JPH10298263A - Urethane-bond-containing polyether ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane-bond-containing polyether ester which has moderate dispersibility and, when added to a thermoplastic resin, can give a composition capable of giving a molding having excellent antistatic properties and good appearance by bonding polyether ester segments having a specified number- average molecular weight to each other through urethane bonds formed as a result of a reaction with a diisocyanate. SOLUTION: This polyether ester is obtained by reacting a polyether ester comprising 15-50 wt.% organic dicarboxylic acid units, 1-15 wt.% organic dihydroxy compound units and 35-84 wt.% poly(oxyalkylene) glycol units with a diisocyanate and having an increased molecular weight. Namely, a urethane- bond-containing polyether polyester having a number-average molecular weight of 120,000-400,000 and prepared by bonding polyether ester segments having a number-average molecular weight of 60,000-100,000 in terms of the polymethyl methacrylate to each other through urethane bonds formed as a result of reaction with a diisocyanate is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel polyetherester having a urethane bond, and more particularly, when blended with various thermoplastic resins, has little coloring, has good surface appearance, and has antistatic properties. The present invention relates to a polyetherester having a urethane bond with high productivity while providing a molded article having excellent durability.

[0002]

2. Description of the Related Art Acrylic resin has transparency, surface gloss,
Because of its excellent surface hardness, weather resistance, etc., vehicle exterior parts such as lighting fixture covers and tail lenses, lenses, light guide plates,
They are widely used for optical components such as video discs and projection television screens, front panels of vending machines, outdoor signs, and store displays.

On the other hand, polycarbonate resins make use of their transparency and impact strength to make use of vehicle exterior components such as transparent skylights for headlamp lenses and sunroofs, optical components such as compact discs, transparent noise barriers on highways, arcade domes, and the like. It is used for applications such as building materials.

[0004] Acrylic resins and polycarbonate resins are used in these applications because they have the characteristic of being substantially amorphous and transparent. These resins are generally used. It has the drawbacks that it is easily charged and dust adheres to the product, so that transparency and surface appearance are impaired, and that it also hinders post-processing of molded articles and sheets. For this reason, in order to prevent such dust from adhering, it is customary to give these resins an antistatic property.

Methods for imparting antistatic properties to acrylic resins and the like include a method of applying an antistatic agent such as a silicon compound to the resin surface, a method of adding and mixing a surfactant to the resin, and a method of imparting hydrophilicity. A method of copolymerizing a monomer having a group or an ionic group and chemically modifying a resin is known.

However, the method of applying an antistatic agent requires an additional application step for a molded article such as a structure or a sheet, which is disadvantageous in terms of cost and
The obtained product has a disadvantage that the effect is easily lost due to contact with other objects or running water such as rainfall, and the durability of the antistatic property is lacking. As a method of mixing a surfactant, for example, a method of kneading a compound having a sulfonic acid group or a polyether with a compound having a sulfonic acid group (JP-A-47-26438, JP-A-3-4344).
No. 0), a method of kneading a compound having a sulfonic acid group, a polyoxyalkylene glycol, and a specific phosphorus compound (Japanese Patent Publication No. 53-30724), etc., are provided, but sufficient antistatic properties are obtained. Requires a relatively large amount of compounding, so that the antistatic agent is liable to bleed out on the surface of the molded product, impairing the surface appearance and causing stickiness. Also, a method of kneading a polyalkylene glycol and a higher fatty acid monoglyceride (JP-B-53-36865) and a method of using a specific phosphorus compound in combination (JP-B-53-15896, JP-A-54-74849). However, since the glass transition temperature of the acrylic resin is relatively high and the migration of monoglyceride to the molded product surface is low, a large amount of monoglyceride is added to impart sufficient antistatic properties. And there is a disadvantage that the surface appearance is impaired. In addition, a method of kneading an alkyl sulfonate or an alkylbenzene sulfonate with a trialkyl phosphite has been proposed (Japanese Patent Application Laid-Open No. 24845/1988), but it is necessary to use a relatively large amount of an alkyl sulfonate or the like. Therefore, there is a disadvantage that the surface appearance of the resin is deteriorated. Further, a drawback common to these methods is that the added surfactant is easily lost from the surface of the molded article due to running water or the like, so that the durability of the antistatic property is low.

Further, the copolymer of a hydrophilic monomer includes, for example, a copolymer of a sulfosuccinate-based monomer and an acrylate-based monomer and an acidic phosphate or an alkylene oxide compound. Compositions (JP-A-59-182837, JP-A-59-18)
No. 2838), which is advantageous from the viewpoint of the durability of the antistatic effect, but it is necessary to copolymerize a relatively large number of special monomers in order to achieve a sufficient effect. It is not only disadvantageous in terms of cost but also inevitably decreases in weather resistance and heat resistance.

On the other hand, in order to improve the durability of the antistatic effect, a method of adding a polymer type antistatic agent, for example, a method of kneading a vinyl copolymer containing hydrophilic and ionic groups, a polyether amide A method of kneading a system polymer has been proposed. Regarding the former method of kneading a vinyl copolymer, for example, a method of kneading a vinyl copolymer having a polyoxyethylene chain and a sulfonate or quaternary ammonium salt structure with an acrylic resin (Japanese Patent Laid-Open No.
5-36237 and JP-A-63-63739) have been proposed. However, since this method uses expensive special monomers, it is inevitable that the cost will increase.
There is a disadvantage that the heat resistance of the acrylic resin is reduced.

As for the method of kneading a polyether amide polymer, for example, a method of kneading a polyether amide polycondensate comprising a polyamide segment and a polyether segment as an antistatic component in an acrylic resin (Japanese Patent Laid-Open No. 64-90246, JP-A-1-30
8444 and JP-A-8-120147), which have a long-lasting effect of antistatic properties, but a polycondensate containing a polyamide segment, when itself comes into contact with air at high temperature. In addition to easy thermal coloring, especially in the case of acrylic resin, a polycondensate containing a polyamide segment causes a cross-linking reaction under heating with this to easily generate an insoluble and infusible gel-like substance, which stays in the extruder The resulting raw material becomes a colored gel and is mixed into an injection-molded product or sheet, which has the disadvantage of significantly impairing the appearance of the product.

In order to improve such disadvantages of gelation and coloring foreign matter, a polyether ester containing a polyether component comprising a polyoxyalkylene glycol segment having a specific molecular weight in a specific ratio and having a specific reduced specific viscosity is used. An antistatic resin composition comprising a system polycondensate and an acrylic resin has been proposed (Japanese Patent Application No. 6-271988).
issue). However, although this polyetherester-based polycondensate is considered to have a relatively easy crystallization property, the fluidity of the polyetherester itself has a considerably large temperature dependence. That is, when taken out of the reactor in a molten state and granulated, the polymer is rapidly solidified from an extremely low viscosity with a decrease in its surface temperature,
There was a problem that stable post-processing was difficult and productivity was poor. Furthermore, when the polyetherester-based polycondensate is mixed with an acrylic resin or the like to prepare an antistatic molding material, it is important to appropriately control the dispersion state from the viewpoint of imparting an antistatic property. However, since the polyetherester polycondensate itself has a large temperature dependence of fluidity, there is a problem that the range of kneading conditions for realizing a good dispersion state is narrow. Further, the polycondensate is
Since the molecular weight is not large enough, when mixed with an acrylic resin, it is easy to be finely dispersed in a domain of 0.03 μm or less, and it is difficult to provide sufficient antistatic properties.

Incidentally, polyetheresters are generally obtained by copolycondensation of poly (oxyalkylene) glycol, diol and dicarboxylic acid or dicarboxylic acid ester, but until now the number average molecular weight is at most about 100,000. (JP-A-6-57153).

The polyetherester has no intermolecular hydrogen bond derived from the polyamide moiety as compared with the polyetheramide polycondensate, and therefore has a much lower melt viscosity even with the same molecular weight. Therefore, when kneading with an acrylic resin or the like, the difference in viscosity between the polyetherester and the matrix resin at the processing temperature (generally, the viscosity of the matrix resin is higher) is higher than that of the polyetheramide polycondensate and the matrix resin. Is larger than the viscosity difference of the polyether amide polycondensate, and it is easy to be miniaturized due to the shear during processing. In view of the effect of imparting antistatic properties, it is considered that it is not preferable that the polymer type antistatic agent is too finely dispersed in the matrix resin. Therefore, polyetherester is used as the polymer type antistatic agent. In this case, it is understood that the viscosity must be compensated for by significantly increasing the molecular weight as compared with the polyetheramide polycondensate.

However, as described above, it has been difficult to increase the number average molecular weight of the polyether ester to more than 100,000, so that the use of the polyether ester as a polymer type antistatic agent is limited. I could not escape.

[0014]

SUMMARY OF THE INVENTION Under such circumstances, the present invention has a proper dispersing property when mixed with a thermoplastic resin such as an acrylic resin or a polycarbonate resin, and has an antistatic property. An object of the present invention is to provide a highly productive polyetherester which is excellent in persistence, has little coloring, and can provide a molded article having a good appearance.

[0015]

The present inventors have conducted various studies on polyetheresters. As a result, the known polyetherester having a low molecular weight is reacted with diisocyanate so as to be linked by a urethane bond. And, the molecular weight can be improved without deteriorating the preferable physical properties inherent in polyetherester, and as a polymer type antistatic agent, it can be blended with acrylic resin or polycarbonate resin with good dispersibility. The present inventors have found that it is possible to provide a molded article having a good appearance without coloring, which can maintain the antistatic property for a long period of time, and have accomplished the present invention based on this finding.

That is, the present invention provides an organic dicarboxylic acid unit of 15 to 50% by weight and an organic dihydroxy compound unit of 3 to
A polyether ester segment having a number average molecular weight of 60,000 to 100,000 in terms of polymethyl methacrylate composed of 20% by weight and 35 to 80% by weight of a poly (oxyalkylene) glycol unit forms a urethane bond formed by reaction with a diisocyanate. And a polyetherester having a number average molecular weight in terms of polymethyl methacrylate of 120,000 to 400,000 and containing a urethane bond.

Incidentally, the number average molecular weight in terms of polymethyl methacrylate in the present invention was obtained by measuring gel permeation chromatography (GPC) at 40 ° C. using hexafluoroisopropanol as a solvent and measuring standard polymethyl methacrylate in advance. This is calculated by comparing with a calibration curve graph of elution count and molecular weight.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyether ester segment in the present invention is a known polyether ester having a low number average molecular weight described in, for example, JP-A-6-57153.
To 50% by weight, 1 to 15% by weight of an organic dihydroxy compound unit and 35 of a poly (oxyalkylene) glycol unit
-84% by weight.

In the present invention, such a low molecular weight polyetherester is reacted with diisocyanate to obtain a higher molecular weight polyetherester. Therefore, the organic dicarboxylic acid unit, the organic dihydroxy compound unit and the poly (oxyalkylene) glycol unit in the polyether ester segment in the present invention are the same as the respective structural units in the polyether ester known so far. These structural units are derived from the organic dicarboxylic acid or its ester organic dihydroxy compound and poly (oxyalkylene) glycol used as raw materials, respectively.

Such organic dicarboxylic acids or esters thereof include, for example, aromatic dicarboxylic acids having 8 to 14 carbon atoms such as terephthalic acid, phthalic acid and isophthalic acid, and 4 carbon atoms such as adipic acid, sebacic acid and malic acid. ~ 24
Aliphatic dicarboxylic acids having 8 to 16 carbon atoms, such as cyclohexane-1,4-dicarboxylic acid,
And methyl, ethyl, propyl, and butyl esters thereof. Among these, terephthalic acid and isophthalic acid, or a combination of terephthalic acid methyl, ethyl ester and isophthalic acid methyl, ethyl ester, the softening temperature of the resulting polyetherester, the temperature dependence of the fluidity of the polymer and It is preferable from the viewpoint of easy handling.

Further, as the organic dihydroxy compound,
Aliphatic dihydroxy compound having 2 to 22 carbon atoms, 6 carbon atoms
To 14 alicyclic dihydroxy compounds, and 6-1 carbon atoms
And 2 aromatic dihydroxy compounds. These can be used alone or in combination of two or more. Specific examples include ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1, Aliphatic dihydroxy compounds such as 8-octanediol, alicyclic dihydroxy compounds such as 1,4-cyclohexanediol and bis-1,4-hydroxymethylcyclohexane, and hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, 4'-dihydroxydiphenyl ether,
Aromatic dihydroxy compounds such as bisphenol A are mentioned. Here, for example, in the case of a high-boiling aliphatic dihydroxy compound having more than 22 carbon atoms, it is difficult to remove excess dihydroxy compound from the reaction system during the polycondensation reaction, which is not preferable. Among them, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4
-Butanediol is preferred, but ethylene glycol and 1,4-butanediol are particularly preferred from the viewpoint of reactivity.

Next, examples of the poly (oxyalkylene) glycol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, ethylene glycol / propylene glycol block copolymer. Other than polyoxyalkylene glycol, such as hydroxynon, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether,
Examples include ethylene oxide adducts such as bisphenol A and propylene oxide adducts. Of these, the use of polyoxyethylene glycol, polyoxypropylene glycol, or an ethylene oxide adduct of bisphenol A or a propylene oxide adduct is preferred because a polycondensate having good antistatic properties can be obtained. These compounds may be used alone or in combination of two or more. Use of a combination of polyoxyethylene glycol and polyoxytetramethylene glycol is preferred because the resulting polyetherester has good antistatic properties and excellent mechanical strength.

The number average molecular weight of the poly (oxyalkylene) glycol is preferably from 400 to 20,000, more preferably from 600 to 12,000, and still more preferably from 20.
The range is from 00 to 9000. When the number average molecular weight of this compound is less than 400, the softening temperature of the obtained polyether ester becomes low, and it becomes sticky even at room temperature, making it difficult to handle. In addition, the water absorption becomes excessive, and the water content is not thoroughly controlled during processing. The resulting polyetherester is not practical because it causes problems such as easy hydrolysis. On the other hand, when the number average molecular weight exceeds 20,000, the effect of imparting the antistatic property of the obtained polyether ester is reduced, and the thermal decomposability of the polyether ester during processing is undesirably increased.

In the polyetherester of the present invention, the organic dicarboxylic acid unit is 15 to 50% by weight, the organic dihydroxy compound unit is 3 to 20% by weight, and the poly (oxyalkylene) glycol unit is based on the total weight of the polyetherester segment. It is necessary that the composition be 35 to 80% by weight.

When the amount of the organic dicarboxylic acid unit is less than 15% by weight, the softening temperature of the polyether ester becomes low,
Even at room temperature, it is not preferable because it becomes sticky. on the other hand,
If the amount exceeds 50% by weight, the solidification temperature of the polyetherester becomes high, and becomes unstable when the polyetherester is taken out of the reactor, and the effect of imparting antistatic properties is undesirably reduced. The organic dihydroxy compound is 3% by weight.
If it is less than 1, the softening temperature of the polyetherester becomes low, and it becomes easy to stick at room temperature, which is not preferable.
On the other hand, when the content exceeds 20% by weight, the effect of imparting the antistatic property of the polyetherester is reduced, which is also not preferable.

On the other hand, if the amount of the poly (oxyalkylene) glycol unit is less than 35% by weight, the molecular weight does not increase even if the organic diisocyanate is reacted, and if it exceeds 80% by weight, the molecular weight does not increase even if the organic diisocyanate is reacted. In addition, the amount of low molecular weight components increases.

The polyetherester segment of the present invention comprises, for example, 30 to 75% by weight of a poly (oxyalkylene) glycol, 20 to 60% by weight of an organic dicarboxylic acid or an ester thereof, and an organic dihydroxy compound 5
A raw material mixture consisting of ４０40% by weight is charged into a reactor, and in the presence or absence of a solvent, polycondensation is performed by removing water or alcohol generated during the reaction to the outside of the reactor to increase the molecular weight. Can be manufactured. In order to remove water or alcohol outside the reactor, it is advantageous to carry out the process by flowing nitrogen gas or by reducing the pressure inside the reactor to a high degree. The temperature during the polycondensation is usually 150 to 3
00 ° C, preferably in the range of 180 to 270 ° C.

In this reaction, an organic dihydroxy compound and an organic dicarboxylic acid or an ester thereof are converted to a compound of the general formula

Embedded image (Wherein R ¹ is a residue obtained by removing two carboxyl groups or ester groups from an organic dicarboxylic acid or an ester thereof;
² is a residue obtained by removing two hydroxyl groups from an organic dihydroxy compound) to form a high molecular weight by combining the structural units derived from poly (oxyalkylene) glycol. . That is, in order to obtain a high molecular weight polyether ester, the total number of moles of the terminal hydroxy group of the poly (oxyalkylene) glycol and the hydroxyl group of the organic hydroxy compound is determined by the number of moles of the carboxyl group of the organic dicarboxylic acid or its ester. The number must exactly match the number, but in order to satisfy this relationship, an organic dihydroxy compound is generally preliminarily charged to the reaction system in advance, and the reaction proceeds while distilling off the excess organic dihydroxy compound outside the reaction system. The method is preferably used. Therefore, if the preparation composition of the poly (oxyalkylene) glycol and the organic dicarboxylic acid or its ester is determined, if the production is carried out under the ordinary conditions in which these do not distill out of the reaction system, the resulting polyether ester It is considered that the ratio of the organic dihydroxy compound unit is automatically determined.

In the polyetherester segment of the present invention, the polyether portion (A) and the polyester portion (B) may each contain one kind,
A mixture of two or more types may be used, but it is necessary that the total of the polyether portion (A) and the total of the polyester portion (B) be in a weight ratio of 3: 7 to 8: 2. is there. When the proportion of the polyether moiety (A) is less than the above range, the effect of imparting the antistatic property of the polyether ester is insufficient, and when it is more than the above range, the effect of imparting the antistatic property also decreases. From the viewpoint of imparting an antistatic property, the polyether portion (A) and the polyester portion (B)
Is particularly preferably in the range from 4: 6 to 7.5: 2.5 by weight. That is, the content ratio of the polyether portion (A) has an optimum range. There are still many unclear points about the mechanism by which this phenomenon occurs. The main component that exhibits antistatic properties is a hydrophilic polyoxyalkylene glycol component, and if the proportion is small, it is considered that the effect of imparting antistatic properties is reduced.
On the other hand, if this ratio is high, the compatibility of the polyetherester with the acrylic resin or the like is improved, and the polyetherester is dispersed very finely in the resin, which is considered to be effective in imparting antistatic properties. It is presumed that the morphological feature of "island structure" is hardly exhibited, and the performance is reduced.

In this polycondensation reaction, a catalyst can be used if desired. Examples of the catalyst include manganese acetate, calcium acetate, cobalt acetate, zinc acetate, antimony trioxide, titanium tetraalkoxide, and an organic zirconium compound. The use of such a catalyst is advantageous in that the reaction time can be shortened, and as a result, coloring and deterioration of the polymer during the reaction can be prevented.

When producing the polyetherester, it is preferable to add a suitable heat stabilizer in order to prevent the polymer from undergoing thermal degradation during the reaction and to realize a high molecular weight. As the heat stabilizer, for example,
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxycinnamide, 4,4'-bis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-
hindered phenol-based stabilizers such as tert-butylphenol) and pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; N, N'-bis (β-naphthyl) -P-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl-1,2-
Examples include amine stabilizers such as dihydroquinoline), sulfur stabilizers such as dilaurylthiodipropionate, and phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite. These may be added to the raw materials in advance by an arbitrary method, such as mixing them in advance during the polycondensation reaction or adding them to the reactor in the middle.

The polyetherester containing a urethane bond of the present invention is produced by reacting the above-obtained etherester with diisocyanate, linking the polyetherester via the urethane bond, and further increasing the molecular weight. You. As the diisocyanate for use in this, for example, compounds represented by the general formula OCN-R ³ -NCO is used. In this general formula, R ³ is an arylene group having 6 to 12 carbon atoms and 2 to 2 carbon atoms.
It is at least one divalent hydrocarbon group selected from 22 alkylene groups and cycloalkylene groups having 6 to 14 carbon atoms. Here, as the arylene group having 6 to 12 carbon atoms, for example, a phenylene group, a naphthylene group, a methylenebisphenylene group or the like, and as the alkylene group having 2 to 22 carbon atoms, for example, a butylene group, a hexamethylene group, an octylene group, or the like can be given. However, examples of the cycloalkylene group having 6 to 14 carbon atoms include a cyclohexylene group and a cyclooctylene group. In the case of an arylene group or a cycloalkylene group, an inert substituent such as a lower alkyl group, a lower alkoxyl group, or a halogen may be introduced into the carbon ring.

Examples of such diisocyanates include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, methylene bis (4-phenyl isocyanate), xylylene diisocyanate, and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexyl isocyanate. Of these, hexamethylene diisocyanate and methylene bis (4-phenyl isocyanate) are particularly preferred. These may be used alone or in combination of two or more.

When the diisocyanate is reacted in this manner, the diisocyanate reacts with the terminal hydroxyl group of the polyether ester to form a compound represented by the general formula

Embedded image (Wherein R ³ has the same meaning as described above), and a structural unit having a urethane bond is formed. The formation of the urethane bond can be easily detected by infrared absorption spectrum and ¹³ C-NMR spectrum (edited by the Society for Analytical Chemistry of Japan, Polymer Analysis Research Council, “Polymer Analysis Handbook”,
507, Asakura Shoten, 1985).

In this case, the amount of the diisocyanate to be used is preferably in the range of the same molar number as the terminal hydroxyl group of the polyetherester to twice the molar number. If the amount is less than 0.01% by weight based on the polyetherester, the molecular weight may be insufficiently increased. On the other hand, if the amount exceeds 1% by weight, crosslinking and gelation may occur due to side reactions during the addition reaction. It is easy to occur.

The addition reaction between the diisocyanate and the terminal hydroxyl group of the polyetherester can be carried out by a method generally used in the production of polyurethane, and is not particularly limited. For example, (1) polyetherester After manufacturing in a reaction tank with a stirrer,
A method of adding a diisocyanate to a reaction vessel and performing an addition reaction while further stirring to produce a high molecular weight polyetherester having a urethane bond. (2) Manufacturing a polyetherester in a reaction vessel equipped with a stirring machine, followed by melting. A method for producing a high-molecular-weight polyetherester having a urethane bond, by supplying the kneader in a state as it is and performing an addition reaction in the kneader while injecting diisocyanate,
(3) After the polyetherester is produced in a reaction vessel equipped with a stirrer, the mixture is once discharged, solidified and granulated, then kneaded with an extruder or a kneader-type kneader, and subjected to an additional reaction. A method for producing a high molecular weight polyetherester having a urethane bond is used. The reaction temperature is not particularly limited and may be selected in consideration of productivity, suppression of side reactions, prevention of decomposition of polyetherester, and the like, but is generally preferably in the range of 150 to 260 ° C. Since diisocyanate easily reacts with moisture in the air, it is necessary to pay attention to nitrogen substitution in a reactor, an extruder and the like when performing an addition reaction.

The polyetherester having a urethane bond of the present invention comprises a component having a molecular weight of 10,000 or less as measured by gel permeation chromatography at 40 ° C. using hexafluoroisopropanol as a solvent.
Preferably, it is less than 1% of the total area of the chromatogram. The components having a molecular weight of 10,000 or less represent 1 of the total area of the chromatogram.
%, When the polyetherester is kneaded with an acrylic resin or the like to produce a molded product, a die-like material tends to precipitate on the lip portion of the die, which adheres to the surface of the molded product. It is not preferable because the surface of the molded article may be fogged or sticky cloudiness may occur on the polishing roll surface to impair the smoothness of the molded product surface.

In order for components having a molecular weight of 10,000 or less to be 1% or less of the total area of the chromatogram, generally,
It is preferable to note the following points. That is, (1) Care should be taken to use a reactor having a good stirring effect provided with a helical ribbon stirring blade and the like so as to eliminate local heating and uneven composition during the reaction, so that the reaction proceeds uniformly. (2) When the molecular weight of the polyoxyalkylene glycol is low, components having a molecular weight of 10,000 or less are easily formed, so that
A high molecular weight polyoxyalkylene glycol is used as a raw material, and the number average molecular weight of the produced polyether ester is increased by the method described above. (3) In order to avoid the thermal decomposition reaction of the polyetherester, the reaction is carried out at a reaction temperature of 260 ° C. or lower while avoiding the incorporation of air.

Further, the polyetherester having a urethane bond of the present invention preferably has a relative viscosity in m-cresol at 30 ° C. in the range of 2.1 to 4.0. When the relative viscosity is less than 2.1, the fluidity of the polymer itself is large, and when kneaded with an acrylic resin or the like,
There is a possibility that the polyetherester is finely dispersed in the resin and the effect of imparting antistatic properties is reduced. On the other hand, when the relative viscosity is more than 4.0, the fluidity of the polymer itself is reduced, making it difficult to take out of the reactor, and when kneaded with an acrylic resin or the like, the polyether ester is hardly dispersed. However, the effect of imparting the antistatic property is undesirably reduced.

Further, the polyetherester having a urethane bond of the present invention has a temperature at which the melt flow rate measured under a load of 1 kg is 1 g / 10 minutes or less, that is, the temperature at which solidification starts substantially ranges from 160 to 220 ° C. Preferably, the temperature is in the range of 170 to 210 ° C. This is for the following reasons. That is, as a method for producing a polyetherester having properties as in the present invention, a melt polycondensation method in a temperature range of 240 to 280 ° C. is generally used. In many cases, a step of taking out, and further pulverizing the polymer itself for convenient packaging and kneading with an acrylic resin is often carried out. Therefore, when the temperature at which the polymer substantially solidifies approaches 220 ° C. and approaches the reaction temperature, the surface of the polymer discharged from the reactor immediately begins to harden, and the polymer discharged in a sheet shape is wound around a cooling drum. In addition, it is difficult to stably carry out a process in which a polymer discharged in the form of a strand is taken out by a roll and introduced into a cutter.
As a result, the polymer cannot be stably taken out of the reactor, and productivity is significantly impaired. On the other hand, when the temperature at which the polymer substantially solidifies is lower than 160 ° C., the polymer taken out of the reactor becomes sticky, and it is also difficult to stably perform the post-treatment step.

Load 1 k of the polyetherester of the present invention
The temperature at which the melt flow rate in g becomes 1 g / 10 minutes or less, that is, the temperature at which solidification substantially starts is 160 to 2
Several methods are conceivable for achieving the range of 30 ° C. It is believed that the solidification phenomenon of the polyetherester is largely defined by the crystallinity of the polyester portion in the polymer. Therefore, in order to reduce the crystallinity of the polyester portion, it is effective to shorten the chain length of the polyether portion incorporated in the polymer and to shorten and connect both blocks of the polyester portion and the polyether portion. . It is also effective to introduce a component having low crystallinity into the polyester portion. For example, an aliphatic dicarboxylic acid component is introduced. However, these methods all have the disadvantage that they cause stickiness of the polymer at room temperature and make handling extremely difficult. Compared to the polymer obtained by these methods, the polyetherester containing a urethane bond of the present invention has less change in fluidity at constant temperature during removal and kneading after the reaction,
Further, even the tackiness at room temperature is improved, which is extremely practical.

The polyetherester having a urethane bond according to the present invention has a number average molecular weight of 120,000 to 400,000 in terms of polymethyl methacrylate measured by gel permeation chromatography at 40 ° C. using hexafluoroisopropanol as a solvent. Must be in range. If the number average molecular weight is less than 120,000, the polymer itself is slightly brittle and easily dispersed when kneaded with an acrylic resin, etc., and the effect of imparting antistatic properties becomes insufficient. The melt viscosity of itself becomes too high, and the handleability during production is poor, and when kneaded with an acrylic resin, it is difficult to uniformly disperse,
Again, the effect of imparting antistatic properties is reduced. The number average molecular weight is particularly preferably in the range of 140,000 to 300,000 from the viewpoints of imparting antistatic properties, polymer properties, and handling properties of the polymer during production.

The polyetherester containing a urethane bond of the present invention can be mixed with a thermoplastic resin such as an acrylic resin or a polycarbonate resin to produce an antistatic resin composition. Further, the resin composition can be extrusion molded to produce an antistatic sheet, or injection molded to produce various molded articles having antistatic properties.

The acrylic resin used here is preferably one comprising 50 to 99% by weight of a methyl methacrylate unit and 1 to 50% by weight of another monomer unit copolymerizable therewith. Other copolymerizable monomers include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl group,
In addition to alkyl acrylates having 1 to 18 carbon atoms, α, β-unsaturated acids such as acrylic acid and methacrylic acid, divalent carboxylic acids containing unsaturated groups such as maleic acid, fumaric acid and itaconic acid, and styrene , Α-methylstyrene, aromatic vinyl compounds such as nuclear-substituted styrene, maleic anhydride, maleimide, N-substituted maleimide and the like, which may be used alone or in combination of two or more. Good. In addition, a copolymer of methyl methacrylate and methacrylic acid or acrylic acid may be subjected to a heat-treatment to remove alcohol or dehydrate to form a 6-membered cyclic anhydride unit, or a mixture of ammonia, amine and imide. The polymer also includes a polymer in which a six-membered ring imide unit is produced by a polymerization reaction. Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoints of light resistance, heat decomposition resistance, and fluidity of the copolymer. ,
Particularly, methyl acrylate, ethyl acrylate and n-butyl acrylate are preferred.

This acrylic resin is used in chloroform.
Those having a reduced viscosity at 5 ° C. of 30 to 90 ml / g are preferably used. When the reduced viscosity is less than 30 ml / g, the mechanical strength of the obtained antistatic resin composition is reduced. On the other hand, when the reduced viscosity is more than 90 ml / g, the obtained antistatic resin composition has Both are not preferred because the fluidity is reduced and extrusion molding and injection molding become difficult.

The method for producing such an acrylic resin is not particularly limited, and includes suspension polymerization, emulsion polymerization, bulk polymerization,
Alternatively, any of known methods such as solution polymerization may be used. As the polymerization initiator, an ordinary peroxide-based or azo-based radical polymerization initiator can be used, and this may be used as a redox-based initiator in combination with a reducing agent. An acrylic resin obtained by an anionic polymerization method using an alkyl lithium or the like, a coordination polymerization method using an organometallic complex, a group transfer polymerization method, or the like may be used. The polymerization temperature is generally about 30 to 100 ° C. for suspension polymerization or emulsion polymerization, and about 80 to 170 ° C. for bulk or solution polymerization.
In order to control the reduced viscosity of the acrylic resin, it may be carried out by using an alkyl mercaptan or the like as a chain transfer agent. In addition, an acrylic resin composition having impact resistance imparted by a multilayer acrylic rubber or the like can be used.

On the other hand, as the polycarbonate resin, a polymer derived from a divalent phenol compound represented by bisphenol A can be used. The polycarbonate resin is not particularly limited, and any resin produced by a phosgene method, a transesterification method, a solid phase polymerization method, or the like can be used. Although there is no particular limitation on the molecular weight of the polycarbonate resin, when it is used as an extruded plate or an injection molded product, the weight average molecular weight obtained from a calibration curve using a GPC method and monodisperse polystyrene as a standard is 20,000 to 100,000. Are preferred,
Those having a molecular weight of 30,000 to 80,000 are particularly preferred.

The thermoplastic resin capable of producing the antistatic resin composition by mixing the polyetherester containing a urethane bond of the present invention is not limited to the above-mentioned acrylic resin and polycarbonate resin. A wide range of common resins can be used. That is,
Polystyrene, high impact polystyrene, ABS resin, M
BS resin, amorphous copolyester, etc. can be used alone or in combination of two or more.

When the antistatic resin composition is produced by mixing the polyetherester containing a urethane bond of the present invention with a thermoplastic resin such as an acrylic resin or a polycarbonate resin, the polyetherester is used in an amount of 30 to 2 parts. %, Preferably 25 to 5% by weight and the thermoplastic resin 70 to
It is advantageous to mix 98% by weight, preferably 75-95% by weight. When the polyether ester is less than 2% by weight, the obtained resin composition has insufficient antistatic properties. On the other hand, when the polyether ester exceeds 30% by weight, the mechanical strength of the obtained resin composition is poor. The strength is undesirably reduced. The mixing method for producing the antistatic resin composition is not particularly limited, and may be, for example, a method of mixing with a drum blender or a Henschel mixer, or a method of mixing with these methods and then using an extruder to prepare a mixture of 200 to 280.
For example, a method of granulating at a temperature of about ° C can be used. In the case of extrusion mixing, in order to suppress the thermal decomposition and hydrolysis of the polyetherester, it is preferable to perform the mixing while paying attention to the extrusion temperature, the water content of the polyetherester, the nitrogen purge in the extruder, and the like.

When the antistatic resin composition is produced by mixing the polyetherester containing a urethane bond of the present invention with a thermoplastic resin such as an acrylic resin or a polycarbonate resin, the antistatic property is further improved. At least one compound selected from organic sulfonates and organic phosphates may be used in combination. Examples of these compounds include aromatic sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid; alkylsulfonic acids such as laurylsulfonic acid and stearylsulfonic acid; diphenyl phosphite; and diphenyl phosphate. And alkaline earth metal salts such as organic phosphoric acid. Sodium salts and potassium salts are preferred from the viewpoint of the antistatic effect of the resin composition.
The amount of the organic sulfonate or organic phosphate is preferably 5 parts by weight or less based on 100 parts by weight of the antistatic resin composition. When the amount is more than 5 parts by weight, the mechanical strength of the obtained resin composition is lowered, and the resin composition is liable to be colored, which is not preferable.

In the production of the polyetherester containing a urethane bond according to the present invention, poly (oxyalkylene) glycol, an organic dihydroxy compound and an organic dicarboxylic acid or an ester thereof are polycondensed to produce a polyetherester. Alternatively, a compound containing a sulfonate or a phosphate in the molecule, for example, isophthalic acid containing a sulfonate or an alkyl ester thereof may be copolycondensed and introduced into the polyetherester. When a compound unit containing a sulfonate or a phosphate is introduced into the molecule, the content is preferably 10% by weight or less, more preferably 5% by weight or less, in the polyetherester. When the compound unit exceeds 10% by weight, the resulting polyetherester has an excessively high hygroscopicity, and hydrolysis is likely to occur unless attention is paid to water control in the production of the resin composition, which is not preferable.

When the antistatic resin composition is prepared by mixing the polyetherester containing a urethane bond of the present invention with a thermoplastic resin such as an acrylic resin or a polycarbonate resin, the amount of the antistatic resin composition is not impaired. For example, various dyes, pigments, organic light diffusing agents such as methyl methacrylate / styrene copolymer beads, inorganic light diffusing agents such as barium sulfate, titanium oxide, calcium carbonate, talc, hindered phenol, phosphoric acid Heat stabilizers such as salts, antioxidants, benzotriazoles, 2-hydroxybenzophenones, ultraviolet absorbers such as salicylic acid phenyl esters, phthalic acid esters, fatty acid esters, trimellitic acid esters, phosphate esters -Based, polyester-based plasticizers, higher fatty acids, higher fatty acid esters, higher Release agents such as mono-, di- or triglycerides of fatty acids, lubricants such as higher fatty acid esters and polyolefins, flame retardants such as phosphorus-based, phosphorus / chlorine-based and phosphorus / bromine-based, reinforcement of glass fiber, carbon fiber, etc. Agents and the like may be mixed and used.

The antistatic resin composition obtained by mixing the polyetherester containing a urethane bond of the present invention with a thermoplastic resin such as an acrylic resin or a polycarbonate resin is prepared by extrusion molding. , And various molded articles can be produced by injection molding. These moldings are preferably performed at a resin temperature of about 180 to 270 ° C. to prevent burning and deterioration of the resin.

[0054]

According to the present invention, the polyetherester containing a urethane bond is mixed with a thermoplastic resin such as an acrylic resin or a polycarbonate resin to produce a polymer type antistatic agent for producing an antistatic resin composition. It is suitable as. In addition, when the polyetherester having a urethane bond of the present invention is mixed with an acrylic resin or the like to produce an antistatic extruded plate or a molding material, it is hardly thermally colored at the time of kneading or extrusion molding, and is crosslinked and gelled. A product with extremely good appearance and excellent durability of antistatic properties can be obtained because of no occurrence of fogging.Furthermore, the polishing roll for extruded plate production and the mold for injection molding are hardly clouded, and the surface appearance is good. Products can be obtained stably. Therefore, the polyetherester containing a urethane bond of the present invention can be used in applications that dislike charging and dust adhesion such as lighting fixture covers, semiconductor component transport containers, fixtures used in clean rooms, front panels of projection televisions, and optical lenses. Is suitable for producing an antistatic resin composition.

[0055]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation and test methods are shown below.

(1) Gel Permeation Chromatography (GPC) Analysis A 5 mg sample was dissolved in 5 ml of hexafluoroisopropanol, and a hexafluoroisopropanol was used. The measurement was performed at a column temperature of 40 ° C. using isopropanol as a solvent. The same measurement was carried out in advance using standard polymethyl methacrylate, a calibration curve of the elution count and the molecular weight was prepared, and the number average molecular weight of the sample was calculated from the chromatogram. Further, the area of the portion having a molecular weight of 10,000 or less was obtained from the obtained chromatogram by an integrator, and the ratio to the total area of the chromatogram was calculated and expressed in%.

(2) Relative viscosity 0.25 g of polymer was precisely weighed, and 50 ml of m-cresol was used.
And dissolved in Ostwald viscometer No. Using 3, 30
The flow time was measured at ° C. The flow time of m-cresol used for dissolution was measured in the same manner. The relative viscosity is
It was calculated as the ratio of the flowing time of the polymer in m-cresol and the flowing time of m-cresol. (3) Polymer composition ¹ H-NMR analysis was performed, and the polymer composition was determined from the intensity ratio of the signal corresponding to each component. (4) Determination of carboxyl terminal group A 0.3 g sample was weighed into a test tube, and benzyl alcohol 5
g was added thereto and dissolved by heating at 190 ° C. for 5 minutes under nitrogen flow. The solution was poured into 40 g of chloroform, and the inside of a test tube was heated with 15 g of hot benzyl alcohol and 10 g of chloroform.
, And each washing solution was added to prepare a titration sample.
Phenolphthalein was titrated with a 0.1N sodium hydroxide solution in benzyl alcohol as an indicator, and the amount of carboxyl terminal groups was calculated from the required amount of sodium hydroxide.

(5) Determination of hydroxyl terminal group A sample of about 1 g was precisely weighed in a flask with branches, 20 ml of α-methylnaphthalene was added, and the mixture was heated to 240 ° C. under nitrogen flow to dissolve. The solution was cooled to 175 ° C., 1 g of succinic anhydride was added and heated for 4 hours. The solution after heating was poured into a large amount of ethanol to precipitate a polymer, which was separated by filtration, then dissolved again in α-methylnaphthalene and purified by reprecipitation. The amount of the carboxyl terminal group of the obtained polymer was quantified by the method of the above (4), and the difference from the amount of the carboxyl terminal group of the polymer not subjected to the succinic anhydride treatment was calculated as the amount of the hydroxyl terminal group.

(6) Melt Flow Rate (MFR) Using a melt indexer manufactured by Toyo Seiki Co., Ltd. while changing the barrel temperature, the melt flow rate (MFF) under a load of 1 kg
R) was measured, and a graph plotting temperature and MFR was created. From this graph, the temperature at which the MFR was 1 g / 10 minutes or less was read. (7) Surface resistance value (Rs) Using an insulation resistance meter Ultra-Megohm meter SM-8200 series SME8311 manufactured by Toa Denpa Kogyo Co., Ltd., 500 V was applied to the molded product at 23 ° C. and a relative humidity of 50% for 45 seconds. After 2 seconds, the surface resistance was measured. For sustainability evaluation, lightly rub the test piece with a cloth while running tap water.
Wipe 0 times, wipe off water droplets, and then
After 4 hours, the surface resistance was measured in the same manner as described above.

(8) Tensile test The tensile test was performed based on JIS K7113. The meanings of the abbreviations are as follows. PEG: polyoxyethylene glycol, and the number in parentheses indicates the number average molecular weight. DBS: Sodium dodecylbenzenesulfonate

Example 1 (1) Production of Polyetherester Precursor (A-1) In a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube, 51 parts by weight of dimethyl terephthalate, ethylene glycol 33
Parts by weight and 0.02 parts by weight of manganese acetate dihydrate were charged and heated at 180 to 230 ° C. for 3 hours to carry out a transesterification reaction while distilling off generated methanol.
Next, 17 parts by weight of polyoxyethylene glycol having a number average molecular weight of 1500 and antimony trioxide of 0.03 were added to the reactor.
Parts by weight and 0.015 parts by weight of trimethyl phosphate were added, and the temperature was raised to 260 ° C. The pressure inside the reactor was gradually reduced, and the internal pressure was raised to 1 while removing excess ethylene glycol.
The polycondensation reaction was carried out for 3 hours while keeping the pressure at or below torr. Thereafter, the valve at the bottom was opened while applying pressure to the reactor with nitrogen, and a small amount of the polymer was discharged to obtain a precursor sample. As a result of GPC analysis of the obtained polyetherester precursor (A-1), the number average molecular weight in terms of polymethyl methacrylate was 65,000, and the ratio of components having a molecular weight of 10,000 or less was 0.8%. The relative viscosity was 1.8. ¹
As a result of H-NMR analysis, the composition was 25% by weight of a polyoxyethylene glycol component, 58% by weight of a terephthalic acid component, and 17% by weight of an ethylene glycol component. The quantification results of the carboxyl group and the hydroxyl group were 3 eq / ton and 28 eq / ton, respectively, indicating that almost all of the hydroxyl groups were occupied.

(2) Polyetherester (A-1-
Production of 1) The valve at the bottom of the reactor was closed again, 0.35 parts by weight of hexamethylene diisocyanate was added, and the post-reaction was carried out at 250 ° C. for 1 hour while maintaining the internal pressure at 1 Torr or less. The valve at the bottom was opened again while applying pressure to the reactor with nitrogen, and the polymer was discharged in the form of a strand and cut with a pelletizer to obtain pellets. The discharge state of the polymer was stable, and the cutting property was also good. As a result of GPC analysis of the obtained polyether ester (A-1-1), the number average molecular weight in terms of polymethyl methacrylate increased to 192,000, and the proportion of components having a molecular weight of 10,000 or less was 0.2% or less. It became. As a result of ¹³ C-NMR analysis, an absorption spectrum derived from a urethane bond was confirmed. The relative viscosity was 2.3. The temperature at which the melt flow rate under a load of 1 kg was 1 g / 10 minutes or less was 230 ° C.

Examples 2 to 6 The same procedures as in Example 1 were carried out except that the charged compositions were changed as shown in Table 1. The production conditions and the results are summarized in Tables 1, 2 and 3.

Example 7 A precursor was produced in the same manner as in Example 1 except that the charged composition was changed as shown in Table 1. Precursor (A-
The quantification results of the carboxyl group and the hydroxyl group in 7) were 3 eq / ton and 22 eq / ton, respectively, and the latter was excessive. The precursor (A-7) was taken out of the reactor, solidified by cooling, and cut into fine particles. 0.35 parts by weight of hexamethylene diisocyanate was added to 100 parts by weight of the precursor (A-7), mixed and supplied to a 30 mm twin-screw extruder while purging with nitrogen, and extruded at 200 ° C. to obtain a polyetherester. (A-7-1) was obtained. As a result of GPC analysis of the obtained polyether ester (A-7-1), the number average molecular weight in terms of polymethyl methacrylate increased to 175,000, and the proportion of components having a molecular weight of 10,000 or less was 0.2% or less. It became. As a result of ¹³ C-NMR analysis, an absorption spectrum derived from a urethane bond was confirmed. The relative viscosity was 2.2. The temperature at which the melt flow rate under a load of 1 kg is 1 g / 10 minutes or less is 210 ° C.
Met. The production conditions and the results are summarized in Tables 1, 2 and 3.

Example 8, Comparative Examples 1 to 4 The same as Example 1 except that the charge composition was changed as shown in Table 1, and that in Comparative Examples 3 and 4, the temperature conditions were further changed as shown in Table 1. I went. The production conditions and the results are summarized in Tables 1, 2 and 3.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

Comparative Example 5 Production of Polyetheresteramide (B-1) Using polyoxyethylene glycol having a number average molecular weight of 1500 and ε-caprolactam as main raw materials, and further using terephthalic acid as a linking agent, a common method was used. Polycondensed. The relative viscosity of the obtained polyetheresteramide (B-1) was 2.1. According to NMR analysis, the composition was 60% by weight of a polyoxyethylene glycol component, 8% by weight of a terephthalic acid component, and 32% by weight of a caprolactam component. Was. The melt flow rate under a load of 1 kg is 1 g /
The temperature that reached 10 minutes or less was 180 ° C.

Reference Example 1 The polyether ester prepared in Example 3 (A-3-
1) 15 parts by weight, 84.5 parts by weight of an acrylic resin “Delpet LP-1” (C-1) manufactured by Asahi Kasei Kogyo Co., Ltd., and 0.5 parts by weight of sodium dodecylbenzenesulfonate were mixed by a drum blender, The mixture was kneaded and granulated at a resin temperature of about 260 ° C. using a 30 mm twin screw extruder. The obtained pellets were extruded at a resin temperature of about 260 ° C. from a 50 mm single screw extruder equipped with a T die having a width of about 30 cm, and a surface temperature of about 100 ° C.
The gap between the polishing rolls at a temperature of ° C. was adjusted to form a sheet having a thickness of 2 mm. No fogging on the polishing roll surface and no fouling on the lip of the T-die were observed during molding. A test piece was cut out from this sheet, placed in a constant temperature room at 23 ° C. and a relative humidity of 50%, and the surface resistance was measured 24 hours later. As a result, it was 8 × 10 ¹⁰ Ω. The test piece was wiped gently with a cloth 60 times with running tap water, wiped off the water droplets, placed in a constant temperature room, and measured the surface resistance 24 hours later. As a result, it was 1 × 10 ¹¹ Ω. I couldn't. Further, a test piece was cut out from the sheet and the tensile elongation was measured. As a result, it was 6%, and there was no remarkable decrease in performance as compared with a normal acrylic resin.

Reference Examples 2 to 6 The same procedure as in Reference Example 1 was carried out except that the kind of the polyether ester and the mixing ratio of the acrylic resin were changed. The sheet was evaluated for surface resistance and tensile elongation. The results are summarized in Table 4.

Reference Example 7 The same operation as in Reference Example 1 was carried out except that polyetheresteramide (B-1) was used instead of polyetherester. Table 4 shows the results.

Reference Example 8 Asahi Kasei Kogyo Co., Ltd. acrylic resin "Delpet LP-1"
(C-1) 89.5 parts by weight, 10 parts by weight of polyethylene glycol having a molecular weight of 5,000 and 0.5 parts by weight of sodium dodecylbenzenesulfonate were mixed in a drum blender, and the resin temperature was about 260 using a 30 mm twin screw extruder. ° C
And kneaded and granulated. The following was carried out in the same manner as in Reference Example 1. Table 4 shows the results. This was inferior in the durability of the antistatic property.

[0074]

[Table 4]

Claims (6)

[Claims] 1. A polymethyl methacrylate-equivalent number average molecular weight of 60,000 composed of 15 to 50% by weight of an organic dicarboxylic acid unit, 3 to 20% by weight of an organic dihydroxy compound unit and 35 to 80% by weight of a poly (oxyalkylene) glycol unit. A polyetherester containing a urethane bond having a number average molecular weight of 120,000 to 400,000 in terms of polymethyl methacrylate, wherein 100,000 to 100,000 polyetherester segments are connected via a urethane bond formed by reaction with a diisocyanate. 2. The polyetherester according to claim 1, wherein the organic dicarboxylic acid unit is an aromatic dicarboxylic acid unit. 3. The polyetherester according to claim 2, wherein the aromatic dicarboxylic acid unit is at least one selected from a phthalic acid unit, a terephthalic acid unit and an isophthalic acid unit. 4. The polyetherester according to claim 1, wherein the organic dihydroxy compound unit is an alkylene glycol unit or a cycloalkylene glycol unit. 5. An organic dihydroxy compound having a unit of 2,2-
The polyetherester according to claim 1, 2 or 3, which is a bis (4-hydroxyphenyl) -propane unit. 6. The polyetherester according to claim 1, wherein the poly (oxyalkylene) glycol unit is at least one selected from a polyethylene glycol unit, a polypropylene glycol unit and a polybutylene glycol unit. .