JPH10251389A - Polyether-ester polycondensate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycondensate suitable for producing a resin composition used for a antistatic extruded board having good appearance, or a molding material by mixing the polycondensate with an acrylic resin. SOLUTION: This polyether-ester polycondensate comprises 20-75wt.% polyoxyalkylene glycol component having 500-20,000 number-average molecular weigh, 10-65wt.% aromatic dicarboxylic aid component, 0.5-30wt.% aliphatic dicarboxylic acid component, 0.01-5wt.% trihydric or more polyhydroxyl compound component and 5-20wt.% dihydroxy compound component, and has 1.2-4.0 relative viscosity measured in 30 deg.C m-cresol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyetherester polycondensate. More specifically, the polyetherester polycondensate of the present invention has excellent antistatic performance when mixed with a thermoplastic resin such as an acrylic resin to form a composition. When producing an antistatic sheet or injection molding to produce an antistatic molded article, a molded article having an excellent surface appearance can be produced. In addition, it has a feature that contamination of a polishing roll and adhesion of a colored decomposed substance to a die lip portion during extrusion molding can be reduced.

[0002]

2. Description of the Related Art Acrylic resin has transparency, surface gloss,
Excellent surface hardness, weather resistance, etc., vehicle exterior parts such as lighting fixture covers, tail lamps, etc., optical parts such as lenses, light guide plates, video discs, projection TV screens, vending machine front panels, outdoor signs, store equipment Widely used for applications such as displays.

[0003] The above-mentioned applications take advantage of the characteristic that the acrylic resin is substantially amorphous and transparent. However, this resin is generally easily charged and dust is formed on the product. In addition to adhesion, the transparency and surface appearance are easily impaired, and there is a drawback that adhesion of dust hinders post-processing of molded articles and sheets. Therefore, in order to prevent the adhesion of dust, it has been required to provide these resins with good antistatic properties.

Therefore, in order to impart an antistatic property to an acrylic resin or the like, a method of applying a silicon-based compound antistatic agent to the resin surface, a method of adding and mixing a surfactant to the resin, a method of adding a hydrophilic group, A method has been proposed in which a monomer having an ionic group or a copolymer is copolymerized to chemically modify the resin. However, the method of applying an antistatic agent requires an application step for a molded article or a sheet, which is disadvantageous in terms of cost, and the obtained product lacks sustainability of an antistatic effect, such as rainfall. There is a disadvantage that the effect is easily lost by running water. As a method of adding a surfactant, for example, a method of kneading a compound having a sulfonic acid group or a compound having a sulfonic acid group and a polyether into an acrylic resin (JP-A-47-26438,
-43440), a compound having a sulfonic acid group,
A method of kneading polyoxyalkylene glycol and a specific phosphorus compound (Japanese Patent Publication No. 53-30724) has been proposed, but in order to obtain a sufficient antistatic effect, a relatively large amount of a component such as polyether is used. Since it must be added, the antistatic agent easily bleeds out on the surface of the molded article, and has the disadvantages of impairing the surface appearance and causing stickiness. Also, a method of kneading a polyalkylene glycol and a higher fatty acid monoglyceride (Japanese Patent Publication No. 53-368)
No. 65) and a method in which a specific phosphorus compound is used in combination (Japanese Patent Publication No. 53-15896, Japanese Patent Application Laid-Open No. 54-748).
No. 49) has been proposed, but since the glass transition temperature of the acrylic resin is relatively high and the transferability of monoglyceride to the surface of the molded article is low, a large amount is required to impart sufficient antistatic properties. There is a disadvantage that monoglyceride needs to be added and the surface appearance is impaired. Others
A method of kneading an alkyl sulfonate or an alkylbenzene sulfonate with a trialkyl phosphite (Japanese Patent Laid-Open No.
JP-A-4-24845) has also been proposed, but since a relatively large amount of an alkyl sulfonate or an alkylbenzene sulfonate needs to be added, deterioration of the resin surface appearance is inevitable. 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, and thus it is difficult to maintain the antistatic property.

Further, copolymers of monomers having a hydrophilic group or an ionic group include, for example, a copolymer of a sulfosuccinate-based monomer and an acrylate-based monomer and an acidic phosphoric acid. Compositions comprising an ester or an alkylene oxide compound (JP-A-59-182837 and JP-A-59-182838) have been proposed, which are advantageous from the viewpoint of the durability of the antistatic effect.
It is necessary to use a relatively large amount of a special monomer as a raw material, which is disadvantageous not only in terms of cost, but also has a disadvantage that the weather resistance and heat resistance of the composition are reduced.

On the other hand, in order to improve the durability of the antistatic effect, for example, a polymer type antistatic agent such as a vinyl copolymer containing a hydrophilic and ionic group or a polyetheramide polymer is kneaded. A method of doing so has been proposed. However, a method of kneading a vinyl copolymer having a polyoxyethylene chain and a sulfonate or quaternary ammonium salt structure with an acrylic resin is disclosed in
JP-A-5-36237 and JP-A-63-63739), a vinyl copolymer produced using an expensive special monomer must be used, which is disadvantageous not only in terms of cost but also acrylic resin. It has the disadvantage of lowering the good heat resistance. Also, a method of kneading a polyether amide polycondensate comprising a polyamide segment and a polyether segment as an antistatic component in an acrylic resin (JP-A-64-90246, JP-A-1-308)
No. 444), the polycondensate itself containing a polyamide segment is easily thermally colored when it comes into contact with air at a high temperature, and the acrylic resin and the polycondensate containing a polyamide segment undergo a crosslinking reaction under heating. Since the insoluble and infusible gel-like substance is easily generated, the composition staying in the extruder becomes a colored gel and is mixed into a molded product or sheet, which has a drawback that the appearance of the product is significantly impaired. .

In order to remedy such drawbacks of gelation and coloring, 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 condensate and an acrylic resin has been proposed (Japanese Patent Application No. 6-271988). However, when trying to obtain a resin composition in which the refractive index of the polyetherester polycondensate is close to that of the acrylic resin, it is necessary to extremely increase the ratio of the polyalkylene oxide component in the polycondensate. For,
Depending on the molding conditions, the polycondensate tends to disperse very finely in the acrylic resin, so that the antistatic performance is hardly exhibited, or the polyether ester polymer is used to further improve the antistatic performance of the composition. When the ratio of the polyester segment component of the condensate is increased, the refractive index difference from the acrylic resin becomes large, and depending on the molding conditions, there is a disadvantage that the appearance of the molded article is significantly impaired. For example, defects such as white streaks occurring on the surface of the laminated sheet when the laminated sheet is manufactured under certain conditions. In general, the antistatic performance is improved by increasing the content of the polyetherester polycondensate, but the occurrence of poor appearance tends to increase. Therefore, at present, an antistatic agent that always gives a good appearance of a molded product has not been obtained irrespective of molding conditions and the amount of addition.

[0008]

According to the present invention, an antistatic sheet is formed by mixing with a thermoplastic resin such as an acrylic resin, forming a composition, and extruding to form an antistatic sheet, or manufacturing an antistatic article by injection molding. The object of the present invention is to provide a polyetherester polycondensate capable of achieving both excellent antistatic performance and excellent appearance of a product.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, a polyetherester polycondensate composition having a specific molecular structure and a relative viscosity has solved the above problems. The inventors have found that the present invention is effective for solving the problem, and have completed the present invention. The present invention relates to a polyoxyalkylene glycol component having a number average molecular weight of 500 to 20,000, 20 to 75% by weight, an aromatic dicarboxylic acid component 10 to 65% by weight, an aliphatic dicarboxylic acid component 0.5 to
30% by weight, trivalent or higher polyhydroxy compound component
01 to 5% by weight and a dihydroxy compound component 5 to 20
A polyether containing 30 to 2 parts by weight of a polyetherester polycondensate having a relative viscosity of 1.2 to 4.0 as measured in metacresol at 30 ° C. An ester polycondensate is provided.

Hereinafter, the present invention will be described in more detail. As the polyoxyalkylene glycol component of the polyetherester polycondensate of the present invention, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, or polyoxyethylene / polyoxypropylene Glycol block copolymer and the like can be mentioned.

[0011] In addition to polyoxyalkylene glycol, ethylene oxide adducts such as hydroquinone, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, bisphenol-A and the like can be mentioned. Among these, the use of an ethylene oxide adduct of polyoxyethylene glycol or bisphenol-A is preferable because the resulting polycondensate has good antistatic performance. These compounds can be used alone or
More than one species may be used in combination.

The polyether ester polycondensate must have a certain melting point from the viewpoint of handling, and the polyoxyalkylene glycol of the present invention is used in order to ensure the antistatic performance of the resin composition. The components have a number average molecular weight of at least 500 or more. On the other hand, if the number average molecular weight is too large, unevenness of the composition distribution is likely to occur in the polycondensate, and not only takes a long time to obtain a desired molecular weight due to a slow polymerization rate, but also the antistatic performance of the resin composition. Is also insufficient, so it is at most 20,000. Furthermore, when the above resin composition is extrusion-molded, the number average molecular weight is preferably from 2,000 to 2,000 to reduce the generation of deposits on the extruder die lip or the formation of thermally degraded colored matters, or to prevent contamination of the polishing roll. 8:00
0, more preferably in the range of 3,000 to 6,000.

When two or more kinds of polyoxyethylene glycols are used in combination, the number average molecular weight of each glycol is selected so as to be within this range depending on the constitution ratio of each glycol. Examples of the dihydroxy compound component of the polyetherester polycondensate of the present invention 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,
Aliphatic dihydroxy compounds such as 1,8-octanediol, 1,4-cyclohexanediol, bis-1,4
An alicyclic dihydroxy compound such as hydroxymethylcyclohexane, and hydroquinone resorcin; 4,
Aromatic dihydroxy compounds such as 4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and bisphenol-A are mentioned.

At the time of the polycondensation reaction, it is necessary to distill an excess of the dihydroxy compound out of the reaction system. However, when an aliphatic dihydroxy compound having a carbon number exceeding 22 and having a high boiling point is used, it is difficult and not preferable. . Among them, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butanediol are preferably used,
From the viewpoint of reactivity, ethylene glycol and 1,4-butanediol are particularly preferred.

The proportion of the dihydroxy compound component in the polyetherester polycondensate of the present invention is 5 to 20% by weight. The dihydroxy compound serves as a linking agent between the polyoxyalkylene glycol component and the aromatic dicarboxylic acid component and the aliphatic dicarboxylic acid component. In order to obtain a polyetherester polycondensate of the desired composition, the sum of the terminal hydroxyl group of the polyoxyalkylene glycol and the terminal hydroxyl group of the dihydroxy compound and the carboxylic acid group of the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid component Must be the same molar number. For this adjustment, a dihydroxy compound component is introduced.
Therefore, the weight percentage of the dihydroxy compound component is automatically determined from the amount of the polyoxyalkylene glycol component, the amount of the aromatic dicarboxylic acid component, and the amount of the aliphatic dicarboxylic acid component.

The aromatic dicarboxylic acid component of the polyetherester polycondensate of the present invention includes, for example, terephthalic acid, isophthalic acid, phthalic acid, and naphthalene-2,6-
Examples include dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, and methyl, ethyl, propyl, and butyl esters of these aromatic dicarboxylic acids. These aromatic dicarboxylic acid compounds or aromatic dicarboxylic acid ester compounds may be used alone or in combination of two or more. Of these, terephthalic acid or an ester thereof is most preferable in terms of handling because the polyetherester polycondensate obtained has a high melting point.

The aliphatic dicarboxylic acid component of the polyetherester polycondensate of the present invention is used as an essential component for adjusting the refractive index and the melting point of the polycondensate. The proportion of the aliphatic dicarboxylic acid component is 0.5 to 30% by weight, preferably 1.0 to 25% by weight. When the polycondensate has crystallinity, after forming a resin composition, a laminate or an injection-molded product under certain molding processing conditions, white streaks are generated and the appearance is poor, so that aliphatic The content of the dicarboxylic acid component is 0.5% by weight or more. If the proportion of the dicarboxylic acid component is increased, the melting point of the polycondensate is lowered, so that the handling becomes difficult and the antistatic performance of the resin composition is reduced. , 30% by weight or less.

The aliphatic dicarboxylic acid component of the polyetherester polycondensate of the present invention includes, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and aliphatic acids thereof. Examples include methyl, ethyl, propyl, and butyl esters of dicarboxylic acids. These aliphatic dicarboxylic acid compounds or aliphatic dicarboxylic acid ester compounds may be used alone or in combination of two or more.

The polyetherester polycondensate of the present invention uses a trihydroxy or higher polyhydroxy compound component. 3
The polyhydroxy compound having a valency or higher is necessary for obtaining a required molecular weight, for facilitating control of melt viscosity, and for controlling morphology of a resin composition, and is at least 0.01% by weight. Further, when the polycondensate in the resin composition is gelled, foreign substances may be generated or appearance of a molded article may be deteriorated, and the content is at most 5% by weight. Preferably 0.03 to 3% by weight,
More preferably, it is 0.05 to 2% by weight.

The polyhydroxy compound having a valence of 3 or more cannot stably exist a compound having less than 3 carbon atoms, and in order to obtain an effective high molecular weight compound without lowering the polycondensation reactivity, it is necessary to use a compound having 30 carbon atoms. Or less, preferably 3 or more and 25 or less. Specific examples of the trivalent or higher polyhydroxy compound having 3 to 30 carbon atoms include natural sugars such as pentaerythritol, trimethylolpropane, glycerin, erythritol, and glucose; low molecular weight natural sugars having 30 or less carbon atoms; and oligomers of polyvinyl alcohol. And the like. Among these, pentaerythritol, trimethylolpropane, in terms of volatility under the production conditions in the polycondensation process, reactivity, control of the reaction is easy, and excellent in thermal decomposition resistance of the polycondensate,
Glycerin and erythritol are more preferred.

The polyetherester polycondensate of the present invention has a relative viscosity of 1 in m-cresol at 30 ° C.
It is preferably from 2 to 4.0, preferably from 1.5 to 3.5. When the relative viscosity of the polycondensate is low, it is finely dispersed in the resin composition, and not only the effect of imparting antistatic property is reduced, but also the mechanical strength of the molded article is reduced, so that at least 1.2 or more. is required. In addition, when the relative viscosity of the polycondensate is high, the flowability of the polycondensate itself is reduced, which makes it difficult to discharge the polycondensate from the reactor. Is reduced to at most 4.0, preferably 1.5 to
3.5.

The method for producing the polyetherester polycondensate of the present invention is not particularly limited. For example, the above polyalkylene glycol compound, an aromatic dicarboxylic acid compound or an ester compound thereof, an aliphatic dicarboxylic acid compound or an ester compound thereof, a raw material mixture composed of a polyhydroxy compound and a dihydroxy compound are charged into a reactor, in the presence of a solvent or In the absence, water or alcohol generated during the reaction is removed from the reactor while polycondensation is performed to increase the molecular weight. To remove water or alcohol outside the reactor,
It is preferable to carry out the process by flowing nitrogen gas or reducing the pressure inside the reactor to a high degree. The temperature during polycondensation is 150 ~
It can be carried out at 300C, preferably 180-270C.

In the production of the polycondensate, the reaction time can be reduced by using manganese acetate, calcium acetate, cobalt acetate, zinc acetate, antimony trioxide, titanium tetraalkoxide, an organic zirconium compound or the like as a catalyst. As a result, it is preferable because coloring and deterioration of the polycondensate during the reaction can be prevented. When producing the polycondensate, it is preferable to add an appropriate heat stabilizer in order to prevent thermal degradation of the polycondensate during the reaction and to realize a high molecular weight. Examples of the heat stabilizer include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4).
-Hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, N, N'-hexamethylenebis (3,5-
Di-tert-butyl-4-hydroxycinnamic amide, 4,
4'-bis (2,6-di-t-butylphenol),
2,2′-methylenebis (4-ethyl-6-t-butylphenol), pentaerythrityltetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Hindered phenol stabilizers such as propionate],
Amines such as N, N′-bis (β-naphthyl) -p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl-1,2-dihydroquinoline) A stabilizer, a sulfur-based stabilizer such as dilaurylthiodipropionate, or a phosphorus compound such as tris (2,4-di-t-butylphenyl) phosphite may be used. 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.

Acrylic resins from which the polyetherester polycondensate of the present invention can be mixed to produce an antistatic resin composition include methyl methacrylate homopolymer or methyl methacrylate and other monomers Is used. The copolymer preferably has at least 80% by weight of methyl methacrylate structural units in the copolymer. Monomers copolymerizable with methyl methacrylate include alkyl methacrylates such as ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. Styrene, vinyltoluene, aromatic vinyl compounds such as α-methylstyrene, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, N-phenylmaleimide, maleimides such as N-cyclohexylmaleimide, maleic anhydride, anhydride Examples include unsaturated carboxylic anhydrides such as itaconic acid and unsaturated acids such as methacrylic acid, acrylic acid and maleic acid. The copolymer of methacrylic acid or acrylic acid includes a copolymer obtained by heat-treating the methacrylic acid or acrylic acid to form a 6-membered acid anhydride by a dehydration reaction or the like. These monomers copolymerizable with methyl methacrylate can be used alone or in combination of two or more.

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, a normal 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 30 to 100 ° C for suspension polymerization or emulsion polymerization, and 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 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. Further, the present invention is not limited to the acrylic resin, and a wide range of general resins can be used. That is, polycarbonate resin, polystyrene, impact-resistant polystyrene, ABS resin, MBS resin, amorphous copolyester and the like can be used alone or in combination of two or more.

When an antistatic acrylic resin composition is produced using the polyetherester polycondensate of the present invention, the polycondensate is added in an amount of 30 to 2% by weight, preferably 25 to 2% by weight.
It is preferable to use a mixture of 5% by weight and 70 to 98% by weight, preferably 75 to 95% by weight of an acrylic resin. When the polycondensate is less than 2% by weight, the antistatic performance of the obtained resin composition is not sufficient. On the other hand, when the polycondensate exceeds 30% by weight, the mechanical strength of the obtained resin composition is high. Is also undesirable. The mixing method for producing the antistatic resin composition is not particularly limited.
A method of mixing with a drum blender or a Henschel mixer, or a method of mixing with these methods, followed by mixing with an extruder.
There is a method of granulating at a temperature of up to 280 ° C. In the case of extrusion mixing, in order to suppress the thermal decomposition and hydrolysis of the polycondensate, it is preferable to carry out the process while paying attention to the extrusion temperature, the moisture of the polycondensate, the nitrogen purge in the extruder, and the like.

When an antistatic resin composition is produced using the polyetherester polycondensate of the present invention, at least one selected from organic sulfonates and organic phosphates is used to further improve the antistatic performance. One compound 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, phosphoric acid Examples thereof include alkali metal salts and alkaline earth metal salts of organic phosphoric acid such as diphenyl. 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. If the amount exceeds 5 parts by weight, the mechanical strength of the obtained resin composition is lowered, and the resin composition is liable to be colored.

When an antistatic resin composition obtained by mixing the polyetherester polycondensate of the present invention is prepared, various dyes, pigments, organic compounds and the like may be used as long as the antistatic properties and the like are not impaired. Methyl methacrylate / styrene copolymer beads as light diffusing agents, barium sulfate, titanium oxide, calcium carbonate, talc, etc. as inorganic light diffusing agents, heat stabilizers, hindered phenols, phosphates as antioxidants, etc. Release agents such as benzotriazole, 2-hydroxybenzophenone and phenyl salicylate as ultraviolet absorbers, phthalate, fatty acid, trimellitate, phosphate and polyester as plasticizers Higher fatty acid, higher fatty acid ester, higher fatty acid mono, di, Such as triglycerides, higher fatty acid ester as a lubricant, a polyolefin such as, a phosphorus as a flame retardant, a phosphorus / chlorine, and phosphorus / bromine-based, glass fibers, may be mixed such as carbon fiber as a reinforcing agent.

The antistatic resin composition obtained by mixing the polyetherester polycondensate of the present invention is used to produce an antistatic sheet or film by extrusion molding, or to produce various molded articles by injection molding. can do. These moldings are preferably performed at a resin temperature of 180 to 280 ° C. in order to prevent burning and deterioration of the resin.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described more specifically with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation and test methods used are shown below. 1. Relative viscosity 0.25 g of polymer was precisely weighed, and m-cresol 50 ml
And dissolved in Ostwald viscometer No. Using 3, 30
The flow time was measured at ° C. It was calculated as the ratio of the flow time of the m-cresol solution used for dissolution to the flow time of m-cresol. 2. Copolycondensate composition ¹ H-NMR analysis was performed, and the composition was determined from the intensity of the signal corresponding to each component. 3. Surface resistance value (Rs) Using an insulation resistance meter Ultra Megohmmeter SM-8200 series SME8311 made by Toa Denpa Kogyo,
500 V was applied to the molded article at 23 ° C. and a relative humidity of 50% for 45 seconds, and the surface resistance value after 15 seconds was measured. 4. Appearance of molded article The appearance of the molded article was visually observed. 5. Refractive index The refractive index of the polyetherester polycondensate was measured by the following method. Using a compression molding machine, thickness 5 at 220 ° C
A film having a thickness of 0 μm was prepared, and the film was brought into close contact with the detection surface of an Abbe refractometer (manufactured by Atago Optical Instruments), and the measurement was performed at 23 ° C.

The following abbreviations were used. PEG (5000): polyoxyethylene glycol The numbers in parentheses indicate the molecular weight. DMT: dimethyl terephthalate DMS: dimethyl sebacate EG: ethylene glycol Penta .: pentaerythritol DBS: sodium dodecylbenzenesulfonate Unless otherwise specified, parts are by weight.

[0032]

Example 1 Production of polyetherester polycondensate.
A reactor equipped with a stirrer, a nitrogen inlet tube, and a distillation tube was charged with 34 parts by weight of dimethyl terephthalate, 5 parts by weight of dimethyl sebacate, 24 parts by weight of ethylene glycol, and 0.02 parts by weight of manganese acetate tetrahydrate, 180-230 ° C
For 3 hours to carry out a transesterification reaction while distilling off generated methanol. Next, 38 parts by weight of polyoxyethylene glycol having a number average molecular weight of 5,000, 0.09 parts by weight of pentaerythritol, 0.03 parts by weight of antimony trioxide, and 0.015 parts by weight of trimethyl phosphate were added to the reactor. The temperature rose. The pressure inside the reactor was gradually reduced, and the polycondensation reaction was carried out for 3 hours while maintaining the internal pressure at 1 Torr or less while distilling off excess ethylene glycol. The relative viscosity of the obtained polyetherester polycondensate was 2.2. From NMR analysis, the composition was as follows: polyoxyethylene glycol component 50% by weight,
The terephthalic acid component was 34% by weight, the sebacic acid component was 5% by weight, the pentaerythritol component was 0.1% by weight, and the ethylene glycol component was 10.9% by weight.

15 parts by weight of the produced polycondensate, 84.5 parts by weight of an acrylic resin "Delpet LP-1" manufactured by Asahi Kasei Corporation, and 0.5 part by weight of sodium dodecylbenzenesulfonate were mixed in a drum blender, and mixed with a 30 mm 2 The mixture was kneaded and granulated at a resin temperature of about 260 ° C. using a 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 the spacing between polishing rolls having a surface temperature of about 100 ° C. was adjusted to form a sheet having a thickness of 2 mm. Molded. No fogging on the polishing roll surface and no fouling on the T-die lip during molding were observed after 8 hours of operation. A test piece was cut out from this sheet, placed in a constant temperature chamber at 23 ° C. and a relative humidity of 50%, and measured for surface resistance 24 hours later.
¹⁰ Ω. The test piece was wiped gently 60 times with a cloth while flowing tap water, wiped off water drops, and then placed in a constant temperature room. After 24 hours, the surface resistance was measured.
¹¹ Ω, and almost no performance degradation was observed.

[0034]

Examples 2 to 6 and Comparative Examples 1 to 3 The same procedures as in Example 1 were carried out except that the charged composition was changed as shown in Table 1. The sheet surface resistance of the sheet was evaluated. The results are summarized in Table 1.

[0035]

[Table 1]

[0036]

The polycondensate of the present invention is a polymer suitable for mixing with an acrylic resin to produce an antistatic resin composition. In addition, when the polycondensate of the present invention is mixed with an acrylic resin to produce an antistatic extruded plate or molded article, it hardly heat-colors and does not generate burn gel during molding, and the polyetherester polycondensate does not appear. The appearance of poor surface appearance such as surface roughness and white streaks caused by mixing the condensate does not occur, and a product with excellent antistatic performance is obtained.Polishing rolls for manufacturing extruded plates and clouding of injection molding dies Is less likely to occur and a product having a good surface appearance can be stably obtained.
Therefore, the polyetherester polycondensate of the present invention is a lighting fixture cover, a semiconductor component transport container, a fixture used in a clean room, a front panel of a projection television,
It is suitable for producing an antistatic resin composition that can be used in applications where charging and dust adhesion are not desired for optical lenses and the like.

Claims (6)

[Claims] 1. A polyoxyalkylene glycol component having a number average molecular weight of 500 to 20,000, 20 to 75% by weight, an aromatic dicarboxylic acid component, 10 to 65% by weight, an aliphatic dicarboxylic acid component, 0.5 to 30% by weight, A polyhydroxy compound component having a valence of 3 or more and 0.01 to 5% by weight and a dihydroxy compound component having a content of 5 to 20% by weight;
1.2-4.0 relative viscosity measured in m-cresol
A polyetherester polycondensate, wherein 2. The polyetherester polycondensate according to claim 1, wherein the polyoxyalkylene glycol component is polyethylene glycol. 3. The polyetherester polycondensate according to claim 1, wherein the aromatic dicarboxylic acid component is terephthalic acid and / or dimethyl terephthalate. 4. The polyetherester polycondensate according to claim 1, wherein the aliphatic dicarboxylic acid component is sebacic acid or adipic acid and a lower alkyl ester thereof. 5. The polyetherester polycondensate according to claim 1, wherein the trivalent or higher polyhydroxy compound component is pentaerythritol. 6. The polyetherester polycondensate according to claim 1, wherein the dihydroxy compound component is ethylene glycol.