JP3132854B2 - Polymeric antistatic agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a specific graft polymer.
And a polymer antistatic agent comprising:

More specifically, a resin composition such as a thermoplastic polyester resin, a polycarbonate resin, an ABS resin and the like, and a polymer-based charge mixed to impart antistatic properties and gloss to various molded articles thereof. Related to inhibitors.

[0003]

2. Description of the Related Art A thermoplastic polyester resin, a polycarbonate resin and an ABS resin have excellent properties, respectively, so that they can be used in automobiles, home electric appliance parts, base parts, fibers, films, sheets and the like. It is widely used as a molding material.

[0004]

However, since these molding resins are hydrophobic, their use in fields requiring antistatic properties may be limited. For example, polyester fibers typified by polyethylene terephthalate have drawbacks that they cause discomfort such as discharge noise and crackling when worn as clothing, and are liable to become dirty or cause various troubles at the time of spinning and processing. is there.

[0005] In addition, OA using ABS resin is used.
There are various problems with electronic parts, such as malfunction of paper feeding of a copier and a printer, electric shock due to static electricity, and adhesion of dust. In order to solve such a problem, attempts have been made to impart hydrophilicity to a hydrophobic molding resin to exhibit antistatic properties, and many proposals have been made so far. For example, a method in which an ionic antistatic agent is added to the molding resin during polymerization, or a method of surface coating or kneading is used.

[0006] In particular, metal sulfonic acid salts are disclosed in JP-A-50-53.
465, JP-A-54-6049 and JP-A-60-60
No. 38123, etc., these ionic antistatic agents and inorganic antistatic agents are used in molding resins.
It is unavoidable that the ionic antistatic agent drops out of the resin due to a significant decrease in the charging effect over time.

[0007] In order to make the charging effect durable, there is known a method of mixing various hydrophilic polymers with a molding resin. The most typical method is to mix a polyalkylene ether with a molding resin.
No. 44, JP-A-3-124760, etc., but polyalkylene ethers have poor compatibility with general hydrophobic molding resins, so that the mechanical strength and heat resistance of this molding resin are low. There is a disadvantage that the performance is greatly reduced. Polyamide elastomer having a polyalkylene ether component as a hydrophilic polymer, a hydrophilic group-containing styrene resin,
Methods of adding a thermoplastic polyurethane or the like are reported in, for example, JP-A-60-39413, JP-A-1-308444, JP-A-2-80460, etc. Although improved, mechanical strength,
At present, heat resistance and other necessary physical properties have not been sufficiently satisfied.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by mixing an appropriate amount with the molding resin, the mechanical strength, heat resistance and the like of the molding resin have been improved. The present inventors have found that a high molecular weight antistatic agent having an effect of imparting excellent antistatic property, gloss, chemical resistance and oil resistance can be obtained without impairing various physical properties, and the present invention has been completed.

The polymer type antistatic agent of the present invention is a graft polymer, wherein the backbone polymer is a polyamide or a branched polymer.
Is composed of a block polymer of a polyalkylene ether and a thermoplastic polyester. Examples of the polyamide which is a trunk polymer of the polymer antistatic agent of the present invention include various polyamides obtained by polycondensation of a lactam having three or more ring members, ω-aminocarboxylic acid, dibasic acid and diamine. .

Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid and 11-aminoundecanoic acid, or
Diamines such as butanediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, meta-xylylenediamine, and terephthalic acid, isophthalic acid, adipic acid, sepatinic acid, dodecane dibasic acid, and glutar Polymers obtained by polycondensation of dicarboxylic acids and the like such as acids, and copolymers thereof are exemplified.

More specifically, aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and nylon 612, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, polyamide containing xylylene group And a multiblock copolymer comprising a polyamide called polyetheramide and polyetheresteramide and a polyether segment.

Of the above-mentioned polyamides, nylon 6, nylon 66, nylon 12, and polyetheramide are particularly preferred.

The number average molecular weight of these polyamides is not particularly limited, but preferably, those having a number average molecular weight in the range of 5,000 to 50,000 can be arbitrarily used depending on the use of the polymer type antistatic agent of the present invention.

The branched polymer of the polymer type antistatic agent of the present invention
The (polyalkylene ether-thermoplastic polyester) block polymer may have any structure as long as it is a block polymer composed of a polyalkylene ether component and a thermoplastic polyester component. In general, in both components, the polyalkylene ether component to impart hydrophilicity, and the thermoplastic polyester component to impart compatibility and mechanical strength to the molding resin, and heat resistance are combined with each other. It is preferable that the chain length is long within the range of the ratio. Most preferably, a block polymer in which a polyalkylene ether component chain called a diblock polymer and a thermoplastic polyester chain are connected by only one covalent bond is used. Examples of the polyalkylene ether component in the branched polymer of the polymer antistatic agent of the present invention include a polymer or copolymer obtained by ring-opening polymerization of a cyclic ether having 2 to 6 carbon atoms. . Specifically, polyethylene oxide, polypropylene oxide, polytetramethylene glycol, poly (ethylene-propylene) oxide,
And polyhexamethylene glycol.

Of the above, polyethylene oxide (polyethylene glycol) is most preferably used.

The number average molecular weight of these polyalkylene ether components is not particularly limited, but those in the range of 30 to 6,000 are most preferably used depending on the use of the polymer antistatic agent of the present invention. The thermoplastic polyester component in the branch polymer of the polymer antistatic agent of the present invention includes:
As the glycol component, a glycol having 2 to 6 carbon atoms, for example, ethylene glycol, propylene glycol, 1,
Glycols such as 4-butanediol, neopentyl glycol and hexamethylene glycol, and dicarboxylic acid components such as terephthalic acid, isophthalic acid, and their alkyl nucleus-substituted and halogen nucleus-substituted products. A polymer or copolymer obtained by polycondensation with a dicarboxylic acid is exemplified.

Specifically, polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate, polybutylene naphthalate, polyethylene
1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate
And polybutylene terephthalate / decanedicarboxylate. Further, dibasic acid halides such as terephthalic acid dichloride and isophthalic acid dichloride,
Also included are polyarylates obtained by polycondensation with divalent phenols such as 2,2-bis- (4-hydroxyphenyl) propane.

Of these, polyethylene terephthalate and polybutylene terephthalate, which are well balanced in mechanical properties and moldability, are preferably used. The number average molecular weight of these thermoplastic polyester components is not particularly limited, but depending on the use of the polymer antistatic agent of the present invention,
Those having a range of 1,000 to 20,000 are most preferably used.

The polymer-based antistatic agent of the present invention can be used as a molding resin, that is, a thermoplastic polyester resin, a polycarbonate resin or the like.
A suitable amount is mixed with the resin and the ABS resin for the purpose of imparting excellent durability and antistatic properties. The mixing ratio of the polymer antistatic agent of the present invention to the molding resin is an appropriate amount, and is not particularly limited, but is generally 1 wt%.
The range of ５０50 wt% is preferred. This mixing ratio is 1wt
%, The antistatic effect can hardly be expected. If it exceeds 50 wt%, various physical properties such as mechanical strength, heat resistance, and moldability of the molding fat change regardless of quality. It is not preferable because it may occur.

In these respects, the mixing ratio is 5 wt% to 2 wt%.
The range of 0 wt% is most preferable.

When the polymer type antistatic agent of the present invention is mixed with a molding resin represented by a thermoplastic polyester resin, a polycarbonate resin and an ABS resin, antistatic properties are imparted to these molding resins. The hydrophilic polymer is a polyamide of the trunk polymer and a polyalkylene ether component in the branch polymer, and has compatibility with the molding resin, and is formed by immobilizing the hydrophilic polymer. The thermoplastic polyester component in the branch polymer plays a role in making the antistatic property durable and at the same time preventing a decrease in mechanical strength, heat resistance and the like caused by mixing the hydrophilic polymer.

The branched polymer of the polymeric antistatic agent of the present invention
The polyalkylene ether component therein has a large effect of imparting antistatic properties, but if the weight ratio in the polymer charging agent is too large, the mechanical strength and heat resistance of the polymer charging agent itself will be high. It is not preferable because it impairs.

The weight ratio of the polyalkylene ether component in the branch polymer to the polymer-based charging agent is 3 to 30 wt.
%, Most preferably 5 to 20 wt%.

In the polymer type antistatic agent of the present invention, the average number of branch polymers grafted to one trunk polymer, the polyamide of the trunk polymer, the polyalkylene ether component in the branch polymer and the heat The number average molecular weight of each of the plastic polyester components is not particularly limited, and any number can be polymerized and used depending on the performance and use of the polymer antistatic agent of the present invention. The method for producing the polymer antistatic agent of the present invention is not particularly limited, and any appropriate method can be used.

As the most general example, the known polyamide according to the present invention is prepared by coexisting an alkali compound with 2 carbon atoms.
After obtaining a β-hydroxyalkylated polyamide by reacting with an alkylene oxide of No. 4 to No. 4, a polycondensation of a thermoplastic polyester from a hydroxyl group of the modified polyamide may be mentioned.

The process for obtaining a β-hydroxyalkylated polyamide by the method described above is described in Journal of Polymer Science, Vol. 15, p. 427, (1955).
) And known methods described in JP-A-1-92223 and the like can be used.

In this process, the composition ratio of the polyamide component and the polyalkylene ether component and the average number of grafted branch polymers are determined. As a typical example of a method of polymerizing and adding a thermoplastic polyester to a β-hydroxyalkylated polyamide obtained by using such a method, the following general formula 3 [III] is used in the presence of the β-hydroxyalkylated polyamide.

[0028]

Embedded image

Wherein R ³ is an alkylene group having 2 to 6 carbon atoms and μ is an integer of 1 to 200. At least one polyester prepolymer is polymerized by a transesterification reaction. .

The range of μ in the general formula [III] is 1 to 20
While between 0, the reactivity of the polyester prepolymer with the β-hydroxyalkylated polyamide decreases with increasing μ. Therefore, the range of μ is preferably 1 to 20.
As the conditions for polycondensing the polyester prepolymer and the β-hydroxyalkylated polyamide, the same conditions as those for general polyester polycondensation are preferably used. That is, the reaction proceeds in a molten state under a reduced pressure of 1 Torr or less, and the thermoplastic polyester component is made high in molecular weight. The addition of an appropriate transesterification catalyst is preferable because the reaction proceeds promptly.

The transesterification catalyst to be used may be any one as long as it is generally used at the time of polycondensation of polyester, and most preferably includes tetrabutyl titanate and the like. In the above-mentioned production method, it is difficult to equalize each component composition, molecular weight, and the number of branch polymers grafted to one trunk polymer of the obtained high molecular weight antistatic agent, but the durability The uniformity of various physical properties such as the effect of imparting electrical properties, mechanical strength, and heat resistance can generally be sufficiently controlled.

In the high molecular weight antistatic agent represented by the general formula [I] or [II] according to claim 2, R ¹ has an alkylene group having 4 to 8 carbon atoms or a substituent. Phenylene group, R ² is an alkylene group having 4 to 14 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, m is 1 to 1,000, n is 1 to 10, p is 1 to 200, q Represents a positive number of 1 to 500, respectively.

Specific examples of R ¹ , R ² and R ³ include:
R ¹ is a butylene group, a hexylene group, an octylene group,
R ² is a butylene group, a hexylene group, a nonylene group, a decylene group, an undecin group, a dodecine group, etc.
³ includes an ethylene group, a propylene group, a butylene group, a hexylene group and the like. The ranges of m, n, p, and q can be easily controlled so as to satisfy required physical properties for each application of the polymer antistatic agent of the present invention.

The above-mentioned necessary physical properties for each application include, for example, a balance between hydrophilicity, mechanical strength, heat resistance and the like.

When the polymer antistatic agent of the present invention is mixed with a molding resin, that is, a thermoplastic polyester resin, a polycarbonate resin, or an ABS resin, the polymer antistatic agent must be imparted with compatibility. The balance between the thermoplastic polyester component and the hydrophilic component in the antistatic agent branched polymer and the balance between the backbone polyamide in the hydrophilic component and the polyalkylene ether component in the branched polymer become ideal. There is a need.

In the balance between the polyamide and the polyalkylene ether component in the hydrophilic component, as the proportion of the polyalkylene ether component in the total hydrophilic component increases, the hydrophilicity increases, but the mechanical strength increases. , Heat resistance etc. decrease.

From these relations, in order to increase the hydrophilicity, m, n and p are increased with respect to q. More specifically, among m, n and p, n and p are increased with respect to m. Increase. In order to increase the mechanical strength, heat resistance, and the like, increasing the amount of q is first mentioned. However, in terms of m, n, and p in the hydrophilic component, it is preferable to increase the amount of m. For this reason, m is 1 to 1,000,
n is preferably 1 to 10, p is preferably 1 to 200, and q is preferably 1 to 500, but m is 10 to 100, and n is 1 to
3, the range where p is 1 to 200 and q is 10 to 500 are most practically preferable.

Examples of the molding resin to which the polymer-based antistatic agent of the present invention is added include thermoplastic polyester resins, polycarbonate resins, and ABS resins.

As the thermoplastic polyester resin, one equivalent to the thermoplastic polyester component in the polymer antistatic agent branch polymer of the present invention is used. That is, glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol, etc. And a dicarboxylic acid component, for example, terephthalic acid, isophthalic acid, and a polymer or copolymer obtained by polycondensation with a dicarboxylic acid such as a substituted alkyl nucleus or a substituted halogen nucleus. .

Specifically, polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4 ' -Dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / decane dicarboxylate and the like. Terephthalic acid dichloride,
Also included are polyarylates obtained by polycondensation of dibasic acid halides such as isophthalic dichloride and divalent phenols such as 2,2-bis (4-hydroxyphenyl) propane.

Of these, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are preferably used.

The number average molecular weight of these thermoplastic polyester resins is not particularly limited, but may range from 10,000 to 35,
000 is preferably used.

Polycarbonate resins are prepared by the phosgene method of reacting various divalent phenols with phosgene, or the ester exchange method of reacting divalent phenol with a carbonate ester such as diphenyl carbonate. The resulting polymer or copolymer.

The divalent phenol used may be 2,2
2-bis- (4-hydroxyphenyl) propane, 2,
2-bis- (4-hydroxyphenyl) butane, 2,2
-Bis- (4-hydroxyphenyl) -4-methylpentane, 4,4'-dihydroxy-2,2,2-triphenylethane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 1,1′-bis- (4-hydroxyphenyl) -para-diisopropylbenzene,
1,1'-bis- (4-hydroxyphenyl) cyclohexane, dihydroxydiphenyl ether and the like can be mentioned.

Of these, polycarbonates obtained by interfacial polycondensation of 2,2-bis- (4-hydroxyphenyl) propane with hasgen and an aqueous alkaline solution of methylene monochloride are most preferably used. The number average molecular weight of these polycarbonate resins is not particularly limited.
Those having a range of 000 to 50,000 are preferred.

The ABS resin is a rubbery polymer 10 to 70.
A monomer comprising 40 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable therewith, based on parts by weight It is a graft copolymer obtained by grafting 30 to 90 parts by weight of a mixture. The rubbery polymer constituting the ABS resin is a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, and a butadiene. There are block copolymers with aromatic vinyl and the like. Styrene and α-methylstyrene monomer are particularly preferred as the aromatic vinyl monomer.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferred. Examples of the vinyl monomer copolymerizable therewith include methacrylates such as methyl methacrylate and ethyl methacrylate, and vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid. The production method of the ABS resin is as follows: in the presence of 10 to 70 parts by weight of a rubbery polymer, 40 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer, and if necessary, It is obtained by polymerizing 30 to 90 parts by weight of a monomer mixture composed of 0 to 40% by weight of a copolymerizable vinyl monomer. This ABS
In the production of the resin-based resin, any generally known polymerization technique can be employed, for example, aqueous heterogeneous polymerization such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and precipitation of the resulting polymer in a non-solvent. There are polymerization and others or a combination thereof. When the polymer antistatic agent of the present invention is added to a molding resin, that is, a thermoplastic polyester resin, a polycarbonate resin, or an ABS resin, a known ionic antistatic agent may be used in combination. Representative examples of these known ionic antistatic agents include metal sulfonates, and specifically, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate and the like are most preferred.

The method and timing of adding the polymer antistatic agent of the present invention to the molding resin are arbitrary and not particularly limited. Although it can be added at any stage of the polymerization process of a molding resin such as a thermoplastic polyester, a method of melting and kneading with a molding resin pellet or the like is preferable.

Among them, a method of melt-kneading the polymer antistatic agent of the present invention and a molding resin such as thermoplastic polyester using an extruder is most preferably used.

The thus obtained durable antistatic molding resin can be used in a conventional manner in various molded parts, fibers, films,
Sheets and the like can be processed without any trouble and provide excellent physical properties.

EXAMPLES Hereinafter, the polymer antistatic agent of the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. In the following examples, “%” and “part” indicate “% by weight” and “part by weight”, respectively.

Production Example 1 In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring rod, 100 parts of Nylon 6 powder (Ube Nylon 6, P1022, manufactured by Ube Industries, Ltd.) was alkalinized. In the coexistence of the compound, 1470 g of β-hydroxyalkylated polyamide (EOA nylon 6 manufactured by Nisso Yuka Co., Ltd.) to which 15 parts of ethylene oxide had been added, 692.8 g of dimethyl terephthalate, and dimethyl isophthalate 17
3.2 g, 1,4-butanediol 844 g and 2.0 g of tetrabutyl titanate as a transesterification catalyst were charged and heated to 200 ° C. while stirring under a nitrogen stream.

After 2 hours, it was confirmed that the theoretical amount of methanol had flowed out by the transesterification reaction. The pressure was reduced to 0.4 mmHg by a vacuum pump, the temperature was further increased to 240 ° C., and an excess amount of 1,4-butanediol was removed. And the polymerization proceeded.

After 3 hours, it was confirmed that the distillation of components such as 1,4-butanediol had ceased, and the pressure was returned to normal pressure to obtain 2300 g of the polymer antistatic agent (1).

Production Example 2 Nylon 66 (Polyplastic Nylon 66 1000-2, manufactured by Polyplastics Co., Ltd.) was used in the same apparatus as in Production Example 1.
Of ethylene oxide 20 per 100 parts of powder
Β-Hydroxyalkylated Polyamide 1 with Added Part
200 g, 996 g of terephthalic acid, 780 g of 1,2-ethylene glycol, and 2.0 g of tetrabutyl titanate as a transesterification catalyst were charged and heated to 210 ° C. while stirring under a stream of nitrogen. After 2 hours, it was confirmed that the inside of the system had become transparent. Then, the pressure was reduced to 0.9 mmHg by a vacuum pump, and the temperature was further increased to 270 ° C. Was confirmed, and the reaction was terminated. As a result, 2258 g of a polymer-based antistatic agent (2) was obtained.

Examples 1 to 6 The polymeric antistatic agent (1) obtained in Production Example 1 and the following thermoplastic polyester resin, polycarbonate resin and ABS resin were prepared in Examples 1 to 6 and Comparative Examples 1-3
Used for

Thermoplastic polyester resin Polybutylene terephthalate << Duranex 400FP manufactured by Polyplastics Co., Ltd., hereinafter referred to as PBT >> Polycarbonate resin Polycarbonate << Mitsubishi Gas Co., Ltd. -Pyrone S
-3000, hereinafter referred to as PC >> ABS resin ABS << Sevien V300 manufactured by Daicel Chemical Industries, Ltd., hereinafter referred to as ABS-V >> High molecular weight antistatic agent (1) obtained in Production Example 1, PB
T, PC and ABS-V were weighed in the proportions shown in Table 1, respectively, and the same amounts of known antioxidants and lubricants were added thereto, and each was placed in a polyethylene bag and dry-blended for 20 minutes using a V-type blender.

The resin mixture after blending was used with Osaka Seiki Co., Ltd.
Extruded at 260 ° C using a 40 mmφ single screw extruder.

During extrusion, neither vent up nor surge was observed. The extruded strand was cooled in a water bath and pelletized. The pellets were dried in a hot air drier at 90 ° C. for 4 hours, and then formed into a test piece for measuring physical properties of an injection molding machine TS-100 manufactured by Nissei Plastic Industry Co., Ltd. The test pieces were a 1/4 inch bar for a tensile test, an ASTM dumbbell (No. 2), a bending test and an Izod impact test, and a color plate for a surface resistivity. ASTM dumbbell and 1/4 inch bar of these molded test pieces were 23 ° C x 60%
After being left overnight in an RH air-conditioned room, physical properties were evaluated.

For the color plate, molding 1
After a lapse of time, the surface resistivity was measured, and then left in an air-conditioned room for one month to measure the surface resistivity again.

The results of the physical properties and surface resistivity measured as described above are also shown in Table 1. One month after molding, the surface resistivity of these molded test specimens was about one order smaller than the surface resistivity immediately after molding. This is due to the absorption of water by the polyamide component in the polymeric antistatic agent.

As described above, these compositions had excellent durability and antistatic properties, had high mechanical strength, and were excellent in appearance of molded articles and extrusion workability.

Comparative Examples 1 to 3 For comparison, PBT, PC and ABS-V were weighed, dry blended, kneaded and extruded, molded and measured for physical properties in the same manner as in Examples 1 to 6, respectively. went. The results thus measured are shown in Tables 1 and 2.

Table 1: Results of Measurement of Physical Properties of Molded Test Specimen Example Composition / Physical Properties Measurement 1 2 3 4 5 6 6 PBT (parts by weight) 80 90----PC (〃)--90 95--ABS-V (〃) − − − − 80 90 Polymer (〃) 20 10 10 5 20 10 Antistatic agent tensile strength (kg / cm ² ) 500 510 590 600 430 400 Tensile elongation (%)> 200 150>200>200>200> 200 Flexural modulus (kg / cm ² ) 19000 20000 20000 21000 18000 17000 Impact resistance test (kg · cm / cm ² ) 15 7 25 18 70 55 Surface resistivity (Ω · cm) 1 hour after molding ^{2x10 12 3x10 13 5x10 13 1x10 14} 7x10 13 9x10 13 1 month after ^{9x10 11 5x10 12 5x10 12 2x10 13} 3x10 12 3x10 13 table 2: results of measured physical properties of molded specimens Comparative example Measurement of composition and physical properties 12 23 PBT (parts by weight) 100--PC (（)-100-ABS-V (〃)--100 Polymer (系)---Tensile strength of antistatic agent (kg / Cm ² ) 510 600 370 Tensile elongation (%) 40 150> 200 Flexural modulus (kg / cm ² ) 20000 22000 17000 Impact resistance test (kg · cm / cm ² ) 3 10 45 Surface resistivity (Ω · cm) One hour after molding Infinity Infinity Infinity One month after infinity Infinity Infinity Examples 7 and 8 Polymeric antistatic agent (2) obtained in Production Example 2 and polyethylene terephthalate (Mitsubishi) Rayon Co., Ltd., Dianite MA-530H, hereinafter referred to as PET) were weighed in the proportions shown in Table 2, placed in a polyethylene bag, and dry-blended for 20 minutes using a V-type blender. Using a 40mmφ single screw extruder manufactured by Seiki Co., Ltd.
The mixture was kneaded and extruded at 80 ° C.

The extruded strand was cooled in a water bath and pelletized. After vacuum drying the pellets at 180 ° C. for 6 hours, the pellets are supplied to a 25 mmφ twin screw extruder manufactured by Haake Co., Ltd., melt-extruded at 280 ° C., and the film is passed through a T-type die via a gear pump and a filter. The molten film is wound around a cooling drum and solidified by cooling to a thickness of 30 mm.
An unstretched film of about 50 μm was obtained. After leaving this film in an air-conditioned room at 23 ° C. × 60% RH for 24 hours and 1 month, a tensile test was performed.

The surface resistivity was measured one hour after the film was formed and then left for one month in an air-conditioned room. Table 3 also shows the values thus measured.

Comparative Example 4 For comparison, PET was weighed, dried, formed into a film, and measured for physical properties in the same manner as in Examples 7 and 8.

The results are shown in Table 3.

Table 3 Result of Measurement of Physical Properties of Film Composition / Physical Properties Measurement Example 7 Example 8 Comparative Example 4 PET (parts by weight) 80 90 100 Polymeric antistatic agent (2) (〃) 20 10- Tensile strength Air conditioning room After 24 hours 610 590 570 (kg / cm ² ) 後 After 1 month 580 570 560 Tensile elongation Air conditioning room After 24 hours>300>300> 300 After 1 month>300>300> 300 Surface resistivity 1 hour after molding 4x10 ¹² 4x10 ¹³後 One month later 8x10 ¹² 6x10 ¹² ∞ FIG. 1 shows an infrared absorption spectrum of the PBT-g-nylon 6 polymer (1). OH‖ | 3300, 1650, 1550 cm -1 amide group of nylon 6 (-CN-) O ‖ The absorption peak at 1720 cm -1 can be confirmed by the absorption peak attributed to the ester group (-CO-) of PBT.

PBT-g-nylon 6 polymer (1)
¹ H-, ¹³ C-nuclear magnetic resonance absorption spectrum of
¹ H and ¹³ C-NMR) are shown in FIGS. 2 and 3, respectively. ^The peak of PBT in ¹ H-NMR is (CF ₃ COO
H, δ, 2.17 (s), 4.62 (s), 8.23
(S)) and other peaks are attributed to EOA Ny-1. ^{In 13} C-NMR, the peak of PBT is (CF ₃ CO
OH, δ, 26.47, 68.51, 131.69, 1
35.69, 171.06) and other peaks are EOA
Ny-1. However, δ1 of ¹ H-NMR
1.5, δ 110.36 to 122.9 of ¹³ C-NMR
The peak at 0, 163.36 to 164.78 is the absorption attributed to the solvent.

Example 9 (Production of PET-g-nylon 66 polymer) Nylon 66 (Polyplastics Co., Ltd.)
Made by adding 5 parts of ethylene oxide to 100 parts of polyplastic nylon 66 1000-2) powder
-Hydroxyalkylated polyamide (hereinafter EOA Ny)
-66) was used as a polyamide having a hydroxyl group in the molecule.

In the same apparatus as in Example 1, 58.2 g of dimethyl terephthalate, 39 g of 1,2-ethylene glycol,
70 g of EOA Ny-66 and 0.1 g of titanium (IV) tetrabutoxide as a transesterification catalyst were charged,
The mixture was heated to 180 ° C. while stirring under a nitrogen stream. Two hours later, it was confirmed that the theoretical amount of methanol had flowed out. The pressure was reduced to 0.9 mmHg by a vacuum pump, and the temperature was further raised to 270 ° C. After 2 hours, there was no outflow of 1,2-ethylene glycol. After confirming the above, the pressure was returned to normal pressure to obtain 122.9 g of PET-g-nylon 66 polymer.

FIG. 3 shows the infrared absorption spectrum of PET-g-nylon 66 polymer. In FIG. 3, 330
At ⁰ , 1650 and 1550 cm ^-1 , peaks attributable to the amide group peak of nylon 66 and at 1725 cm ^-1 the absorption peak attributed to the ester group of polyethylene terephthalate (hereinafter referred to as PET) can be confirmed. In addition, PET-g-nylon 6
As a result of measuring ¹ H- and ¹³ C-NMR of the 6 polymer, ¹ H
In NMR, the peak of PET is (CF ₃ COOH, δ,
2.9 (s), 8.2 (s)) and other peaks are EO
A Ny-66. PET in ¹³ C-NMR
Peaks (CF ₃ COOH, δ, 66.1, 132.
0, 135.6, 170.0), and other peaks are EO
A Ny-66.

[0074]

Conventionally, ionic low molecular weight compounds and hydrophilic polymers have been used as antistatic agents for molding resins, but they have problems such as a reduction in the antistatic effect and a decrease in physical properties. When the polymer antistatic agent of the present invention is used, various molded parts, fibers, films, sheets, and the like having advantages such as semi-permanent antistatic effect, gloss imparting, and improvement in physical properties can be obtained. Was.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a PBT-grafted nylon 6 polymer obtained in Production Example 1.

FIG. 2 is a ¹ H-NMR spectrum of the PBT-grafted nylon 6 polymer obtained in Production Example 1.

FIG. 3 is a ¹³ C-NMR spectrum of the PBT-grafted nylon 6 polymer obtained in Production Example 1.

FIG. 4 is an infrared absorption spectrum of the PBT-grafted nylon 66 polymer obtained in Production Example 2.

[Explanation of symbols]

 None (margin)

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08G 69/00-69/50 C09K 3/16 CA (STN) REGISTRY (STN )

Claims (2)

(57) [Claims] (1) Polyamide containing a polyamide as a trunk polymer and polyalkylene ether and a nucleus-substituted dicarboxylic acid as a branch polymer.
An antistatic agent for a thermoplastic resin, which is a graft polymer composed of a block polymer with a ester . 2. The following chemical formulas 1 and 2 Embedded image << where R ¹ is a butylene group, a hexylene group, an octylene
Group, 1,3-phenylene group, 1,4-phenylene group,
A taxylylene group , R ² is an alkylene group having 4 to 14 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, m is 1 to 1 ,
000, n is 1 to 10, p is 1 to 200, q is 1 to 50
The polymer antistatic agent according to claim 1, which is represented by [I] or [II].