JP3406695B2 - Method for producing polyamide ether ester - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a novel polyamide ether ester. More specifically, it relates to a novel method for producing a polyamide ether ester, which is useful as a modifier for a thermoplastic synthetic polymer capable of imparting excellent permanent antistatic property.

[0002]

2. Description of the Related Art Thermoplastic synthetic polymers have excellent properties as materials and are widely used in various industrial fields. However, since thermoplastic synthetic polymers are generally hydrophobic, they are easily charged with static electricity. This is because, in addition to the appearance problem that dust is likely to adhere to the product, when it is used in the electronics field which is rapidly advancing in recent years, static electricity of high voltage charged may damage the circuit or cause malfunction. Has become a major issue that affects the performance of products.

In order to solve these problems, a thermoplastic synthetic polymer excellent in antistatic performance has been developed.

For example, it has been disclosed that a specific polyether ester amide is used as an antistatic agent for a thermoplastic resin (JP-A-62-273252, JP-A-1-162252, and JP-A-5-162). 38747 publication). This polymer provides a permanent antistatic effect as an antistatic agent, but such a polymer is not sufficient in terms of heat resistance, and a thermoplastic resin to be melt-mixed, temperature conditions at that time, and further The use temperature of the obtained resin composition may be limited. Further, when polyamide is synthesized from its raw material, there is a problem that a part of the starting raw material escapes during the polymerization reaction process. It has also been pointed out that the use of poly (alkylene oxide) glycol having a large number average molecular weight makes it difficult to obtain a polyamide ether ester having a high degree of polymerization.

[0005]

The object of the present invention is to add a polyamide ether ester having high heat resistance, which imparts excellent antistatic property by adding it to a thermoplastic polymer, to a number average of poly (alkylene oxide) glycol. An object of the present invention is to provide a simple production method regardless of the molecular weight.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have added a specific aromatic monohydroxy compound to a specific aliphatic polyamide and polyether ester to obtain an ester. It has been found that a polyamide ether ester having excellent heat resistance can be easily obtained by heating and melting in the presence of an exchange catalyst, and then distilling off the aromatic monohydroxy compound, and arrived at the present invention.

That is, according to the present invention, the above-mentioned object of the present invention is represented by the following formula (1):

[0008]

[Chemical 6]

[Wherein R ¹ is an alkylene group having 4 to 12 carbon atoms. ] And the following formula (2)

[0010]

[Chemical 7]

[Here, R ² is an alkylene group having 4 to 12 carbon atoms, and R ³ is an alkylene group having 4 to 12 carbon atoms. ] The polyamide (a) which consists essentially of at least one of the repeating units represented by the following, and the following formula (3)

[0012]

[Chemical 8]

[Wherein R ⁴ is an alkylene group having 2 to 12 carbon atoms, R ⁵ is an alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 250. ] The aliphatic polyether ester (b) or its raw material which consists essentially of the repeating unit represented by the following formula (4)

[0014]

[Chemical 9]

[Here, Ar is a trivalent aromatic group having 6 to 10 carbon atoms, R ⁶ is an alkylene group having 2 to ⁶ carbon atoms, and n is an integer of 1 to 250. M ⁺ represents an alkali metal ion, an alkaline earth metal ion, a phosphonium ion or an ammonium ion. ] A sulfonate-containing polyether ester (c) or a raw material thereof, and 5 to 100 parts by weight of an aromatic monohydroxy compound per 100 parts by weight of the total weight of the above (a), (b) and (c) ( d) is carried out by heating and melting reaction in the presence of a transesterification catalyst, and then distilling off the aromatic monohydroxy compound.

The polyamide (a) used as the raw material of the present invention is represented by the above formula (1) and / or the above formula (2).

In the above formula (1), R ¹ has 4 to 4 carbon atoms.
12 alkylene groups. Such an alkylene group may be linear or branched. Straight-chain is preferred. Examples of such an alkylene group include tetramethylene, pentamethylene, hexamethylene, decamethylene, undecylene and the like. Of these, pentamethylene is preferred. When R ¹ is pentamethylene, the above formula (1) has the following formula (1) -a

[0018]

[Chemical 10]

It is represented by Polyamide composed of repeating units of this structure is generally called nylon 6.

As the polyamide comprising the repeating unit represented by the above formula (1), other than the above, for example,

[0021]

[Chemical 11]

The following can be mentioned.

In the above formula (2), R ² is an alkylene group having 4 to 12 carbon atoms, and R ³ is 4 to 12 carbon atoms.
12 alkylene groups.

The alkylene group having 4 to 12 carbon atoms represented by R ² and R ³ may have a straight chain structure or a branched chain structure,
Alternatively, it may be annular.

Examples thereof include tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, neopentylene, 2,4,4-trimethylhexamethylene and 1,4-cyclohexylene.

Of these, hexamethylene is preferable as R ^{2 and} tetramethylene is preferable as R ³ . In this case, the above formula (2) is the following formula (2) -a

[0027]

[Chemical 12]

It is represented by Polyamide composed of this repeating unit is generally called nylon 6,6.

As the polyamide comprising the repeating unit represented by the above formula (2), other than the above, for example,

[0030]

[Chemical 13]

And the like. Of these, nylon 6 and nylon 6,6 are preferable as the polyamide.

The polyamide (a) can be synthesized by a conventionally known method using a lactam, a salt of a dicarboxylic acid and a diamine, or a dicarboxylic acid halide and a diamine component. Although it may be actually synthesized by these methods, it is simpler and preferable to use commercially available polymer chips as they are, which is one of the major features of the present invention.

The polyamide used in the present invention has an intrinsic viscosity of 0.5 to 3.0 measured at a temperature of 35 ° C. with m-cresol as a solvent. It is preferable in terms of heat resistance, and one having 1.0 to 2.0 is more preferable.

Regarding the polyether ester (b) used as a raw material of the present invention, in the above formula (3), R ⁴ is an alkylene group having 4 to 12 carbon atoms, and R ⁵ is 2 to 2 carbon atoms.
6 is an alkylene group.

The alkylene group represented by R ⁴ may be linear, branched, or cyclic.

As examples thereof, ethylene, trimethylene,
Tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, neopentylene, 2,
Mention may be made of 4,4-trimethylhexamethylene, 1,4-cyclohexylene and methylene-cyclohexylene-methylene.

Specific examples of R ⁵ include ethylene group, propylene group and tetramethylene group.
Further, two or more kinds may be mixed, for example, ethylene groups and propylene groups may be mixed at an arbitrary ratio.

M is a positive integer indicating the degree of polymerization, and is 1 to 2.
It may be in the range of 50, preferably 1 to 150, and more preferably 1 to 100. Moreover, m may use 2 or more types simultaneously.

As the polyether ester composed of the repeating unit represented by the above formula (3), for example,

[0040]

[Chemical 14]

And the like can be preferably used.

The polyether ester (b) composed of the repeating unit represented by the above formula (3) can be synthesized by a conventionally known method using the dicarboxylic acid component and the diol component which are the constituents.

Examples of the dicarboxylic acid component include adipic acid, sebacic acid, adipic acid dimethyl ester, sebacic acid dimethyl ester, adipic acid diethyl ester, and sebacic acid diethyl ester. Among these, adipic acid, sebacic acid, adipic acid dimethyl ester and sebacic acid dimethyl ester are preferable, and adipic acid dimethyl ester and sebacic acid dimethyl ester are more preferable.

As the diol component, a compound represented by the following formula (8) can be used.

[0045]

[Chemical 15]

In the above formula (8), R ⁷ is the same as R ^{5 in the} formula (3), and y is an integer of 1 to 250 like m.

Specific examples of such diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and poly (alkylene oxide) glycols such as polyethylene glycol and polypropylene glycol. The number average molecular weight of the poly (alkylene oxide) glycol is determined by R15 and y, but is generally 1
It is preferably about 00 to 10000, more preferably about 100 to 6000, and even more preferably about 100 to 4000. Among these diol compounds, triethylene glycol and tetraethylene glycol are preferable. The above compounds may be used alone or in combination of two or more.

Further, in order to efficiently copolymerize the above (b) and (c) and to increase the degree of polymerization of the polyether ester copolymer, another diol having a low boiling point is added, and the number of moles of the entire diol component is adjusted to It is preferable to add a little excess of the total number of acid components. As the diol component that can be added, ethylene glycol, propylene glycol, tetramethylene glycol, 3-methylpentanediol, neopentylene glycol or the like can be used. Especially ethylene glycol is preferable.

The above polyether ester (b) used in the present invention has a concentration of 1.2 g in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40).
/ Dl, the reduced viscosity measured at a temperature of 35 ° C is 0.1 to
It is preferably 2.0 in terms of antistatic property and mechanical properties of the obtained polyamide ether ester, and 0.2 to 1.
It is more preferable that it is 5.

Further, the sulfonic acid group-containing polyether ester (c) which is a raw material of the present invention will be described. In the above formula (4), Ar is a trivalent aromatic group having 6 to 10 carbon atoms, and is preferably a benzene ring or a naphthalene ring. Particularly preferred is a benzene ring.

R ⁶ is the same as R ⁵ in the above formula (3).

M ⁺ is an alkali metal ion such as Na ⁺ and K ⁺ , an alkaline earth metal ion such as Mg ²⁺ and Ca ²⁺ , a phosphonium ion or an ammonium ion.

Examples of the phosphonium ion include those represented by the following formula.

[0054]

[Chemical 16]

In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each is an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group or a propyl group, a carbon group such as a phenyl group or a naphthyl group. It represents an aryl group of the formulas 6-18.

Examples of ammonium ions include those represented by the following formula.

[0057]

[Chemical 17]

In the formula, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and each is an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group or a propyl group, a carbon group such as a phenyl group or a naphthyl group. It represents an aryl group of the formulas 6-18.

Of these, alkali metal ions and phosphonium ions are preferred.

As the polyether ester composed of the repeating unit represented by the above formula (3), for example,

[0061]

[Chemical 18]

And the like can be preferably used.

N is a positive integer indicating the degree of polymerization and is 1 to 2
It may be in the range of 50, preferably 1 to 150, and more preferably 1 to 100. Moreover, n may use 2 or more types simultaneously.

The polyether ester (c) can be synthesized by a conventionally known method using a sulfonic acid group-containing dicarboxylic acid component and a diol component, which are constituent components.

Examples of the sulfonic acid group-containing dicarboxylic acid component include compounds represented by the following formula (9).

[0066]

[Chemical 19]

In the formula (9), Ar 'is the above formula (4).
It is the same as Ar in the inside. R ¹⁶ and R ¹⁷ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ⁺ is the same as in formula (4).

Examples of the dicarboxylic acid component include 5-sodium sulfo-isophthalic acid and 2-potassium sulfo-
Sulfophthalic acid alkali metal salts such as terephthalic acid, 5-
Sodium sulfo-isophthalic acid dimethyl ester, 2
-Potassium sulfo-terephthalic acid dimethyl ester or other sulfophthalic acid dimethyl ester alkali metal salt, 5-
Sodium sulfo-isophthalic acid diethyl ester, 2
-Potassium sulfo-terephthalic acid diethyl ester etc. sulfophthalic acid diethyl ester alkali metal salt, 5-
Sulfoisophthalic acid tetrabutylphosphonium salt, 2-
Sulfoterephthalic acid tetrabutylphosphonium salt and other sulfophthalic acid alkylphosphonium salts, 5-sulfoisophthalic acid-tetrabutylphosphonium salt dimethyl ester, 2-sulfoterephthalic acid-tetrabutylphosphonium salt dimethyl ester and other sulfophthalic acid dimethylester alkylphosphonium salts, 5-sulfoisophthalic acid tetrabutylphosphonium salt diethyl ester, 2
-Sulfoterephthalic acid tetrabutylphosphonium salt diethyl ester and other sulfophthalic acid diethyl ester alkylphosphonium salts, sulfophthalic acid alkylammonium salts and their esters, sulfonaphthalenedicarboxylic acid alkali metal salts and their esters, etc.

As the diol component, the same ones as those represented by the above formula (8) can be used.

The above polyether ester (c) used in the present invention has a concentration of 1.2 g in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40).
/ Dl, the reduced viscosity measured at a temperature of 35 ° C is 0.1 to
It is preferably 2.0 in terms of antistatic property and mechanical properties of the obtained polyamide ether ester, and 0.2 to 1.
It is more preferable that it is 5.

According to the present invention, the polyamide (a) consisting essentially of the repeating units represented by the above formulas (1) and / or (2) and the above formulas (3) and (4). A polyether ester (b) comprising a repeating unit,
(C) is heated and melted in the presence of 5 to 100 parts by weight of an aromatic monohydroxy compound (d) and a transesterification catalyst per 100 parts by weight of the total weight of (a), (b) and (c). Excuse me.

As the aromatic monohydroxy compound, those represented by the following formula (5) are preferable.

[0073]

[Chemical 20]

In the above formula (5), X has 1 to 3 carbon atoms.
Is an alkyl group, a halogen atom, and z is an integer of 0 to 3.

Examples of such aromatic monohydroxy compounds include phenol, m-cresol, p-cresol, o-cresol, 2,3-dimethylphenol,
2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, m-ethylphenol, o-ethylphenol, p-ethylphenol, m-propylphenol, o-propylphenol, p-propylphenol, m-chlorophenol,
o-chlorophenol, p-chlorophenol, 2,4
-Dichlorophenol, 2,3-dichlorophenol,
2,5-dichlorophenol, 2,4,6-trichlorophenol and the like can be mentioned. Of these, phenol, p-chlorophenol, m-cresol, p-
Cresol is preferred.

The amount of the aromatic monohydroxy compound used is
The total amount of polyamide (a), polyether ester (b) and (c) is 5 to 100 parts by weight based on 100 parts by weight. When the amount of the aromatic monohydroxy compound used is less than 5 parts by weight based on 100 parts by weight of the total amount of the polyamide and the polyether ester, the action of the compound as a compatibilizing agent is insufficient, and (a), ( The reactions of b) and (c) do not proceed sufficiently. If it is more than 100 parts by weight, it takes a long time to distill off the aromatic monohydroxy compound from the polymerization system after polymerization, which is not preferable. The amount of the aromatic monohydroxy compound used is preferably 1 with respect to 100 parts by weight of the total amount of the polyamide and the aliphatic polyether ester.
It is 0 to 50 parts by weight, more preferably 20 to 40 parts by weight. In carrying out the above reaction, the polyamide (a)
Even if it is carried out using the above raw material, the reaction does not proceed sufficiently and polyamide ether ester cannot be obtained.

When carrying out the above melting reaction, a catalyst is added in order to accelerate the reaction. As the catalyst, a known transesterification catalyst is used. Preferred transesterification catalysts include, for example, alkali metal compounds, alkaline earth metal compounds, metal compounds such as titanium, tin, zinc, antimony, manganese, cobalt and germanium. The amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1% by weight, more preferably 0.01 to 0.05% by weight, based on the produced polyamide ether ester.

The amounts of the above (a), (b) and (c) used preferably satisfy the following formulas (6) and (7).

[0079]

## EQU00002 ## 10 / 90.ltoreq.A / (B + C) .ltoreq.80 / 20 (6) 5 / 95.ltoreq.C '/ B'.ltoreq.50 / 50 (7) where A, B and C are the above ( a), (b) and (c) are the weights based on the repeating units, B'and C'are (b),
It represents the molar amount of (c). In the formula (6), when the left side is smaller than 10/90, a polyamide ether ester having sufficient strength and heat resistance cannot be obtained, and when the right side is larger than 80/20, antistatic property is not exhibited.

In the formula (7), if the left side is smaller than 10/90, sufficient antistatic property cannot be obtained, and if the right side is larger than 50/50, the physical properties are remarkably deteriorated and it cannot be actually used. The composition ratios of (a), (b), and (c) are expressed by the following formula (6)-
It is preferable to satisfy 1 and (7) -1.

[0081]

## EQU00003 ## 20 / 80.ltoreq.A / (B + C) .ltoreq.70 / 30 (6) -1 10 / 90.ltoreq.C '/ B'.ltoreq.30 / 70 (7) -1 Above (a), (b) The order in which (c) and (c) are present in the reaction system is not particularly limited, and examples thereof include (a) and (b).
And (c) are simultaneously added to the aromatic monohydroxy compound, (b) and (c) are previously copolymerized in the same system, and then (a) and the aromatic monohydroxy compound are prepared. Is added, a method in which (a) and (b) and (a) and (c) are copolymerized in advance is prepared in advance, and is added to the aromatic monohydroxy compound, or the above ( It is possible to appropriately use a method in which the respective constituent components as the raw materials of b) and (c) and the polyamide (a) are allowed to be present at the same time and added to the aromatic monohydroxy compound and reacted therewith. Preferably, a method in which (b) and (c) are copolymerized in the same system in advance and then (a) and the aromatic monohydroxy compound are added are prepared.

The reaction temperature during the heating reaction is the above-mentioned (a),
In the polymerization reaction system, (b) and (c) must be at a temperature at which they are melted or dissolved, usually 180 to 250 ° C.
It is desirable to do in. If the reaction temperature is lower than 180 ° C., the polymerization does not proceed so much, and if it is higher than 250 ° C., thermal decomposition occurs, which is not preferable. The preferred reaction temperature is in the range of 200-230 ° C.

The melting time is not particularly limited and may vary depending on the polymer composition, the polymerization temperature, etc., but is generally about 30 minutes to
It is about 8 hours, preferably 1 to 6 hours, more preferably 2 to 5 hours.

As the final stage of the method for efficiently producing the above polyamide ether ester, it is necessary to distill the aromatic monohydroxy compound from the polymerization system to substantially remove it. Examples of the method for removing the aromatic monohydroxy compound include a method in which the melting temperature is higher than the boiling point of the aromatic monohydroxy compound under the polymerization conditions. Gradually reducing the pressure of the reaction system in the latter stage of the melting step is effective for lowering the boiling point of the aromatic monohydroxy compound and distilling it off, and can be preferably carried out. The polyamide ether ester of the present invention can be obtained by distilling off the aromatic monohydroxy compound.

Thus, it is preferable that the atmosphere during the polymerization is atmospheric pressure or increased pressure in an atmosphere of an inert gas such as nitrogen or argon in the initial stage of the reaction and gradually reduced in the latter stage of the reaction.

The polyamide ether ester obtained according to the present invention has a common logarithmic value (LogR) of the surface specific resistance value R (Ω) measured at room temperature of 20 ° C. and relative humidity of 65%.
Indicates a value of 11.0 or less. When the surface resistivity is more than 11.0, when mixed with other thermoplastic synthetic polymer, it may not be possible to impart sufficient antistatic property for practical use. The surface resistivity is preferably 10.0 or less.

The polyamide ether ester obtained by the present invention has a reduced viscosity of 1.2 g in a phenol / tetrachloroethane mixed solvent (weight ratio 60/40).
/ Dl, measured at a temperature of 35 ° C.) is preferably 0.3 to 3.0. If it is less than 0.3, when mixed with other thermoplastic synthetic polymer, it causes a remarkable decrease in physical properties,
If it exceeds 3.0, it is difficult to mix and mold, which is not preferable. A polyamide ether ester having an intrinsic viscosity of about 0.4 to 2.5 is desirable.

The polyamide ether ester obtained by the present invention can be mixed with a thermoplastic synthetic polymer for molding in an appropriate amount to prevent the polymer from deteriorating its antistatic performance without deteriorating physical properties such as mechanical strength and heat resistance. It is possible to provide a resin composition having excellent antistatic property and excellent antistatic property.

Examples of the thermoplastic resin for molding include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyester carbonate resins, polystyrene resins such as ABS resins, polyamide resins, polyether resins and polyether ester resins. One kind or two or more kinds thereof can be used. In such a resin composition, the polyamide ether ester is used in an amount of 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 3 to 30% by weight, based on the resin composition.
By including it, the surface resistivity (L
ogR) is 13.0 or less, and excellent antistatic performance is exhibited.

As a method for producing the above resin composition, a conventionally known method using a melt extruder such as an extruder can be applied. Further, when mixing, there is no problem even if a surfactant type additive which has been conventionally used to further improve antistatic performance is added.

For example, dodecylbenzenesulfonic acid N
a, K dodecylbenzene sulfonic acid, and Li dodecyl benzene sulfonic acid.

Other various additives used as necessary include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium whisker, fibrous reinforcing agents such as carbon fiber, talc, Calcium carbonate,
Various fillers such as mica, clay, titanium oxide, aluminum oxide, glass flakes, milled fibers, metal flakes, metal powders, heat stabilizers represented by phosphoric acid esters and phosphorous acid esters, light stabilizers, Additives such as lubricants, pigments, flame retardants, flame retardant aids, plasticizers and the like may be appropriately mixed.

[0093]

INDUSTRIAL APPLICABILITY According to the present invention, a polyamide ether ester can be produced by a simple method by directly using a polyamide and using an aromatic monohydroxy compound as a reaction medium. Such a polyamide ether ester is expected to have a polyamide introduced into the polymer in blocks, and has a better heat resistance than conventional polyamide ether esters.

By mixing the polyamide ether ester obtained by the present invention with various thermoplastic polymers, a resin composition having excellent antistatic performance can be provided.

[0095]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. In the examples, "parts" means parts by weight.

(Viscosity measurement) The reduced viscosity of the obtained polyamide ether ester was 1.2 g / dl at a temperature of 35 ° C. in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40). It was measured at.

The intrinsic viscosity of the polyamide was measured at a temperature of 35 ° C. using m-cresol as a solvent.

Further, the reduced viscosity of the polyether ester was 1.2 g / dl in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40).
It was measured at a temperature of 35 ° C. (Thermal property) The melting point (Tm) of the polymer was measured by DSC under the conditions of a temperature rising rate and a temperature lowering rate of 10 ° C / min. The heat distortion temperature (HDT) of the resin composition molded product is ASTM D
According to 648, 1/4 inch, load 18.6 kg / cm
Measured at ² .

(Impact Strength) The impact strength of a resin composition molded product containing a polyamide ether ester is ASTM
Measured at 1/8 inch according to D256.

(Surface specific resistance) The surface solid resistance of the polyamide ether ester and the polyamide ether ester-containing resin composition molded product is 20 ° C. and the relative humidity (HR) is 6
After leaving it in a 0% constant temperature and humidity room for 1 day, an applied voltage of 1000 V was applied with a super insulation meter (SM-8210 manufactured by Toa Denpa Kogyo KK)
Was measured.

(Evaluation of permanent antistatic property) Polyamide ether ester whose surface specific resistance was measured in advance and its molded article were continuously poured with tap water at a flow rate of 500 ml / min.
After dipping in a constant temperature shaking tank at 0 ° C. for 2 hours to wash with water, water was wiped off and dried, and the surface specific resistance was measured again as described above.

[Reference Example 1] (Synthesis of Polyether Ester) 174 parts of dimethyl adipate (70 mol% based on the total carboxylic acid component), 296 parts of 5-sodium sulfo-isophthalic acid dimethyl ester (based on the total carboxylic acid component) 30 mol%), tetraethylene glycol 194 parts (90 mol% based on all carboxylic acid components), ethylene glycol 110 parts (110 mol% based on all carboxylic acid components), and tetrabutyl titanate 0.15 parts. It was placed in a reaction vessel equipped with a stirrer and a vacuum distillation system, and heated to 200 ° C. under a normal pressure in a nitrogen stream. After a predetermined amount of methanol flowed out, the reaction temperature was gradually raised to 230 ° C finally. Next, the temperature was maintained at 230 ° C., and the pressure was gradually reduced to a high vacuum state of about 20 mmHg after 10 minutes and 1 mmHg or less after 10 minutes. During this time, ethylene glycol was distilled from the polymerization system.

The resulting polymer was a slightly yellowish transparent polymer in the melt and had a reduced viscosity of 0.28.

[Example 1] Intrinsic viscosity 1.41, terminal COO
H group amount 66 equivalent / 10 ⁶ g, terminal NH 2 group amount 15 equivalent / 1
35 parts of granular chips of nylon 6 (hereinafter abbreviated as Ny6) of 0 ⁶ g, 65 parts of the aliphatic polyether ester obtained in Reference Example 1, 33 parts of phenol, and 0.01 part of tetrabutyl titanate were stirred and vacuumed. It was placed in a reaction vessel equipped with a distillation system and heated to 230 ° C. under a nitrogen stream under normal pressure. About 1
After 0 minutes, it became a cloudy solution. After about 6 hours, the reaction melt became homogeneous. Next, the temperature was maintained at 230 ° C, and the pressure was gradually reduced to about 20 mmHg after 10 minutes and 1 m after 10 minutes.
A high vacuum state of about mHg or less was set, and the reaction was performed for 30 minutes under the same conditions. During this time, phenol distilled from the polymerization system.

The polymer obtained is a slightly yellowish transparent polymer in the melt and has a reduced viscosity of 0.75, D
From the SC measurement result, Tm (melting point) = 186 ° C., and surface resistivity logR was 7.0.

Example 2 Of the total amount of 100 parts of Ny6 and aliphatic polyether ester charged, the compositional weight ratio of Ny6 and aliphatic polyether ester (A / (B +
Polymerization was performed in the same manner as in Example 1 except that C)) was changed to 20/80.

The polymer obtained is a slightly yellowish transparent polymer in the melt and has a reduced viscosity of 0.95, D
From SC measurement results, Tm = 180 ° C, surface resistivity log
R was 7.3.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that triethylene glycol was used instead of tetraethylene glycol.

The polymer obtained was a transparent polymer in the molten state, and had a reduced viscosity of 1.00 and a Tm from the DSC measurement results.
= 182 ° C., surface resistivity logR was 7.7.

Example 4 Instead of 5-sodium sulfo-isophthalic acid dimethyl ester used in Reference Example, 5
Polymerization was carried out in the same manner as in Example 1 using a polyether ester synthesized using tetrabutylphosphonium sulfoisophthalate salt.

The polymer obtained was a transparent polymer in the molten state, had a reduced viscosity of 0.90 and was
m = 178 ° C., and the surface resistivity logR was 7.1.

[Example 5] A chip obtained by grinding the polymer obtained in Example 1 was mixed with a polycarbonate resin (PC) chip ("Panlite" L-1250 manufactured by Teijin Chemicals Ltd.) in a predetermined amount, and then a cylinder Temperature 260 ℃, mold temperature 4
Molding was performed under the condition of 0 ° C., and various physical properties and permanent antistatic property of the obtained molded product were evaluated. The results are shown in Table 1 below.

[Comparative Example 1] A polycarbonate resin chip ("Panlite" L-1250 manufactured by Teijin Chemicals Ltd.)
Molding was performed under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C., and various physical properties and permanent antistatic property of the obtained molded product were evaluated. The results are shown in Table 1 below.

Example 6 The polymer crushed chips obtained in Example 1 were mixed with ABS resin chips (UT-61 manufactured by Mitsui Toatsu Co., Ltd.), and the cylinder temperature was 230 ° C.
Molding was carried out under the condition that the mold temperature was 40 ° C., and various physical properties and permanent antistatic property of the obtained molded product were evaluated. The results are shown in Table 1 below.
Shown in.

[Comparative Example 2] ABS resin chips (UT-61 manufactured by Mitsui Toatsu Co., Ltd.) were molded under the conditions of a cylinder temperature of 230 ° C and a mold temperature of 40 ° C, and various physical properties of the molded product obtained. And the permanent antistatic property was evaluated. The results are shown in Table 1 below.

Example 7 Chips obtained by pulverizing the polymer obtained in Example 1 were used as polybutylene terephthalate resin (P
BT) chips (manufactured by Teijin Ltd., intrinsic viscosity 0.88), and then molded under the conditions of a cylinder temperature of 230 ° C and a mold temperature of 40 ° C. The sex was evaluated. The results are shown in Table 1 below.

[Comparative Example 3] Polybutylene terephthalate resin (PBT) chip (manufactured by Teijin Ltd., intrinsic viscosity 0.8)
8) was molded under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., and various physical properties and permanent antistatic property of the obtained molded product were evaluated. The results are shown in Table 1 below.

[Examples 8 to 11] Chips obtained by crushing the polymers obtained in Examples 1 to 4, polycarbonate resin (PC) chips ("Panlite" L-1250 manufactured by Teijin Chemicals Ltd.) and ABS. Resin chips (UT-61 manufactured by Mitsui Toatsu Co., Ltd.) were mixed at the weight ratio shown in Table 2, and then molded under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., and each molded product obtained. The various physical properties and the antistatic property were evaluated. The results are shown in Table 1 below.

[0119]

[Table 1]

(P1 to P4: Polyamide Ether Ester Corresponding to Examples 1 to 4) The resin composition using the polyamide ether ester obtained according to the present invention effectively reduces the surface resistance without lowering the physical properties. You can see that I have lowered.

Continuation of front page (56) Reference JP-A-5-140541 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 69/00-69/50

Claims (3)

(57) [Claims] 1. The following formula (1): [Here, R ¹ is an alkylene group having 4 to 12 carbon atoms. ] And a repeating unit represented by the following formula (2): [Here, R ² is an alkylene group having 4 to 12 carbon atoms,
R ³ is an alkylene group having 4 to 12 carbon atoms. ] A polyamide (a) consisting essentially of at least one of the repeating units represented by the following formula, and the following formula (3): [Here, R ⁴ is an alkylene group having 2 to 12 carbon atoms,
And R < ⁵ > is a C2-C6 alkylene group and m is an integer of 1-250. ] Or an aliphatic polyether ester (b) substantially consisting of a repeating unit represented by the following formula and the following formula (4): [Here, Ar is a trivalent aromatic group having 6 to 10 carbon atoms, R ⁶ is an alkylene group having 2 to ⁶ carbon atoms, and n is 1
Is an integer of ˜250. M ⁺ represents an alkali metal ion, an alkaline earth metal ion, a phosphonium ion or an ammonium ion. ] A sulfonate-containing polyether ester (c) or a raw material thereof, and 5 to 100 parts by weight of an aromatic monohydroxy compound (per 100 parts by weight of the total weight of the above (a), (b) and (c) ( A process for producing a polyamide ether ester, which comprises subjecting d) to a heat-melting reaction in the presence of a transesterification catalyst, and then distilling off the aromatic monohydroxy compound. 2. The aromatic monohydroxy compound (d) is represented by the following formula (5): [Here, X is an alkyl group having 1 to 3 carbon atoms, a halogen atom, and z is an integer of 0 to 3. ] It is a compound represented by these, The manufacturing method of the polyamide ether ester of Claim 1 characterized by the above-mentioned. 3. The polyether according to claim 1, wherein the amounts of (a), (b) and (c) used satisfy the weight ratio of the following formula (6) and the molar ratio of (7). Method for producing ester. ## EQU1 ## 10/90 ≤ A / (B + C) ≤ 80/20 (6) 5/95 ≤ C '/ B' ≤ 50/50 (7) [where A, B and C are respectively The above (a),
Weight based on repeating units (b) and (c). B ',
C'is a molar amount based on the repeating units of (b) and (c) described above. ]