JPH11349820A - Antistatic agent for thermoplastic resin - Google Patents

Abstract

(57) [Summary] [PROBLEMS] An antistatic agent for a thermoplastic resin having excellent durability with excellent antistatic properties and heat resistance that does not hinder practical use, and further, by using the antistatic agent, An object of the present invention is to provide a thermoplastic resin having excellent electrical properties and high quality, and a molded product thereof. SOLUTION: The polyalkylene glycol represented by the following general formula (1) has a structure in which both terminals are blocked with a linear polyester, and has a number average molecular weight of 4,500.
~ 30,000 antistatic agents for thermoplastic resins. (Wherein, R ₁ is a linear alkylene group having 4 to 6 carbon fibers, R ₂ is an alkylene group mainly composed of an ethylene group, n is an integer of 90 to 455, and m and k are the same or different.
Is an integer greater than or equal to. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent for a thermoplastic resin, and more particularly, to an antistatic agent having excellent durability and heat resistance.
And the molded article.

[0002]

2. Description of the Related Art Most thermoplastic resins typified by polyesters have physical and physical properties higher than natural fibers such as cellulose.
Although it has excellent chemical properties, it has a great disadvantage that it is easily charged with static electricity due to friction because it is hydrophobic and has high electrical insulation. This tendency is particularly large in polyesters having high hydrophobicity among thermoplastic resins.

Conventionally, to solve this problem, a method of applying an antistatic agent to the surface of a molded article of a thermoplastic resin, a method of kneading the molded article into a thermoplastic resin, and the like have been proposed. The antistatic agent specifically used in these methods is mainly a polyalkylene glycol, which is in a form of dispersion on a muscle along the fiber axis direction.

However, polyalkylene glycols have poor water resistance due to water solubility, and have poor compatibility with matrix polymers, so they easily fall off from the matrix polymers, and the antistatic effect of the final product decreases with time. was there. Furthermore, due to the low heat resistance of the polyalkylene glycol, there is also a problem that thermal deterioration occurs in the melting stage of the polymer before being formed into fibers, films and resins, whereby the final product is yellowed and colored, and its quality is reduced.

In order to solve this drawback, Japanese Patent Publication No. 45-1
No. 7547 and Japanese Patent Publication No. 46-7461 propose a block copolymer block polyetheramide in which polyalkylene glycol blocks and polyamide blocks are randomly arranged. In this method, a hydrophobic polyamide is copolymerized with a hydrophilic polyalkylene glycol, thereby imparting a hydrophobic function to the antistatic agent, thereby achieving antistatic durability.

However, this method is effective when a polyamide such as nylon is used as a matrix polymer, but has a durable antistatic property due to poor compatibility between polyester and polyamide. Has not been obtained. Another problem is that the yellowing due to thermal degradation during the melting stage of the polymer before molding is further promoted by the thermal decomposition of the polyamide.

A block polyetherester copolymer in which polytetramethylene glycol and polybutylene terephthalate are randomly arranged is disclosed in JP-A-6-15842.
No. 9 proposes this. Here, in order to impart a hydrophobic function to the antistatic agent, by using polybutylene terephthalate, which is an aromatic polyester, even when the polyester is used as a matrix polymer, good compatibility between the two provides durability. A certain antistatic property is secured. However, while the above two antistatic agents are water-insoluble,
There is a problem that the hydrophilicity of the polyalkylene glycol is impaired and the antistatic property is reduced.

As an antistatic agent which suppresses a decrease in hydrophilicity due to the imparting of hydrophobicity, a special polyethylene glycol compound in which both ends of polyethylene glycol are blocked with an organic group having a plurality of long-chain alkyl groups in side chains. Is Tokuho 7-
No. 5,166,163. In this antistatic agent, since both ends of the hydrophilic polyalkylene glycol are blocked with the hydrophobic organic group, the decrease in hydrophilicity is certainly suppressed. However, since this type of antistatic agent has a long-chain alkyl group in the side chain in order to impart hydrophobicity necessary for antistatic durability only at both ends, tertiary carbon is present. ing. At present, the hydrogen bonded to the carbon has a strong activity, and the problem of thermal degradation in the melting stage of the polymer has not been solved yet.

As described above, an antistatic agent for a thermoplastic resin having excellent durability and excellent antistatic properties and heat resistance which does not hinder practical use has not yet been proposed. The emergence of is strongly desired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a durable and excellent antistatic property and a heat-resistant thermoplastic which does not hinder practical use. An object of the present invention is to provide an antistatic agent for a resin. Another object of the present invention is to provide a thermoplastic resin having excellent antistatic properties and high quality by using the antistatic agent, and a molded product thereof.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the number average molecular weight is 450
It has been found that a polyester ether block copolymer having a specific composition of 0 to 30,000 exhibits a durable and excellent antistatic property without losing the antistatic property of the polyalkylene glycol.

Thus, according to the present invention, the following general formula (1)

[0013]

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(Wherein, R ₁ is a linear alkylene group having 4 to 6 carbon fibers, R ₂ is an alkylene group mainly composed of an ethylene group, n is an integer of 90 to 455, and m and k are the same.) Or a different integer of 3 or more), which has a structure in which both ends of the polyalkylene glycol are blocked with a linear polyester.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The antistatic agent of the present invention comprises a polyalkylene glycol having polyethylene glycol as a main component, and having both ends of a specific aliphatic polyester [HO- (R ₁ -OCO) as shown in the above formula 1. m and (CO-R ₁ -O) kH]. The polyethylene glycol referred to here is
A copolymer of propylene glycol and tetramethylene glycol may be used as long as the antistatic property is not impaired. The molecular weight of polyethylene glycol is preferably 4000 or more from the viewpoint of heat resistance.

In the conventional randomly arranged block copolymer, a hydrophobic component is present not only at the end of the polyalkylene glycol but also inside the polyalkylene glycol. Therefore, even if an attempt is made to ensure a sufficient chain length of the polyalkylene glycol to sufficiently exhibit the antistatic performance, the chain length of the final copolymer is determined from the viewpoint of melt miscibility with the matrix polymer, so that the hydrophilicity is high. It is difficult to achieve a balance between the properties that are opposite to each other.

Therefore, it is necessary that the antistatic agent of the present invention is an aliphatic polyester which selectively blocks only the terminal of the polyalkylene glycol. Therefore, aliphatic polyesters formed by polycondensation of a divalent carboxylic acid and a dihydric alcohol are not included because ordinary polycondensation results in randomly arranged block copolymers.

The aliphatic ester that imparts hydrophobicity to the modified polyalkylene glycol must naturally have thermally stable properties from the viewpoint of heat resistance. Therefore, aliphatic polyesters having highly reactive hydrogen, ie, having tertiary carbon with an alkyl group added to the side chain, are not included.

A specific aliphatic polyester has a repeating unit in which an ester group is added to an alkyl group having 4 to 6 carbon atoms. When the number of carbon atoms is 3 or less, the hydrophobicity of the aliphatic polyester is low, and durable antistatic property cannot be obtained. Further, when the number of carbon atoms is 7 or more, there is a concern that a synthesis problem may occur. In particular, since ε-caprolactone can utilize ring-opening addition polymerization in blocking both ends of the polyalkylene glycol, the amount of the aliphatic polyester to be added can be easily controlled, which is preferable.

Further, the number average molecular weight of the modified polyalkylene glycol of the present invention as a whole is 4500 to 300.
00 or less, preferably 5000 or more and 250 or less.
00 or less. When the molecular weight is less than 4500, the modified PEG (A) is difficult to form a streak-like dispersed form having a sufficient length in the polyester fiber, so that the initial antistatic performance becomes insufficient. When the molecular weight exceeds 30,000, the modified PEG (A) becomes insufficient. Melt miscibility in the modified polyalkylene glycol began to deteriorate,
Dispersibility decreases.

A polyalkylene glycol residue [(R
₂ O) n] as a hydrophilic part, and an aliphatic polyester residue [HO-
When (R ₁ -OCO) m and (CO-R ₁ -O) kH] are the hydrophobic parts, the HLB value of griffin is preferably in the range of 8 to 18. When the HLB value is larger than 18, the aliphatic ester portion added to the terminal is small, so that the effect of improving heat resistance is not sufficiently exhibited, and the durability such as washing and alkali treatment is insufficient. Conversely, if it is less than 8, the heat resistance is improved, but the contribution of the hydrophobicity is too large and the antistatic property is poor. However, the HLB value of Griffin complies with the following definition.

[0022]

(Equation 2)

The antistatic agent of the present invention may be used alone, but is preferably used in combination with an electrolyte. This is because the electrolyte functions to further promote the antistatic performance of the antistatic agent. Any electrolyte may be used as long as it has a high degree of ionization, whether inorganic or organic. Particularly preferred examples are
It is an organic sulfonic acid metal salt of an alkyl group having 3 to 30 carbon atoms, an aryl group or an alkylaryl group having 7 to 40 carbon atoms, and an alkali metal.

Specific examples of the organic sulfonic acid metal salt include dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid nonylbenzenesulfonic acid, dibutyl naphthalenesulfonic acid, and hexadecylsulfonic acid. There is an alkali metal salt of sulfonic acid formed from an alkali metal such as sodium, potassium, lithium and the like such as dodecylsulfonic acid. Further, those represented by the following general formula can also be preferably exemplified.

[0025]

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(Wherein R 'is a monovalent hydrocarbon group, R "is an alkylene group having 2 to 4 carbon atoms, a is an integer of 1 to 100, b is an integer of 2 to 4, M is Na, K , Li, etc.) Among them, sodium dodecylbenzenesulfonate, a mixture of sodium alkylsulfonate having an average of 14 carbon atoms,

[0027]

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Metal salts of sulfonic acids such as Such organic metal salts may be used alone or in combination of two or more.

The mixing ratio (weight ratio) of the modified polyoxyalkylene glycol compound and the organic sulfonic acid metal salt compound is preferably in the range of 90:10 to 55:45.
When the mixing ratio of the organic sulfonic acid metal salt compound is less than 10% by weight, the effect of promoting the antistatic property by the electrolyte is not sufficiently exhibited. No remarkable promoting effect on electrical conductivity is exhibited.

The thermoplastic resin to which the antistatic agent of the present invention is applied is typified by polyester, polyamide, polyolefin and the like, but polyester is preferable from the viewpoint of compatibility with the antistatic agent of the present invention. The polyester referred to in the present invention is an aromatic polyester having an aromatic ring in a chain unit of a polymer, and is obtained by reacting a bifunctional aromatic carboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. It is united.

Specific examples of the polymer include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis-
(Phenoxy) ethane-4,4'-dicarboxylate, etc., polyethylene isophthalate terephthalate,
Copolyesters such as polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate, and the like can be given. Among them, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are particularly preferred.

The antistatic agent of the present invention may be applied to the surface of the thermoplastic resin and the molded product, or may be kneaded inside. Particularly preferred is the latter method from the viewpoint of imparting durable antistatic properties.

When the antistatic agent of the present invention is kneaded into, for example, polyester, the mixing amount is 0.5 to 20% by weight based on the weight of the above-mentioned polyester-based matrix polymer from the viewpoint of ensuring antistatic properties. , Preferably 1 to 10%
Contained. If the mixing amount of the antistatic agent is less than 0.5%,
If the antistatic property is not enough, even if it exceeds 20%,
Significant antistatic improvements can no longer be obtained.

When a metal salt of an organic sulfonic acid is added in combination, the mixing amount of the metal salt of an organic sulfonic acid is 0.1 to 10% by weight based on the weight of the matrix polymer from the viewpoint of antistatic properties and the quality of the final product. Is suitable, and particularly preferably in the range of 0.1 to 5% by weight. Since the antistatic agent of the present invention has a terminal blocked with a thermally stable aliphatic ester, the thermal deterioration during the process of increasing the temperature of the antistatic agent is extremely small as compared with the conventional antistatic agent. However, it is naturally preferable that the period during which the heat history is received is short. So the antistatic agent is
It is desirable to add during the melting stage of the polymer before molding. That is, a method of preparing and adding a preliminarily compounded matrix polymer using a usual kneader, dissolving the modified polyalkylene glycol by heat, or using a dispersing medium to form a solution, and melt the matrix polymer. It is preferable to adopt a method of adding to the mixture. When the antistatic agent and the organic metal sulfonate of the present invention are used in combination, the two may be directly melt-kneaded into a matrix polymer polymerization system or a chip after polymerization, or in another case, The polymers to which the above agents have been separately added may be further melt-mixed.

The antistatic polyester composition of the present invention may contain, for example, an antioxidant, a heat stabilizer, and an ultraviolet absorber. In addition, if necessary, a flame retardant, a fluorescent whitening agent, an antifoaming agent, a coloring agent, inert fine particles and other optional additives may be blended. The antioxidant suppresses thermal decomposition of the modified polyalkylene glycol polymer due to high temperature, low discharge speed, long residence time, and the like in the melt-out stage of the polymer before molding, so as to make the modified polyalkylene glycol polymer soluble in water and alkali. It is possible to prevent a decrease in durability or the like.

Among the various agents described above, it is a preferable embodiment to use an antioxidant in combination in order to particularly maintain the heat resistance of the antistatic agent. The type of the antioxidant is not limited as long as it has an antioxidant ability. Preferred antioxidants used in the present invention include hintered phenol compounds, thioflovionate compounds, and phosphite compounds.
The species may be used alone or in combination of two or more. The compounding ratio of the antioxidant is preferably in the range of 0.02 to 3% by weight based on the aromatic polyester. When blending the matrix polymer with an antioxidant or the like, any method can be adopted, and the above components can be blended simultaneously or separately in any order. That is, before the polycondensation reaction of the Yoshiharu polyester,
In the course of the polycondensation reaction, at the end of the polymerization condensation reaction, but still in the molten state, in the state of powder or granules, or in the melting stage of the polymer before molding, etc., melt and mix each of the Hoshun group polyester and the additional components in advance. It may be added in a single operation, or may be added in two or more portions. After separately adding the respective components to the aromatic polyester in advance, these components are added in the melting stage of the polymer before molding. You may mix. Furthermore, when the additional component is added before the middle stage of the polycondensation reaction, it may be added by dissolving or dispersing in a solvent such as glycol.

The polyester composition into which the antistatic agent of the present invention has been kneaded can be formed into products of any shape such as fibers, films, sheets and various containers by any method. When the composition is formed into a fiber, the composition may be used alone for spinning, or may be spun so as to be disposed as one component of a composite fiber.

In particular, when the conjugate fiber has a core / sheath structure comprising a core / sheath, the antistatic composition is used for the core component, and the substantially non-antistatic fiber-forming thermoplastic polymer is used for the sheath component. It is preferable to use coalescence. In this case, the sheath component prevents the antistatic agent from falling off from the matrix polymer as the core component. The fiber-forming thermoplastic polymer used for the sheath component is not particularly limited as long as it has compatibility with the antistatic composition. Here, “substantially” means that the antistatic agent is 0.5 wt.
%.

For example, when producing a core-sheath type composite fiber,
Using a composite spinning apparatus, a non-static fiber-forming thermoplastic polymer on the sheath side and the antistatic composition on the core side can be produced under any spinning conditions. For example, 500-2
A method of melt-spinning at a winding speed of 500 m / min, stretching and heat treatment, a method of melt-spinning at a winding speed of 1500 to 5000 m / min and performing stretching and false twisting simultaneously or successively, 5000 m / min or more Any production conditions can be adopted, such as a method of melt-spinning at a high winding speed and a method of omitting a stretching step depending on the application.

The outer cross section of the core-sheath type conjugate fiber of the present invention and the shape of the core component can take any shape according to the purpose of the woven or knitted material, such as bulkiness, tension, waist, feeling, and gloss. For example, in addition to a circular cross section, irregular cross sections such as a triangle, a flat, a square, a pentagon, a star, a hexagon, a V, and a C can be exemplified. Making it into an atypical cross section gives you a sense of swelling, drape,
This is preferable for obtaining a feeling such as resilience. Although the outer shape and the shape of the core may be different shapes, the core component and the sheath component must be substantially concentric, that is, the core component and the navy component are not eccentric by 20% or more. It is preferable from the viewpoint.

The obtained antistatic fibers are woven fabrics of various shapes,
Used for knits and non-woven fabrics. In particular, in the case of a medical fabric, a polyester fabric having an excellent texture can be obtained by subjecting the fabric to an alkali weight reduction treatment of 10 to 30 wt%.

In particular, in the case of a core-sheath type composite fiber, the core / sheath composite ratio when the alkali is reduced is preferably in the range of 5/95 to 70/30% by weight. 7 core / sheath composite ratio
If it exceeds 0/30, the polyester portion constituting the sheath component becomes thin, and the effect of suppressing the antistatic agent from falling off from the matrix polymer cannot be sufficiently exhibited. Also core /
When the composite ratio of the sheath is less than 5/95% by weight, the effect of the antistatic agent blended in the core of the polyester fiber is not sufficiently exhibited. Specifically, the thickness of the thinnest portion of the sheath component after alkali reduction is 1 μm or more, and more preferably 2 μm, in a state in which micropores communicating with the core portion are formed in the sheath portion.
It is desirable to reduce the weight so as to be at least m. This thickness is preferably at most 10 μm. As the alkaline compound, sodium hydroxide, potassium hydroxide or the like is used, and the concentration of the alkaline compound can be arbitrarily selected.

In the finishing step of the woven or knitted fabric, heat treatment may be performed at a temperature of 100 ° C. or more to promote the stabilization of the structure and the appropriate arrangement by transferring the antistatic agent and various additives contained in the fiber. preferable. Further, if necessary, a heat treatment for relaxing the ribbon may be used. The use of a mixed yarn of the fiber obtained as described above and a fiber having a different heat shrinkage, a single fiber measure or a cross-sectional shape is also necessary to obtain a feeling of swelling, drape, resilience and the like. It is a good thing.

If necessary, the antistatic polyester fiber of the present invention or a woven or knitted fabric produced from this fiber may be subjected to an appropriate post-hydrophilization process. As the post-hydrophilization processing, for example, a method of treating with an aqueous dispersion of a polyester polyether block copolymer composed of terephthalic acid and / or isophthalic acid or a lower alkyl ester thereof, a lower alkylene glycol, and a polyalkylene glycol. Alternatively, a method in which a hydrophilic monomer such as acrylic acid or methacrylic acid is graft-polymerized, and then the resultant is converted into sodium salt can be preferably employed.

[0045]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. In the Examples and Comparative Examples, parts and% indicate parts by weight and% by weight, respectively. The durability of the antistatic property and the heat resistance of the antistatic agent were measured by the following methods.

(1) Friction charge voltage Dyeing and JIS L-1018-77 6.36
Wash the dyed product equivalent to 10 times of washing (referred to as L10) according to the H method in a desiccator at 30 ± 2% RH at 10 ± 2 ° C. and 40 ± 2% RH at 20 ± 2 ° C. all day and night. A test piece was prepared by allowing the sample to stand for 10 to 2 ° C.
30 ± 2% RH at 40 ± 2% RH at 20 ± 2 ° C.
Using a rotary static tester in a room in an atmosphere of H, the frictional charged voltage was measured according to JIS L-1094 8.2 B method. Note that the friction band voltage is 1.5 k
If it is less than V, the antistatic effect is judged to be sufficient.

(2) Heat resistance Differential scanning calorimeter (THERMOFLEX TAS- manufactured by Rigaku Corporation)
200 TG8110D) and 10 mg of sample
2, the temperature was increased at a temperature increasing rate of 20 ° C./minute, the temperature was maintained at 290 ° C., and after maintaining at 290 ° C. for 25 minutes, the weight loss rate was measured.

Example 1 100 parts by weight of polyethylene terephthalate (intrinsic viscosity = 0.64) obtained according to a conventional method was polyethylene glycol (Mn = 800).
0), poly-ε-caprolactone (Mn = 3200)
Modified polyalkylene glycol (Mn =
11200) in an amount of 10 parts by weight and G as an antioxidant
0.4 parts of A-80 (manufactured by Sumitomo Chemical Co., Ltd.) and 0.2 parts of TP-D (manufactured by Sumitomo Chemical Co., Ltd.) are simultaneously melted at 275 ° C. using a single-screw kneader (MKS30, manufactured by Buss). The mixture was kneaded, extruded, and pelletized to obtain a modified polyalkylene glycol-containing polyethylene terephthalate (A).

Apart from the modified polyalkylene glycol-containing polyethylene terephthalate, dimethyl terephthalate 10
0 parts, ethylene glycol 60 parts, calcium acetate monohydrate 0.06 parts (0.06 parts based on dimethyl terephthalate)
6 mol%) and cobalt acetate tetrahydrate 0.
009 parts (0.107 mol% based on dimethyl terephthalate) were charged into a transesterification vessel, and the mixture was added under a nitrogen gas atmosphere.
The ester exchange reaction was carried out while evaporating the methanol generated by elevating the temperature from 140 ° C. to 220 ° C. over time to the outside of the system. After the transesterification reaction, 0.058 parts of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) as a stabilizer and 0.024 parts of dimethylpolysiloxane as an antifoaming agent were added to the reaction mixture. Then 10
One minute later, 0.14 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added, and the temperature was raised to 240 ° C. while simultaneously removing excess ethylene glycol, and then transferred to a polymerization reactor. The pressure in the reactor is then increased to 760 by the reaction mixture for 1 hour.
The pressure is reduced from 3 mmHg to 3 mmHg.
g., 10 minutes later, 4 parts of sodium dodecylbenzenesulfonate as a metal salt of an organic sulfonic acid was added.
(4 wt% based on polyethylene terephthalate obtained)
%) Was added under reduced pressure. The pressure was further reduced to 1 mmHg, and at the same time, the temperature of the reaction mixture was reduced to 24 hours over 1 hour and 30 minutes.
The temperature was raised from 0 ° C to 280 ° C. Under a reduced pressure of 1 mmHg or less, polymerization was carried out at a polymerization temperature of 280 ° C. for another 2 hours, and then for another 30 minutes. The intrinsic viscosity of the obtained polymer was in the range of 0.645 to 0.655, and the polymer was formed into chips by a conventional method to obtain polyethylene terephthalate (B) containing an organic sulfone metal salt.

The polyethylene terephthalate (A) and (B) obtained above are used as a core component polymer (A):
(B) = 1: 1 weight ratio (in this case, the final concentration of the core of the modified polyalkylene glycol is 5% by weight and the final concentration of sodium dodecylbenzenesulfonate is 2% by weight). It was melted in an extruder and fed via a gear pump to a two-component composite spinning head to form a core component. On the other hand, a polyethylene terephthalate chip having an intrinsic viscosity of 0.64 as a polymer for the sheath component was dried by a conventional method, melted by a screw-type extruder, and similarly supplied to a composite spinning head. The supply amounts of the polymer for the core component and the polymer for the sheath component were as follows: core / sheath = 85/15
It was set to be% by weight. The molten polymer of the core component and the sheath component supplied at the same time is obtained by using a composite spinneret in which 20 composite spin holes each having a round cross-sectional shape in both the core and the sheath are provided.
After extrusion at 280 ° C., 150
It was wound once at a speed of 0 m / min. Then, the drawn yarn was subjected to a drawing heat treatment with a heating roller at 90 ° C. and a drawing heater at 170 ° C. at a draw ratio such that the elongation of the drawn yarn was 30% to obtain a drawn yarn of 50 denier / 20 filaments. .

The obtained drawn yarn is formed into a knitted fabric, and scouring, presetting, 20% alkali weight loss,
For the dyed and knitted fabric that has been dyed and final set, wash 0
Times (referred to as L = 0) and washing 10 times (L =
10) at a temperature of 20 ° C. and a relative humidity of 40% RH, and at a temperature of 10 ° C. and a relative humidity of 3%.
It was measured under an atmosphere of 0% RH. Table 1 shows the results.

The PEG molecular weight and CL-added molecular weight in Table 1 are the molecular weight of the polyethylene glycol moiety and the molecular weight of the poly-ε-caprolactone moiety present in the modified polyalkylene glycol, respectively.

[Examples 2 to 7] The molecular weight and the final concentration of the modified polyalkylene glycol, the amount of poly-ε-caprolactone added, the core-sheath ratio, and the final concentration of the organic sulfonic acid metal salt are adjusted as shown in Table 1. Except for this, the procedure was the same as in Example 1. Table 1 shows the results.

Comparative Example 1 Polyethylene glycol (Mn = 2000) was used instead of the modified polyalkylene glycol.
The experiment was performed in the same manner as in Example 1 except that the final concentration was adjusted as shown in Table 1 using (0). Table 1 shows the results. The antistatic agent of the present invention to which poly-ε-caprolactone is added as shown in Examples has a heat resistance index of 20% or less, which is superior to the conventional antistatic agent. Is shown. In addition, sufficient antistatic performance can be exerted even under low temperature and low humidity conditions, and such excellent antistatic performance has a durability that does not exceed the target value of the frictional band voltage of 1500 V even by repeated washing. Has achieved antistatic performance.

Comparative Example 2 Polyethylene glycol (Mn = 500) was used instead of the modified polyalkylene glycol.
0), except that the final concentration was adjusted as shown in Table 1 using an antistatic agent whose both terminals were blocked with an oxyethylene glycol compound having an α-olefin residue in the side chain and having one terminal blocked. The experiment was performed as in Example 1. The structure of the compound having the α-olefin residue in the side chain is shown in the following general formula. Table 1 shows the results.

[0056]

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Each of the antistatic agents of the present invention to which poly-ε-caprolactone was added as shown in the Examples had a weight reduction rate of 20% or less, which is an index of heat resistance, and was superior to conventional antistatic agents. Heat resistance. In addition, sufficient antistatic performance can be exerted even under low temperature and low humidity conditions, and such excellent antistatic performance has a durability that does not exceed the target value of the frictional band voltage of 1500 V even by repeated washing. Has achieved antistatic performance.

[0058]

[Table 1]

[0059]

The antistatic agent of the present invention is a modified polyalkylene glycol different from the conventional one, and has excellent durable antistatic property and excellent heat stability. Therefore, in imparting antistatic properties by kneading it into a thermoplastic resin, there is little deterioration of the antistatic agent due to the heat history at a high temperature received in the melting stage of the polymer before molding, and it is excellent in operation stability and high quality molding Goods are obtained. Furthermore, the obtained fibers have excellent antistatic properties that are durable even when subjected to washing, dyeing, alkali weight reduction, and the like, and therefore, they are used for women's inner uses such as lingerie and lining, and further, dust-free. It can also be used as a dressing surface required by clothing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D01F 6/92 307 D01F 6/92 307C 8/14 8/14 A

Claims (12)

[Claims] 1. An antistatic agent for a thermoplastic resin comprising a modified polyalkylene glycol compound represented by at least the following general formula (1) and having a number average molecular weight of 4,500 to 30,000 as a main component. Embedded image (Wherein, R ₁ is a linear alkylene group having 4 to 6 carbon fibers, R ₂ is an alkylene group mainly composed of an ethylene group, n is an integer of 90 to 455, and m and k are the same or different.
Is an integer greater than or equal to. ) 2. The thermoplastic resin antistatic agent according to claim 1, wherein R ₁ is pentamethylene. 3. A polyoxyalkylene glycol residue [(R ₂ O) n] is used as a hydrophilic part, and an aliphatic ester residue [HO
The HLB value of griffin when-(R ₁ -OCO) m and (CO-R ₁ -O) kH] is a hydrophobic part is in the range of 8-18, The method according to any one of claims 1 to 2. Antistatic agent for thermoplastic resin. However, the HLB value of Griffin complies with the following definition. (Equation 1) 4. A thermoplastic material comprising the modified polyoxyalkylene glycol compound according to claim 1 and a metal salt of an organic sulfonic acid represented by the following general formula (2): Antistatic composition for resins. Embedded image R: an alkyl group having 3 to 30 carbon atoms, an aryl group or an alkylaryl group having 7 to 40 carbon atoms, M: an alkali metal 5. Mixing ratio (weight ratio) of a modified polyoxyalkylene glycol compound and an organic sulfonic acid metal salt compound.
The antistatic composition for a thermoplastic resin according to claim 4, wherein is in the range of 90:10 to 55:45. 6. The method according to claim 1, wherein the weight of the polyester-based matrix polymer is based on the weight of the matrix polymer.
An antistatic polyester composition comprising the antistatic agent for a thermoplastic resin according to item 1 in an amount of 0.5 to 20% by weight. 7. The method according to claim 4, wherein the weight of the polyester-based matrix polymer is based on the weight of the matrix polymer.
0.5 to 20% by weight of the modified polyoxyalkylene glycol compound described in the item 1, and 0.5 to 20% by weight of the organic sulfonic acid metal salt compound.
An antistatic polyester composition containing 1 to 10% by weight. 8. An antistatic polyester fiber comprising the polyester composition according to claim 6 as a main component. 9. The polyester according to claim 6, wherein at least two or more fiber-forming thermoplastic polymers are arranged adjacent to each other, and one of the fiber-forming thermoplastic polymers is used as the polyester. An antistatic composite fiber, comprising a composition. 10. The composite fiber having a core / sheath composite ratio of 5
8/95 to 70/30% by weight, wherein the sheath is a non-static fiber-forming thermoplastic polymer in a sheath portion, and the core component is a core component. 10. The core-sheath type antistatic conjugate fiber according to claim 9, wherein the antistatic polyester composition is disposed. 11. A method for producing a polyester fabric having an improved texture, comprising subjecting a polyester-based fabric containing the antistatic polyester fiber according to any one of claims 8 to 10 to an alkali treatment. 12. The polyester fabric with improved texture according to claim 11, wherein the antistatic polyester fiber is a core-sheath composite fiber, and the thinnest portion of the sheath component after alkali treatment is adjusted to 0.1 μm or more. Manufacturing method.