JPH09176497A - Permanent antistatic resin composition and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a permanent antistatic resin compsn. which has both a permanent and excellent antistatic effect which does not decrease by water washing and wiping and good physical properties, moldability and heat resistance by incorporating a specified polyether ester into a thermoplastic resin. SOLUTION: This resin compsn. consists of 5-50 pts.wt. polyether ester (A) consisting of a 4-20C para-oriented arom. dicarboxylic acid ingredient (A1), a sulfonic acid base-contg. diol ingredient (A2) of the formula (wherein R<1> and R<2> are each a 2-4C divalent alkylene group and (m) and (n) are each an integer of 1-10 and Ar is a 6-20C trivalent arom. group and M<+> is a metal ion, a tetraalkyl phosphonium ion or an ammonium ion), a 2-10C glycol ingredient (A3) and a polyalkylene oxide ingredient (A4) contg. two ester-forming functional groups in the molecule and with a no. average mol.wt. of 200-50,000 and 95-60 pts.wt. thermoplastic resin (B) except (A).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having antistatic properties, and more specifically, a resin composition having an excellent antistatic effect and having a permanent antistatic property in which such effect is not deteriorated even by washing with water. Regarding

[0002]

2. Description of the Related Art Plastic materials make good use of their excellent characteristics to make electric and electronic parts, automobile parts, medical parts,
It is used as a household item and various molded products. By the way, plastics generally have the characteristic of high electrical insulation, but because of this, the static electricity that is charged is rather difficult to dissipate, dust adheres to products, electric shock to workers, malfunctions of instruments and IC chips, etc. The problem has arisen. Therefore, studies on antistatic methods have been conducted for various plastic materials.

As an antistatic method for plastics, there are an internal addition type and a coating type. The coating type requires a separate process, and the internal addition type is more advantageous in the manufacturing process.

In the internal addition type method, a method in which an ionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate is kneaded into a polymer has been generally adopted because of its excellent effect and economy. It was

Above all, a system utilizing an alkyl (aryl) sulfonate as an ionic surfactant has been well studied, and as a large antistatic effect, for example, the secondary position of an alkane is substituted with a sulfonic acid metal salt. Japanese Patent Application Laid-Open No. 5-222241 and Japanese Patent Application Laid-Open No. 62-230835 disclose the use of a phosphonium salt. However, in the method using such a low-molecular-weight surfactant, such a surfactant seeps out onto the resin surface, and although the antistatic effect is high, the effect is reduced when wiping or washing with water. There is.

Therefore, a method of mixing an antistatic polymer with a resin is described as a method for imparting a permanent antistatic effect which is not lost even after washing with water. For example, JP
JP-A-2-273252 describes that a polyether ester amide is used as an antistatic polymer for a resin composed of a polycarbonate and a polystyrene polymer. Further, in JP-A-5-97984, a graft polymer in which a trunk polymer is a polyamide and a branch polymer is a block polymer of a polyalkylene ether and a polyester is described as a high molecular weight antistatic agent. The effect of reducing is mentioned. Regarding the antistatic polymer having a structure in which an aromatic ring is substituted with a sulfonate salt, US Pat. No. 4,0061,123 and US Pat.
No. 5346 describes a polyamide having a phosphonium sulfonate in the molecule and having a glass transition temperature of 25 ° C. or lower. However, in order to enhance the antistatic effect, it is necessary to mix a relatively large amount of such a polymer with the resin, so the heat resistance and mechanical properties that the resin originally possessed are impaired, and Therefore, there is a problem that the production cost is high, and the glass transition temperature of such a polymer is low, which makes it difficult to handle.

By the way, Japanese Patent Application Laid-Open No. 6-57153 discloses a polyether ester composed of polyalkylene glycol, glycol and polyvalent carboxylic acid. Although the change with time of the antistatic property is small, the effect (size) of the antistatic property is not sufficient with such a polymer alone. Therefore, the use of an ionic surfactant such as sodium dodecyl sulfonate in order to further improve the antistatic effect is also described. However, when such an agent is used in combination, the antistatic effect is reduced by washing with water. Furthermore, although this polyether ester has been described as an application as an antistatic agent for various thermoplastic polymers, there is also a problem that it is not very effective for polymers having a good affinity with a polyether component such as polycarbonate. is there.

As described above, at present, a resin composition having both good physical properties and heat resistance and a permanent and large antistatic effect has not been obtained.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to have a great antistatic effect permanently without being deteriorated by washing with water or wiping, and to have good physical properties, moldability and heat resistance. Another object is to provide a resin composition.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a para-oriented aromatic dicarboxylic acid component and a diol component nucleus-substituted with a sulfonic acid group are contained. The specific polyether ester
It has been found that, by containing a specific amount in the thermoplastic resin, a large antistatic effect can be permanently imparted without impairing various properties of the thermoplastic resin, and the present invention has been accomplished.

That is, the present invention relates to (A) (A1) a para-oriented aromatic dicarboxylic acid component having 4 to 20 carbon atoms, (A2)
The following formula (1)

[0012]

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[In the formula (1), R ¹ and R ² are each independently a divalent alkylene group having 2 to 4 carbon atoms, and m and n are each independently an integer of 1 to 10. Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion], and a sulfonate group-containing diol component represented by (A3) carbon number A polyether ester comprising 2 to 10 glycol components and (A4) a poly (alkylene oxide) component having two ester-forming functional groups in the molecule and having a number average molecular weight of 200 to 50,000, which comprises (A2) The content is in the range of 5 to 50 mol% with respect to the total dicarboxylic acid component, and (A
5-40 parts by weight of a polyether ester having a content of (A4) within the range of 10-50% by weight based on the total amount of the four components 1), (A2), (A3) and (A4), and B) A permanent antistatic resin composition comprising 95 to 60 parts by weight of a thermoplastic resin other than (A).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The permanent antistatic resin composition of the present invention comprises a polyether ester (A) and a thermoplastic resin (B) other than (A).

The aromatic dicarboxylic acid component, which is one of the components constituting the polyether ester (A) of the present invention, is a para-oriented aromatic dicarboxylic acid component (A having 4 to 20 carbon atoms).
1). Examples of such para-oriented aromatic dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid, dimethyl terephthalate, diethyl terephthalate, 2, Dimethyl 6-naphthalenedicarboxylate, 2,
Diethyl 6-naphthalenedicarboxylate, biphenyl-
Dimethyl 4,4'-dicarboxylate, biphenyl-4,
Aromatic dicarboxylic acid esters such as diethyl 4′-dicarboxylic acid can be mentioned. These may have a substituent such as an alkyl group or halogen on the aromatic ring.

These aromatic dicarboxylic acid components may be used alone or in combination of two or more. Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, and 2,6-naphthalenedicarboxylic acid dimethyl are preferred from the viewpoint of handleability when the obtained polyether ester is mixed with another thermoplastic resin. It is preferable to use an aromatic dicarboxylic acid component such as dimethyl biphenyl-4,4′-dicarboxylate.

By using a para-oriented aromatic dicarboxylic acid component having 4 to 20 carbon atoms, the polymerizability of the polyether ester, the handleability when mixed with the thermoplastic resin (B), the moldability and the like are excellent, A good antistatic effect can be imparted to the plastic resin.

The aromatic dicarboxylic acid component (A1)
Is within a range that does not deteriorate the physical properties such as the glass transition temperature and crystallinity of the polyether ester (A) that influences the antistatic performance (for example, 30 mol% or less, preferably 20 mol% or less of the total amount of (A1), and more preferably Other dicarboxylic acid component having 4 to 20 carbon atoms may be used. Examples of the other dicarboxylic acid component having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-sulfonyldibenzoic acid. Aromatic dicarboxylic acids such as 5-sodium sulfo-isophthalic acid, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl sebacate,
Aliphatic dicarboxylic acid ester such as diethyl sebacate,
In addition, dimethyl isophthalate, diethyl isophthalate,
Dimethyl 2,7-naphthalenedicarboxylate, Diethyl 2,7-naphthalenedicarboxylate, Dimethyl 4,4'-sulfonyldibenzoate, Diethyl 4,4'-sulfonyldibenzoate, Dimethyl 5-sodiumsulfo-isophthalate, 5 -Aromatic dicarboxylic acid esters such as sodium sulfo-diethyl isophthalate and the like can be mentioned.

[0020] As used in the present invention (A2) sulfonate ^- The diol component containing (-SO ₃ M ^+), the following equation (1)

[0021]

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It is represented by the diol component represented by

In the above formula (1), M ⁺ represents an ion selected from a metal ion, a tetraalkylphosphonium ion and a tetraalkylammonium ion.
M ⁺ is an alkali metal ion such as sodium ion, potassium ion or lithium ion, an alkaline earth metal ion such as calcium ion or magnesium ion,
Examples thereof include metal ions such as zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion, tetrabutylammonium ion, tetramethylammonium ion and the like. Among these ions, metal ions are preferable, and alkali metal ions and zinc ions are more preferable.
However, in the case of a divalent metal ion, 1 mol of the metal ion corresponds to 2 mol of the sulfonate group.

Ar in the above formula (1) is a trivalent aromatic group having 6 to 20 carbon atoms such as a benzene ring, a naphthalene ring, a biphenyl ring, etc., and these are also alkyl group, phenyl group, halogen, It may have a substituent such as an alkoxy group.

R ¹ and R ² are divalent alkylene groups having 2 to 4 carbon atoms such as ethylene, propylene and butylene groups, and among these, ethylene and propylene groups are preferable.

M and n are each independently an integer of 1 to 10, preferably 1 to 5 and more preferably 1 to 3.

[0027] Such sulfonate group ^- as the diol component containing (-SO ₃ M ⁺⁾ are preferably used those represented by the following formula.

When M ⁺ is sodium ion (Na ⁺ );

[0029]

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[0030]

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[0031]

[Chemical 6]

(In the formula, Ph represents a benzene ring, and Np
Represents a naphthalene ring, and Bp represents a biphenyl ring. ) When M ⁺ is a potassium ion (K ⁺ );

[0033]

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[0034]

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[0035]

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(In the formula, Ph represents a benzene ring, and Np
Represents a naphthalene ring, and Bp represents a biphenyl ring. ) Among the above formulas (2) -1 to (2) -24, (2) -1,
(2) -3, (2) -5, (2) -13, (2) -1
It is preferable to use the compounds represented by No. 5, (2) -17, and more preferably the compounds represented by (2) -1, (2) -13.

The above-mentioned sulfonate group-containing component (B2) is
You may use it combining 1 type, or 2 or more types of the diol component represented by said Formula (1).

The content of the above (A2) is 5 to 50 mol% with respect to the total dicarboxylic acid component.

Here, the total dicarboxylic acid component in the present invention means (1) (A1) a para-oriented aromatic dicarboxylic acid component having 4 to 20 carbon atoms, and (2) an ester-forming compound (A4) described later. When the poly (alkylene oxide) component having two functional groups is the dicarboxylic acid component represented by the formula (6), it means the sum of all the dicarboxylic acid components of (1) and (2).

When the proportion of the component (A2) is less than 5 mol%, the antistatic effect is insufficient, the antistatic effect is durable against washing with water, and the antistatic effect when the surface of the resin composition of the present invention is wiped off. Not durable enough.

In particular, as a result of the interaction between the sulfonate group which is the ionic group represented by the above formula (1) and the ionic surfactant copolymerized in the (A) polyether ester, an electrostatic charge is generated. It is presumed that the prevention effect is synergistically improved, and the outflow of the surfactant, which has been a problem in the past, is suppressed and the antistatic effect is maintained.

On the other hand, when the content of the component (A2) exceeds 50 mol%, the polymerization reaction becomes difficult and it becomes difficult to obtain the polyether ester (A) having a sufficient degree of polymerization, and the handleability deteriorates.

The proportion of the component (A2) is preferably 6 to 40 mol%, more preferably 7 to 30 mol% based on the total dicarboxylic acid components.

By using such a diol component represented by the above formula (1), a polyether ester having excellent polymerizability, handleability when mixed with the thermoplastic resin (B), and moldability is obtained. Thus, the thermoplastic resin can be provided with a good antistatic effect.

Specific examples of the glycol component having 2 to 10 carbon atoms (A3) used in the present invention include ethylene glycol, 1,4-butanediol, propylene glycol,
Examples thereof include 1,6-hexanediol and 3-methyl-1,5-pentanediol. The component (A3) is
It may contain an ether bond like diethylene glycol and a thioether bond like thiodiethanol.

Further, the following equations (2), (3) and (4)
A diol component having 10 to 30 carbon atoms as shown in
For example, it can be used as a part of the glycol (A3), if necessary, for example, by improving the refractive index of the entire polyether ester (A).

[0047]

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In the above formulas (2), (3) and (4), A
r ¹ is a trivalent aromatic group having 6 to 20 carbon atoms such as a benzene ring, a naphthalene ring, a biphenyl ring, and R ³ and R ⁴ are alkylene groups having 1 to 6 carbon atoms, such as methylene, Examples thereof include ethylene, propylene, normal butylene and isobutylene. Ph is a benzene ring. These may also have a substituent such as an alkyl group, a phenyl group, a halogen or an alkoxy group. Also, -X-
Is

[0049]

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Is selected from Here, R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as methyl and ethyl. , Propyl,
Examples include normal butyl, isobutyl, pentyl, cyclohexyl and phenyl. R ³ and R ⁴ may be bonded to each other, in which case they form a cycloalkane ring.

These glycol components may be used alone or in combination of two or more. Of these, 1,6-hexanediol and diethylene glycol are preferable from the viewpoint of antistatic effect.

Poly (alkylene oxide) having two ester-forming functional groups in the molecule (A4) which is one of the constituent components of the (A) polyether ester in the present invention.
The components include the following formulas (5), (6) and (7)

[0053]

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Mainly selected from the components represented by:

In the above formulas (5), (6) and (7), R ⁷ ,
R ^8, R ⁹ are ethylene, propylene, a divalent alkylene group having 2 to 4 carbon atoms such as butylene group, among these, ethylene, propylene group are preferred. R ¹⁰ is a hydrocarbon group having 1 to 12 carbon atoms, preferably a methyl, ethyl, propyl, butyl or phenyl group. When R ¹⁰ is a phenyl group, an alkyl group, a phenyl group, a halogen,
It may have a substituent such as an alkoxy group. p, q,
r represents a repeating unit of the alkylene oxide component, and is an integer of 4 to 1200, preferably 10 to 7.
00, more preferably 20 to 500 are used.

The poly (alkylene oxide) glycol component represented by the above formula (5) is preferably one mainly composed of polyethylene glycol in which R ⁷ is ethylene. Further, polypropylene glycol or the like may be contained as a copolymerization component.

The poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000 is used. If the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. Also, from a practical point of view,
The upper limit of the molecular weight is about 50,000. The preferred molecular weight of poly (alkylene oxide) glycol is 50.
0 to 30000, more preferably 1000 to 20
000.

Such poly (alkylene oxide) glycol components may further have such a molecular weight within the above range.
Decrease the polymerization degree of polyether ester by using alcohol of ester-forming component at one end and poly (alkylene oxide) alcohol such as poly (ethylene glycol) monophenyl ether which does not have ester-forming component at the other end. It may be partially contained to the extent that it is not allowed.

The poly (alkylene oxide) glycol component may also have an aromatic ring in the molecule within such a molecular weight range. Examples of such poly (alkylene oxide) glycols include those having the structures of the following formulas (8) and (9).

[0060]

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In the above formulas (8) and (9), Ar ² is a benzene ring, naphthalene ring, biphenyl ring or the like having 6 to 2 carbon atoms.
0 is a divalent aromatic group, and Ph is a benzene ring.
These may also have a substituent such as an alkyl group, a phenyl group, a halogen or an alkoxy group. Also, s,
t, u, and v represent integers from 2 to 60. -X- is

[0062]

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Selected from: Here, R ¹¹ and R ¹² are the same as R ³ and R ⁴ described above.

The compounds represented by the above formulas (8) and (9) can be used as the poly (alkylene oxide) glycol (A4) component itself which is one of the constituent components of the polyether ester (A). It is also available as part of it.

As the poly (alkylene oxide) component represented by the above formula (6), poly (alkylene glycol) bis (carboxymethyl) ether such as poly (ethylene glycol) bis (carboxymethyl) ether in which R8 is ethylene. Is preferred. Further, poly (propylene glycol) bis (carboxymethyl) ether or the like may be contained as a copolymerization component.

The poly (alkylene oxide glycol) bis (carboxymethyl) ether having a number average molecular weight of 200 to 50,000 is used. If the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. From the viewpoint of practicality, the upper limit of the molecular weight is 5
It is about 0000. The preferred molecular weight of the poly (alkylene oxide glycol) bis (carboxymethyl) ether is 500 to 30,000, more preferably 10
It is 00 to 20000.

Examples of the poly (alkylene oxide) glycol component represented by the above formula (7) include polyoxyethylene glycol-monomethyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-monoethyl-mono-2, 3-dihydroxypropyl ether, polyoxyethylene glycol-monoisopropyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-mono-n-butyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol- Monooctyl-mono-
2,3-dihydroxypropyl ether, polyoxyethylene glycol-monononyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-monocetyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-monophenyl- Mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-mononaphthyl-mono-
2,3-dihydroxypropyl ether, polyoxyethylene glycol-mono-4,4'-biphenyl-mono-2,3-dihydroxypropyl ether,

Polyoxypropylene glycol-monomethyl-mono-2,3-dihydroxypropyl ether,
Polyoxypropylene glycol-monoethyl-mono-
2,3-dihydroxypropyl ether, polyoxypropylene glycol-monoisopropyl-mono-2,3
-Dihydroxypropyl ether, polyoxypropylene glycol-mono-n-butyl-mono-2,3-dihydroxypropyl ether, polyoxypropylene glycol-monooctyl-mono-2,3-dihydroxypropyl ether, polyoxypropylene glycol-monononyl -Mono-2,3-dihydroxypropyl ether, polyoxypropylene glycol-monocetyl-mono-2,3-dihydroxypropyl ether, polyoxypropylene glycol-monophenyl-mono-2,3
-Dihydroxypropyl ether, polyoxypropylene glycol-mononaphthyl-mono-2,3-dihydroxypropyl ether, polyoxypropylene glycol-mono-4,4'-biphenyl-mono-2,3-dihydroxypropyl ether,

Polyoxyethylene glycol / polyoxypropylene glycol copolymer monomethyl-mono-
2,3-Dihydroxypropyl ether, polyoxyethylene glycol / polyoxypropylene glycol copolymer monoethyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol / polyoxypropylene glycol copolymer monophenyl-mono Mention may be made of polyoxyalkylene glycol-mono-2,3-dihydroxypropyl ether derivatives such as -2,3-dihydroxypropyl ether.

Among these, polyoxyethylene glycol-monomethyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-monoethyl-mono-2,3-dihydroxypropyl ether, polyoxyethylene glycol-monoisopropyl-mono −
2,3-dihydroxypropyl ether and polyoxyethylene glycol-monophenyl-mono-2,3-dihydroxypropyl ether are preferred.

Such polyoxyalkylene glycol-
A mono-2,3-dihydroxypropyl ether derivative having a number average molecular weight of 200 to 50,000 is used. If the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. Further, from the viewpoint of practicality, the upper limit of the molecular weight is about 50,000. The molecular weight of the polyoxyalkylene glycol-mono-2,3-dihydroxypropyl ether derivative is preferably 500 to 30,000, more preferably 1,000 to 20,000.

The poly (alkylene oxide) component having two ester-forming functional groups in the molecule (A4) is
From the viewpoint of transparency and antistatic effect of the finally obtained resin composition, the total amount of the polyether ester (A) is 10 to 50.
It must be in the range of weight percent. That is, the amount of the poly (alkylene oxide) component having two ester-forming functional groups in the molecule is such that the content of (A4) constituting the polyether ester (A) is (A
1), (A2), (A3) and (A4) are added in an amount of 10 to 50% by weight based on the total amount. If the amount is less than 10% by weight, the antistatic effect is not sufficient, and if the amount is more than 50% by weight, the degree of polymerization of the polyether ester (A) is difficult to increase and handling during molding becomes difficult.
The content of (A4) is preferably 10 based on the total amount of the four components (A1), (A2), (A3) and (A4).
-40% by weight, more preferably 12-35% by weight, still more preferably 15-30% by weight.

The polyether ester (A) in the present invention is phenol / tetrachloroethane (weight ratio: 6).
The reduced viscosity (concentration: 1.2 g / dl) measured at 35 ° C. in a mixed solvent of 0/40) is preferably 0.3 or more. When the reduced viscosity is less than 0.3, it causes heat resistance and mechanical property deterioration. Since the polymer is a substantially linear polymer, the upper limit of the reduced viscosity is preferably higher in terms of the antistatic effect and mechanical properties, but the practical upper limit is about 4.0. is there. The reduced viscosity is more preferably 0.4 or more, and further preferably 0.5 or more.

The polyether ester (A) in the present invention comprises the above components (A1), (A2), (A3) and (A4) in an amount of 150 to 300 in the presence of a transesterification catalyst.
It can be obtained by heating and melting at 0 ° C. to cause a polycondensation reaction.

The transesterification catalyst is not particularly limited as long as it can be used in a usual transesterification reaction. Such transesterification catalysts include antimony compounds such as antimony trioxide, tin compounds such as stannous acetate, dibutyltin oxide and dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate and calcium acetate. Calcium compounds such as sodium carbonate,
Examples thereof include alkali metal salts such as potassium carbonate. Of these, tetrabutyl titanate is preferably used.

The amount of the above catalyst used may be that used in a normal transesterification reaction, and is generally preferably 0.01 to 0.5 mol% relative to 1 mol of the acid component used, and 0.03. ˜0.3 mol% is more preferred.

It is also preferable to use various stabilizers such as antioxidants together during the reaction.

The temperature at which the above components (A1) to (A4) are heated and melted and polycondensed is 150 ° C. to 200 ° C. as the initial reaction for several tens of minutes to several tens of hours and the esterification reaction and / or
Alternatively, after carrying out the transesterification reaction while distilling off the distillate, a polymerization reaction for increasing the molecular weight of the reaction product is carried out from 180 ° C. to 3
Perform at 00 ° C. This is because if the temperature is lower than 180 ° C., the reaction does not proceed, and if the temperature is higher than 300 ° C., side reactions such as decomposition easily occur. The polymerization reaction temperature is more preferably 200 ° C to 280 ° C, further preferably 220 ° C to 250 ° C. Although the reaction time of this polymerization reaction depends on the reaction temperature and the amount of catalyst, it is usually several tens of minutes to several tens of hours.

The permanent antistatic resin composition of the present invention mainly comprises 5 to 40 parts by weight of the polyether ester (A) and 95 to 60 parts by weight of the thermoplastic resin (B) other than (A). If the amount of the polyetherester (A) is less than 5 parts by weight, the antistatic effect of the resin composition may be insufficient. If it exceeds 40 parts by weight, the physical properties of the thermoplastic resin (B) itself may be significantly deteriorated. A preferable ratio is 7 to 30 parts by weight of the polyether ester (A) and 93 to 70 parts by weight of the thermoplastic resin (B).

The thermoplastic resin (B) other than the polyether ester (A) is, for example, a polycarbonate resin mainly composed of bisphenol A and carbonic acid or a derivative thereof, a polyester resin such as polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate. , Polyphenylene ether resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyoxymethylene resin, polyphenylene sulfide resin, poly (styrene-acrylonitrile-butadiene) copolymer (ABS resin), poly (acrylonitrile-styrene) copolymer Polystyrene resin such as polymer (AS resin) or high impact polystyrene (HIPS), acrylic resin such as polymethylmethacrylate, polyamide resin It can be mentioned. These can be used alone or in combination of two or more. Among these, it is preferable to use a polycarbonate resin, a polyester resin, or a polystyrene resin from the viewpoint of compatibility when mixing the polyether ester in the present invention, since a more excellent antistatic effect is exhibited.

Although the permanent antistatic resin composition of the present invention has an antistatic effect by itself, the addition of the ionic surfactant (C) further improves the antistatic effect. be able to.

Generally, it is a conventionally known method to add a surfactant in order to exert an antistatic effect on the resin, but in such a method, the antistatic effect is lowered by washing with water or wiping. On the other hand, in the case of the resin composition of the present invention containing the polyether ester (A) copolymerized with a sulfonate-substituted diol component, surprisingly, an ionic surfactant is added. The antistatic effect improved by doing so is not impaired even by washing with water or wiping.

The ionic surfactant (C) used in the permanent antistatic resin composition of the present invention is an alkyl sulfonate, an alkylbenzene sulfonate, or a compound represented by the following formula (10).

[0084]

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[Here, R ¹³ and R ¹⁴ are each independently an alkyl group having 3 to 20 carbon atoms, u is an integer of 0 to 4, and v is an integer of 0 to 3. M has the same meaning as M in the above formula (1). Ionic surfactants such as alkylnaphthalenesulfonate represented by the formula (1):

As the alkyl sulfonate, sodium dodecyl sulfonate, potassium dodecyl sulfonate,
Examples thereof include alkyl metal sulfonate alkali metal salts having 3 to 20 carbon atoms such as sodium decyl sulfonate, potassium decyl sulfonate, sodium cetyl sulfonate, and potassium cetyl sulfonate.

As the alkylbenzene sulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate,
Examples thereof include alkali metal salts of alkylbenzene sulfonic acid having 3 to 20 carbon atoms such as sodium cetylbenzene sulfonate and potassium cetylbenzene sulfonate. If the alkyl chain of such an alkyl sulfonate or an alkyl benzene sulfonate has less than 3 carbon atoms, it tends to be difficult to dissolve in the above-mentioned component (A) or (B), which may cause deterioration of mechanical properties, which is not preferable. .

Further, examples of the alkylnaphthalene sulfonate include sodium mono-, di-, or tri-isopropyl naphthalene sulfonate, potassium mono-, di-, or tri-isopropyl naphthalene sulfonate, sodium octyl naphthalene sulfonate, potassium octyl naphthalene sulfonate. Alkyl naphthalene sulfonic acid alkali metal salts such as sodium dodecyl naphthalene sulfonate and potassium dodecyl naphthalene sulfonate can be mentioned.

The above ionic surfactants can be used alone or in combination of two or more kinds.

The above ionic surfactant is preferably contained in a proportion of 1 to 12 parts by weight per 100 parts by weight of the permanent antistatic resin composition of the present invention. When the content is less than 0.5 part by weight, the antistatic effect by addition may not be sufficiently exhibited, and when the content is more than 12 parts by weight, the physical properties of the resin composition may be reduced, or the handleability may be reduced. Because there is. The mixing amount of the ionic surfactant is more preferably 1 to 6 parts by weight.

The method for producing the permanent antistatic resin composition of the present invention is not particularly limited, but the polyether ester (A), a thermoplastic resin (B) other than (A), and further are required. Depending on the ionic surfactant (C)
Further, various additives described below can be easily mixed and produced by melt-kneading by a commonly used method. Of these, melt-kneading using a twin-screw extruder is preferable. The mixing temperature depends on the thermoplastic resin (B) used, but is generally about 180 to 300 ° C, preferably 220 to 280 ° C.

When the ionic surfactant (C) is used,
Regarding the order of mixing the respective components (A), (B) and (C), a method of simultaneously mixing three kinds, a method of mixing two kinds in advance, and then mixing with another one component Methods and the like. Among these methods, (a) a method of simultaneously mixing three kinds, (b) components (A) and (C) are mixed in advance, and then (B) component and, if necessary, various types described later. Although the method of mixing the additive of (1) is preferable, from the viewpoint of the permanent property of the antistatic effect, (b), that is, (A) and (C) are mixed in advance, and then (B) and Accordingly, a method of mixing various additives described below is particularly preferable.

As a method for simultaneously mixing all of the three components (a), (A), (B) and (C), a uniaxial or biaxial melt extruder is used, and if necessary, various additives described later are added. And melt-mix. The temperature for mixing these is approximately 250 ° C to 320 ° C. 250 ° C
Mixing at lower temperatures may not be sufficient 32
When the temperature is higher than 0 ° C, deterioration such as decomposition may occur, which is not preferable. Melt mixing temperature is preferably 260 ° C
To 300 ° C.

In the method (b), which is a more preferable method, after the components (A) and (C) have been mixed in advance, the component (B) and, if necessary, various additives described below are added. Mix. Here, as a method of melt-mixing the polyether ester (A) and the ionic surfactant (C), for example, after the polyether ester has undergone a polymerization reaction, the ionic surfactant to be directly added to the polymerization tank is added. Examples thereof include a method of mixing and a method of mixing both using a uniaxial or biaxial melt extruder. The melting and mixing temperature is generally 140 ° C to 300 ° C. If the temperature is lower than 140 ° C, the mixing may not be sufficient, and if the temperature is higher than 300 ° C, deterioration such as decomposition may occur, which is not preferable. The melt mixing temperature is preferably 160 ° C to 270 ° C, more preferably 2 ° C.
The temperature is from 00 ° C to 250 ° C.

As a method for melt-mixing the component (B) and optionally various additives to be described later into the mixture of the components (A) and (C) thus produced, uniaxial or biaxial melt extrusion is used. The method of mixing both using a machine is mentioned. The temperature for mixing these is approximately 25
0-320 ° C. If the temperature is lower than 250 ° C, the mixing may not be sufficient, and if the temperature is higher than 320 ° C, deterioration such as decomposition may occur, which is not preferable. The melt mixing temperature is preferably 260 to 300 ° C.

Further, the permanent antistatic resin composition of the present invention preferably has a surface specific resistance of 10 ¹³ (Ω / □) or less in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65%.
This is because when the surface resistivity exceeds 10 ¹³ (Ω / □), the substantial antistatic effect is insufficient. The lower limit is better as long as the resistivity is sufficient to exhibit the antistatic effect, but it is usually about 10 ⁸ (Ω / □).

If desired, various additives may be added to the permanent antistatic resin composition of the present invention. Such various additives include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker titanate,
Carbon fiber, fibrous reinforcement such as asbestos, talc,
Various fillers such as calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flakes, milled fiber, metal flakes, metal powders, heat stabilizers and catalysts represented by phosphate esters and phosphite esters Quencher, oxidation stabilizer, light stabilizer, lubricant, pigment,
Various additives such as a flame retardant, a flame retardant aid, and a plasticizer may be appropriately compounded.

[0098]

EFFECTS OF THE INVENTION According to the present invention, a permanent antistatic resin composition having a permanent antistatic effect, which does not deteriorate the antistatic performance even when washed with water, is obtained without impairing the original physical properties of the thermoplastic resin. You can When such a resin composition further contains an ionic surfactant, the antistatic effect and its permanent property are remarkably increased. Therefore,
Such a composition is useful for OA equipment, electronic parts, automobile housings, medical parts, various containers, covers, films, sheets and the like.

[0099]

EXAMPLES The preferred embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to the examples.

In the examples, "part" means "part by weight".

The reduced viscosity is a value measured in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40) at a concentration of 1.2 (g / dl) at 35 ° C., unless otherwise specified.

The glass transition temperature (Tg) and melting point (Tm) of the polymer were measured by DSC at a heating rate of 10 ° C./min.

Impact strength is 1 / according to ASTM D256
8 inches, heat distortion temperature (HDT) ASTM D64
8 was measured at 1/8 inch and a load of 18.6 kg / cm ² .

The surface resistivity (R) was measured by measuring the molded product (test sample) in an atmosphere of 20 ° C. and a humidity of 60%.
After standing for 4 hours, it was measured at an applied voltage of 1000 V using a super insulation meter (SM-8210 manufactured by Toa Denpa Kogyo Co., Ltd.). The molded product was washed with running water at 30 ° C. for 2 hours, and the water was wiped off with clean paper. Then, it dried under the same conditions and the surface specific resistance was measured.

[Reference Example 1] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexane. A diol, 1043 parts of polyethylene glycol (number average molecular weight 2000, 41% by weight with respect to the polymer), and
3 parts of tetrabutyl titanate was placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The obtained polyether ester has a reduced viscosity of 1.50 and a Tm of 4
It was 3 ° C and 130 ° C, and Tg could not be detected.

[Reference Example 2] 1342 parts of dimethyl 2,6-naphthalenedicarboxylate (total acid component), 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol based on total acid component) %), 7
Reaction of 78 parts of 1,6-hexanediol, 1226 parts of polyethylene glycol (number average molecular weight 2000, 41% by weight based on the polymer), and 1.3 parts of tetrabutyl titanate equipped with a rectification column and a stirrer Put it in a bowl,
After replacing the inside of the container with nitrogen, the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that point, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg,
A highly viscous polymer was obtained. The reduced viscosity of the obtained polyether ester is 1.34, Tm is 45,150 ° C.,
Tg could not be detected.

Reference Example 3 1485 parts of dimethyl 4,4'-biphenyldicarboxylate (total acid component), 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 parts based on total acid component) Mol%), 7
Reaction of 78 parts of 1,6-hexanediol, 1321 parts of polyethylene glycol (number average molecular weight 2000, 41% by weight based on the polymer), and 1.3 parts of tetrabutyl titanate equipped with a rectification column and a stirrer Put it in a bowl,
After replacing the inside of the container with nitrogen, the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that point, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg,
A highly viscous polymer was obtained. The resulting polyether ester had a reduced viscosity of 1.33 and a Tm of 41,141 ° C.,
Tg could not be detected.

[Reference Example 4] 854 parts of dimethyl terephthalate (80 mol% of all acid components), 400 parts of 4,4 '
Dimethyl sulfonyldibenzoate (20 mol% of total acid components), 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on total acid components), 778 parts of 1,6 -Hexanediol,
1167 parts of polyethylene glycol (number average molecular weight 2
000, 41% by weight with respect to the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then, under normal pressure, 2
The temperature was raised to 00 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was reduced to 0.
A high-viscosity polymer was obtained with a pressure of 2 mmHg. The reduced viscosity of the obtained polyether ester is 1.02, Tm and T
g could not be detected.

Reference Example 5 1014 parts of dimethyl terephthalate (95 mol% of all acid components), 81 parts of dimethyl 5-sodium sulfoisophthalate (5 mol% of all acid components), 248 parts of 1,4- Bishydroxyethoxybenzene-2-sodium sulfonate (15 mol% based on all acid components), 778 parts of 1,6-hexanediol,
1028 parts of polyethylene glycol (number average molecular weight 2
000, 41% by weight with respect to the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then, under normal pressure, 2
The temperature was raised to 00 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was reduced to 0.
A high-viscosity polymer was obtained with a pressure of 2 mmHg. The reduced viscosity of the obtained polyether ester was 0.79, Tm and T
g could not be detected.

Reference Example 6 1043 parts of polyethylene glycol having a number average molecular weight of 4000 (4
Polymerization was performed in the same manner as in Reference Example 1 except that 0% by weight) was used to obtain a high-viscosity polymer. The reduced viscosity of the obtained polyether ester was 1.55, Tm was 48,135 ° C., and Tg could not be detected.

[Reference Example 7] Polymerization was performed in the same manner as in Reference Example 1 except that 1043 parts (40% by weight based on the polymer) of polyethylene glycol having a number average molecular weight of 20,000 was used to obtain a high-viscosity polymer. . The reduced viscosity of the obtained polyether ester was 1.70, Tm was 49,140 ° C., and Tg could not be detected.

[Reference Example 8] 992 parts of dimethyl terephthalate (93 mol% of all acid components), 330 parts of 1,4-
Bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexanediol, 1200 parts of poly (ethylene glycol) bis (carboxymethyl) ether (number average molecular weight of 3000 , 45% by weight with respect to the polymer, 7 mol% of the total acid component), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirring device, and the inside of the vessel was replaced with nitrogen, The temperature was raised to 200 ° C. under normal pressure.
After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, while distilling off the reaction distillate under normal pressure.
It heated up to 240 degreeC over 20 minutes. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The reduced viscosity of the obtained polyether ester was 1.11 and Tm was 150 ° C., and Tg could not be detected.

Reference Example 9 Polyoxyethylene glycol-monophenyl-mono-2 having a number average molecular weight of 2000,
Polymerization was performed in the same manner as in Reference Example 1 except that 1043 parts (41% by weight based on the polymer) of 3-dihydroxypropyl alcohol was used to obtain a high-viscosity polymer. The obtained polyether ester has a reduced viscosity of 0.85 and a Tm of 12
It was 5 ° C, and Tg could not be detected.

[Reference Example 10] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexane. A diol, 842 parts of polyethylene glycol (number average molecular weight 2000, 36% by weight with respect to the polymer), and
3 parts of tetrabutyl titanate was placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure inside the reaction system was gradually reduced to 0.2 mmHg after 60 minutes, and after 100 minutes, poly (ethylene glycol) monophenyl ether (number average molecular weight 2000
0, 5% by weight of the total polymer produced). After the addition, the pressure inside the reaction system was reduced again to 0.2 mmHg, and 60
A polymer was obtained after a minute. The resulting polyether ester had a reduced viscosity of 1.23, a Tm of 43,130 ° C., and a T
g could not be detected.

[Reference Example 11] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 511 parts of ethylene glycol,
878 parts of polyethylene glycol (number average molecular weight 20
00, 40% by weight with respect to the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then, under normal pressure, 20
The temperature was raised to 0 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C.
At that point, the pressure inside the reaction system was gradually reduced, and after 70 minutes, 0.2 m
High viscosity polymer was obtained with mHg. The obtained polyether ester had a reduced viscosity of 0.87 and a Tm of 43,20.
It was 7 ° C, and Tg could not be detected.

[Reference Example 12] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 742 parts of ethylene glycol,
961 parts of polyethylene glycol (number average molecular weight 20
00, 40% by weight with respect to the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then, under normal pressure, 20
The temperature was raised to 0 ° C. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C.
At that point, the pressure inside the reaction system was gradually reduced, and after 70 minutes, 0.2 m
High viscosity polymer was obtained with mHg. The obtained polyether ester had a reduced viscosity of 0.80 and a Tm of 43,18.
It was 0 ° C., and Tg could not be detected.

[Reference Example 13] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 454 parts of 1,6-hexane Diol (70 mol% based on all acid components), 375 parts ethylene glycol, 1022 parts polyethylene glycol (number average molecular weight 2000, 41% by weight based on polymer), and 1.3 parts tetrabutyl titanate were purified. It was placed in a reactor equipped with a distillation column and a stirrer, the inside of the vessel was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a highly viscous polymerization. The reduced viscosity of the obtained polyether ester is 1.4.
7, Tm was 43,140 ° C., and Tg could not be detected.

[Reference Example 14] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 531 parts of α, α'- Xylylene glycol (70 mol% based on all acid components), 375 parts of ethylene glycol, 1073 parts of polyethylene glycol (number average molecular weight of 2,000, 40 of polymer)
% By weight), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After reacting for 180 minutes while distilling off methanol at 200 ° C.,
The reaction product was placed in a reactor having a vacuum distillation system equipped with a stirrer, and the temperature was raised to 240 ° C. over 120 minutes while distilling the reaction product under atmospheric pressure. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The reduced viscosity of the obtained polyether ester was 0.66, and Tm and Tg could not be detected.

[Reference Example 15] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexane. The diol and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 120 minutes. The temperature was raised to 240 ° C. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The reduced viscosity of the obtained polyetherester was 0.
79, Tm was 135 ° C., and Tg could not be detected.

Reference Example 16 1067 parts of dimethyl terephthalate, 778 parts of 1,6-hexanediol, 9
09 parts of polyethylene glycol (number average molecular weight 200
0, 41% by weight with respect to the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was replaced with nitrogen, and then, under normal pressure, 200
The temperature was raised to ° C. Distilling off methanol at 200 ° C 1
After performing the reaction for 80 minutes, the reaction product was placed in a reactor having a vacuum distillation system equipped with a stirrer, and heated to 240 ° C. over 120 minutes while distilling the reaction distillate under normal pressure. At that point, the pressure in the reaction system was gradually reduced, and after 70 minutes, 0.2 mm
Hg was used to obtain a high-viscosity polymer. The obtained polyether ester had a reduced viscosity of 1.10 and a Tm of 62,204.
C., and Tg could not be detected.

[Examples 1 to 14] ABS resin (UT-61 manufactured by Mitsui Toatsu Chemicals, Inc.) was mixed with the indicated amount of each polyether ester produced in Reference Examples 1 to 14 by 30 mmφ co-rotating biaxial. Extruder (made by Ikegai Tekko KK, P
CM30) was melt-kneaded under the conditions of a polymer temperature of 240 ° C. and an average residence time of about 10 minutes, and pelletized. Next, an injection molding machine (M-50 manufactured by Meiki Seisakusho Co., Ltd.)
Using B), cylinder temperature 240 ℃, mold temperature 50
Injection molding was performed at 0 ° C. to obtain 4 types of 2 mm thick molded products, and the surface resistivity was measured. The results are shown in Tables 1 and 2 together with the mechanical properties.

[Comparative Examples 1 and 2] Each polyether ester produced in Reference Examples 15 and 16 was melted in an ABS resin (UT-61 manufactured by Mitsui Toatsu Chemicals, Inc.) in the same manner as in Examples 1 to 4. The mixture was mixed and the molded product was evaluated. The results are also shown in Table 2.

[0123]

[Table 1]

[0124]

[Table 2]

As is clear from the above Examples 1 to 14 and Comparative Examples 1 and 2, the permanent antistatic resin composition of the present invention has a surface resistivity which does not change before and after washing with water, and a permanent control. It showed an electric effect. In addition, compared to a polymer not containing the diol component (A2) containing a sulfonate group represented by the above formula (1), and having a number average molecular weight of 200 to 50,000 having two ester-forming functional groups in the molecule. It can be seen that the antistatic effect is larger than that of the polymer having no poly (alkylene oxide) component (A4).

[Reference Example 17] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexane. A diol, 1043 parts of polyethylene glycol (number average molecular weight 2000, 41% by weight based on the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and nitrogen was introduced into the vessel. After the replacement, the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was placed in a reactor having a vacuum distillation system equipped with a stirring device, and under normal pressure,
While distilling off the reaction distillate, the temperature was raised to 240 ° C. over 120 minutes. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The obtained polyether ester had a reduced viscosity of 1.50 and a Tm of 43,130 ° C. Further, 509 parts of sodium dodecylbenzenesulfonate was added thereto, and the inside of the container was replaced with nitrogen, and then the mixture was stirred at 240 ° C. under reduced pressure for 1 hour. The Tm of the obtained composition was 115 ° C. This composition is
Let it be 1.

Reference Example 18 The same procedure as in Reference Example 17 was carried out except that polymerization was carried out in the same manner as in Reference Example 1 and then sodium diisopropylnaphthalenesulfonate was used instead of sodium dodecylbenzenesulfonate. The Tm of the obtained composition was 123 ° C. This composition is
Let it be 2.

[Reference Example 19] 1067 parts of dimethyl terephthalate, 330 parts of 1,4-bishydroxyethoxybenzene-2-sodium sulfonate (20 mol% based on all acid components), 778 parts of 1,6-hexane. A diol, 1043 parts of polyethylene glycol (number average molecular weight 2000, 41% by weight based on the polymer), and 1.3 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was filled with nitrogen. After the replacement, the temperature was raised to 200 ° C. under normal pressure. After carrying out the reaction for 180 minutes while distilling off methanol at 200 ° C., the reaction product was placed in a reactor having a vacuum distillation system equipped with a stirring device, and under normal pressure,
While distilling off the reaction distillate, the temperature was raised to 240 ° C. over 120 minutes. At that time, the pressure in the reaction system was gradually reduced, and after 70 minutes, the pressure was adjusted to 0.2 mmHg to obtain a high-viscosity polymer. The obtained polyether ester had a reduced viscosity of 1.50 and a Tm of 43,130 ° C. The obtained polymer was taken out of the reactor, and 20 parts of sodium dodecylbenzenesulfonate was rotated in the same direction with a 30 mmφ twin-screw extruder (made by Ikegai Tekko KK, PCM3) with respect to 100 parts of the polymer.
0) was melt-kneaded under the conditions of a polymer temperature of 220 ° C. and an average residence time of about 7 minutes, and pelletized. This composition is designated as E3.

[Examples 15 to 17] To 100 parts of ABS resin (UT-61 manufactured by Mitsui Toatsu Chemicals, Inc.), 12 parts of the compositions (E1 to E3) of Reference Examples 17 to 19 were added.
mmφ co-rotating two-axis extruder (PCM30 manufactured by Ikegai Tekko KK) using a polymer temperature of 210
The mixture was melt-kneaded with the ABS resin under the conditions of ℃ and an average residence time of about 5 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), injection molding was performed at a cylinder temperature of 210 ° C. and a mold temperature of 30 ° C. to 2 mm.
A thick molded product was obtained and the surface resistivity was measured. The results are shown in Table 3 together with the mechanical properties.

[0130]

[Table 3]

As is clear from Examples 15 to 17, the permanent antistatic resin composition of the present invention exhibited a permanent antistatic effect with its surface specific resistance unchanged before and after washing with water.

[Example 18] A composition of the polyether ester prepared in Reference Example 17 and sodium dodecylbenzenesulfonate (E) based on 100 parts of a polycarbonate resin ("Panlite" L1250 manufactured by Teijin Chemicals Ltd.)
1) Using the indicated amount, a 30 mmφ co-rotating biaxial extruder (PCM30 manufactured by Ikegai Iron Works Co., Ltd.) was used to melt the polycarbonate resin under the conditions of a polymer temperature of 270 ° C. and an average residence time of about 5 minutes. It was kneaded and pelletized. Next, injection molding machine (M manufactured by Meiki Seisakusho Co., Ltd.)
-50B), injection molding is performed at a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. to obtain a molded product having a thickness of 2 mm.
The surface resistivity was measured. The results are shown in Table 4 together with the mechanical properties.

[Example 19] ABS resin (UT-61 manufactured by Mitsui Toatsu Chemicals, Inc.), polycarbonate resin ("Panlite" L1250 manufactured by Teijin Chemicals, Ltd.), Reference Example 1
The polyether ester prepared in 7 and sodium dodecylbenzenesulfonate composition (E1) in the indicated amounts,
Polymer temperature 260 using a 30 mmφ co-rotating biaxial extruder (PCM30 manufactured by Ikegai Tekko KK)
The mixture was melt-kneaded under the conditions of ℃ and average residence time of about 10 minutes, and pelletized. Next, injection molding machine (Meiki Seisakusho Co., Ltd.)
Manufactured by M-50B), injection molding was performed at a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. to obtain a molded product having a thickness of 2 mm, and the surface resistivity was measured. The results are shown in Table 4 together with the mechanical properties.

[Example 20] The composition (E1) of the polyether ester and sodium dodecylbenzenesulfonate prepared in Reference Example 17 was added to 100 parts of the glass-reinforced PBT resin (C7030N manufactured by Teijin Limited). , 30 mmφ co-rotating biaxial extruder (PCM30 manufactured by Ikegai Tekko Co., Ltd.) was used for polymer temperature 2
It was melt-kneaded with the PBT resin under the conditions of 50 ° C. and an average residence time of about 5 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), injection molding was performed at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C.
A molded product having a thickness of 2 mm was obtained, and the surface resistivity was measured.
The results are shown in Table 4 together with the mechanical properties.

Example 21 PBT resin (reduced viscosity 1.
5) Based on 100 parts, the composition (E1) of the polyether ester and sodium dodecylbenzenesulfonate produced in Reference Example 17, the indicated amount, a 30 mmφ co-rotating twin-screw extruder (manufactured by Ikegai Tekko KK, PCM3
0) was melt-kneaded with the PBT resin under conditions of a polymer temperature of 250 ° C. and an average residence time of about 5 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), a cylinder temperature of 250
Injection molding was performed at a temperature of 70 ° C. and a mold temperature of 70 ° C. to obtain a molded product having a thickness of 2 mm, and the surface resistivity was measured. The results are shown in Table 4 together with the mechanical properties.

[Example 22] Polymethylmethacrylate (PMMA) resin (Delpet 80 manufactured by Asahi Kasei Corporation)
N) With respect to 100 parts, the composition (E1) of the polyether ester and sodium dodecylbenzenesulfonate produced in Reference Example 17 was used in the indicated amount, and a 30 mmφ co-rotating twin-screw extruder (manufactured by Ikegai Tekko KK, PCM3
0) was melt-kneaded with the PMMA under the conditions of a polymer temperature of 250 ° C. and an average residence time of about 5 minutes, and pelletized. Next, injection molding machine (M-5 manufactured by Meiki Seisakusho Co., Ltd.)
0B) with a cylinder temperature of 250 ° C. and a mold temperature of 5
Injection molding was performed at 0 ° C. to obtain a molded product having a thickness of 2 mm, and the surface resistivity was measured. The results are shown in Table 4 together with the mechanical properties.
Shown in

[Example 23] To 100 parts of AS resin (Cevian N050 manufactured by Daicel Chemical Industries, Ltd.),
The composition (E1) of the polyether ester and sodium dodecylbenzene sulfonate prepared in Reference Example 17 was used, and the polymer temperature was measured using a 30 mmφ co-rotating twin-screw extruder (PCM30, manufactured by Ikegai Tekko KK). It was melt-kneaded with the AS resin under the conditions of 210 ° C. and an average residence time of about 5 minutes, and pelletized. Next, using an injection molding machine (M-50B manufactured by Meiki Seisakusho Co., Ltd.), injection molding was performed at a cylinder temperature of 210 ° C. and a mold temperature of 30 ° C. to obtain a molded product having a thickness of 2 mm, and a surface resistivity of The measurement was performed. The results are shown in Table 4 together with the mechanical properties.

[0138]

[Table 4]

As is clear from Examples 18 to 23, the polyether ester according to the present invention provides a thermoplastic resin with an excellent antistatic effect.

Claims (6)

[Claims] 1. (A) (A1) a para-oriented aromatic dicarboxylic acid component having 4 to 20 carbon atoms, (A2) the following formula (1): [In the formula (1), R ¹ and R ² each independently have 2 carbon atoms.
To 4 are divalent alkylene groups, and m and n are each independently an integer of 1 to 10. Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion], and a sulfonate group-containing diol component represented by (A3) carbon number 2-10 glycol components,
A polyether ester comprising (A4) a poly (alkylene oxide) component having two ester-forming functional groups in the molecule and having a number average molecular weight of 200 to 50,000, wherein the content of (A2) is a total dicarboxylic acid component. Against 5
Within the range of 50 mol% and (A1), (A
2), 5 to 40 parts by weight of a polyether ester in which the content of (A4) is in the range of 10 to 50 wt% based on the total amount of the four components of (A3) and (A4), and (B) (A 95 to 60 parts by weight of a thermoplastic resin other than the above), a permanent antistatic resin composition. 2. A permanent antistatic resin further comprising 0.5 to 12 parts by weight of an ionic surfactant (C) based on 100 parts by weight of the permanent antistatic resin composition according to claim 1. Composition. 3. The permanent charge according to claim 2, wherein the ionic surfactant (C) is at least one compound selected from the group consisting of alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. Preventive resin composition. 4. The reduced viscosity (concentration: 1.2 g / d) of the polyether ester (A) measured at 35 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40).
The permanent antistatic resin composition according to any one of claims 1 to 3, which is 1 or more and is 0.3 or more. 5. The permanent antistatic resin composition according to claim 1, which has a surface specific resistance of 10 ¹³ (Ω / □) or less in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. 6. In producing the permanent antistatic resin composition according to claim 2 or 3, the polyether ester (A) and the ionic surfactant (C) are melt-mixed in advance, and then the thermoplastic resin. The method for producing a permanent antistatic resin composition according to any one of claims 1 to 5, which comprises melt-mixing with (B).