength were measured as follows. The results are shown in Tables 1 and 2.

Electrostatic Characteristics After storing the molded test pieces for 3 days at a temperature of 23 ° C. and a humidity of 50%, a super-insulation meter (DSM-8 manufactured by Toa Denpa Kogyo KK) was used.
103, using the electrode for a flat plate SME-8310), the surface resistance was measured (initial), and one month later, it was measured again (one month later).

Heat Deformation Temperature The test piece of the resin composition was measured for the heat deformation temperature according to JIS K7206.

Izod Impact Strength Izod impact strength of a test piece of the resin composition was measured in accordance with JIS K 7110.

Comparative Example 3 A test piece was prepared in the same manner as described above except that a commercially available product 1 (ethylene oxide / epihalohydrin copolymer) was used as an antistatic agent, and the surface resistivity, heat deformation temperature and Izod impact strength were measured. Was measured. Table 2 shows the results.

Comparative Example 4 A test piece was prepared in the same manner as described above, except that an antistatic resin modifier was not added to ABS resin (Psycolac L (registered trademark) manufactured by Ube Sycon Co., Ltd.). For this test piece, the surface resistivity, heat deformation temperature, and Izod impact strength were measured in the same manner as described above. Table 2 shows the results.

[0054]

[Table 1]

[0055]

[Table 2]

Example 10 A 500 mL separable flask equipped with a magnetic stirrer was charged with a styrene / maleimide / maleic anhydride copolymer (number-average molecular weight: 100,000, styrene / maleimide / maleic anhydride molar ratio = 37.5 / 11.5 / 1, acid value 21.94m
gKOH / g), 0.1 g of antioxidant and polypropylene oxide monobutyl ether (number average molecular weight 28
23.3 g (0.008 mol) was heated and melted at a temperature of 240 to 270 ° C. in a nitrogen atmosphere. -A reaction product of a maleic anhydride copolymer and polypropylene oxide monobutyl ether was obtained. The conversion of the target product was 98%, and the molar ratio of polypropylene oxide monobutyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.1%.
It was 4. Hereinafter, this is referred to as BA-1-1.

Example 11 Twin screw extruder (BT-3 manufactured by Plastic Engineering Laboratory Co., Ltd.)
0-S2-42-L) was charged with 1000 g of a styrene / maleimide / maleic anhydride copolymer as in Example 10, 1 g of an antioxidant, and 233 g (0.08 mol) of polypropylene oxide monobutyl ether as in Example 10. ,
Heat to a temperature of 240-270 ° C under a nitrogen atmosphere,
The mixture was melted and kneaded for 1 minute to obtain a reaction product of a target product of styrene / maleimide / maleic anhydride copolymer and polypropylene oxide monobutyl ether. The conversion of the target product was 99%, and the molar ratio of polypropylene oxide monobutyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.4. Hereinafter, this is referred to as BA-1-2.

Example 12 100 g of a styrene / maleimide / maleic anhydride copolymer, 0.1 g of an antioxidant and the same polypropylene oxide monobutyl ether 43 as in Example 10 were placed in a 500 mL separable flask equipped with a magnetic stirrer. .6g
(0.015 mol) and sodium acetate (0.8 g) were added and heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere to be melted. As obtained. The reaction rate determined from the acid value of this precursor was 9
8%. Next, 43.6 g (0.015 mol) of the above-mentioned polypropylene oxide monobutyl ether and 0.2 g of sodium acetate were added to this precursor, and the mixture was added at 200 ° C to 23 ° C.
The mixture was heated to a temperature of 0 ° C. and reacted for 1 hour to obtain a reaction product of styrene / maleimide / maleic anhydride copolymer and polypropylene oxide monobutyl ether, which was the target substance. The conversion of the target product was 98%, and the molar ratio of polypropylene oxide monobutyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SBA-1A.
That.

Example 13 Twin screw extruder (BT-3 manufactured by Plastic Engineering Laboratory Co., Ltd.)
0-S2-42-L) was charged with 1000 g of a styrene / maleimide / maleic anhydride copolymer as in Example 1, 1 g of an antioxidant, and 436 g (0.15 mol) of polypropylene oxide monobutyl ether as in Example 10. Then, the mixture was heated to a temperature of 250 to 270 ° C. under a nitrogen atmosphere and melt-kneaded for 30 minutes to obtain a target precursor as a solid. The reaction rate determined from the acid value of this precursor was 99%. Next, 436 g (0.15 mol) of the same polypropylene oxide monobutyl ether as in Example 10 was added to this precursor, and the mixture was heated to a temperature of 200 ° C to 230 ° C and melt-kneaded to obtain the desired product, styrene / maleimide / anhydrous. A reaction product of a maleic acid copolymer and polypropylene oxide monobutyl ether was obtained. The conversion of the target product was 99%, and the molar ratio of polypropylene oxide monobutyl ether to the maleic anhydride component of the styrene / maleimide / maleic anhydride copolymer was 0.38. Hereinafter, this is referred to as SBA-1L.

(Preparation of Test Piece and Evaluation of Antistatic Resin Modifier) Extruder (UE manufactured by Union Plastics Co., Ltd.)
Examples 10 to 1 were applied to ABS resin (EX-120 (registered trademark) manufactured by Ube Sicon Co., Ltd.) using a V-type extruder.
After mixing the antistatic resin modifier prepared in 3 in the ratio shown in Table 3, kneading and mixing at a temperature of 190 to 240 ° C., an injection molding machine (TOSHIBA MACHINE Battenfeld PLUS 250)
Was used to form a test piece of 8 cm × 5 cm × 3 mm. Each test piece had a good appearance and had no sticky surface. With respect to these test pieces, electrostatic characteristics (surface resistivity), heat deformation temperature, and Izod impact strength were measured by the same methods as described above. Table 3 shows the results.

Comparative Example 5 An ABS resin (EX-120 (registered trademark) manufactured by Ube Sicon Co., Ltd.) was mixed with no antistatic resin modifier.
A test piece was prepared in the same manner as described above. For this test piece, the surface resistivity, heat deformation temperature, and Izod impact strength were measured in the same manner as described above. Table 3 shows the results.

Comparative Example 6 The antistatic resin modifier prepared in Comparative Example 2 was AB
A test piece was molded in the same manner as described above except that it was blended with S resin (EX-120 (registered trademark) manufactured by Ube Sycon Co., Ltd.), and the electrostatic properties (surface resistivity), heat deformation temperature and Izod impact The strength was measured as follows. The electrostatic characteristics, heat distortion temperature and Izod impact strength were measured by the same methods as described above. Table 3 shows the results.

Comparative Example 7 A test piece was prepared in the same manner as described above except that a commercially available product 2 (polyetheresteramide) was used as an antistatic agent, and the surface resistivity, heat distortion temperature and Izod impact strength were measured. did. Table 3 shows the results.

[0064]

[Table 3]

[0065]

As described above, the modifier according to the present invention comprises:
Various thermoplastic resins, especially high impact polystyrene (H
IPS) and excellent compatibility with styrenic resins such as ABS resins. Such styrenic resins can be used without impairing their inherent thermal and mechanical properties.
It is possible to provide an antistatic property that is maintained over a long period of time, and it is also possible to improve the moldability of these styrene resins.

Further, the modifier according to the present invention has an effect of increasing the dispersibility and compatibility of various fillers and additives in the styrene resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 35/06 C08L 35/06 71/02 71/02 F term (reference) 4J002 BC031 BC042 BC051 BC061 BC071 BC081 BC091 BC111 BH022 BN182 CH052 FD010 FD020 FD030 FD040 FD060 FD070 FD090 FD130 FD160 FD170 GG02 GN00 GQ00 4J031 AA13 AA22 AA53 AB01 AC03 AD01 AF10 AF11 AF19 AF23 AF30 4J100 AB02P AK32RAM43Q BA04HBAH08 DA08

Claims (9)

[Claims] 1. A copolymer of (A) styrene / maleimide / maleic anhydride, and (B) at least one selected from polyalkylene oxide monoalkyl ethers, polyalkylene oxide monophenyl ethers and polyalkylene oxide monoalkyl phenyl ethers An antistatic resin modifier comprising, as an active ingredient, a reaction product of the above with a polyalkylene oxide monoether or a metal salt thereof. 2. A reaction product of a polyalkylene oxide monoether with 0.05 to 1.5 mol parts per 1 mol part of a maleic anhydride component of a styrene / maleimide / maleic anhydride copolymer, or a reaction product thereof. 2. The antistatic resin modifier according to claim 1, comprising a metal salt as an active ingredient. 3. The styrene / maleimide / maleic anhydride copolymer has a number average molecular weight in the range of 5,000 to 300,000, and the ratio of the styrene component to 1 mol part of the maleic anhydride component is in the range of 1 to 50 mol parts. The resin modifier according to claim 1, wherein a ratio of the maleimide component is in a range of 1 to 20 mol parts. 4. The polyalkylene oxide monoether is 4
2. The composition according to claim 1, which has a number average molecular weight in the range of 00 to 5000.
Or the resin modifier according to 2. 5. The resin modifier according to claim 1, wherein the polyalkylene oxide monoether is polyethylene oxide monononylphenyl ether. 6. The resin modifier according to claim 1, wherein the polyalkylene oxide monoether is polypropylene oxide monobutyl ether. 7. The resin modifier according to claim 1, wherein the metal salt is a lithium, sodium, potassium, magnesium, aluminum or zinc salt. 8. A thermoplastic resin composition comprising the thermoplastic resin and the modifier according to claim 1 in an amount of 0.1 to 30% by weight. 9. A molded article comprising the thermoplastic resin composition according to claim 8.