JPH1129630A - Polyetherester polycondensate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polycondensate giving an excellent persistent antistatic performance, when mixed with an acrylic resin to produce a composition, by polycondensing a specific polyoxyalkylene glycol, specific dicarboxylic acids and/or their esters and a dihydroxy compound. SOLUTION: This polycondensate is obtained by polycondensing 20-75 wt.% of a polyoxyalkylene glycol having a number-average mol.wt. of 3000-6000, 20-65 wt.% of dicarboxylic acids and/or their esters containing 1-40 mol.% of a sulfonate group-substituted dicarboxylic acid of the formula (R<1> , R<2> are each H, a 1-6C alkyl, a 6-12C aryl; R<3> is a >=2C alkylene and/or a 6-12C trivalent aromatic group; M<+> is a metal ion, etc.), and/or its ester, and a hydroxy compound at 180-270 deg.C. The polycondensate has a relative viscosity of 1.2-4.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyetherester polycondensate. More specifically, when the polyetherester polycondensate of the present invention is mixed with an acrylic resin to form a composition, the polyetherester polycondensate has excellent sustained charging without adding an anionic surfactant and / or a cationic surfactant. Extrusion molding of the composition to produce an antistatic sheet, or injection molding to produce an antistatic article, and to produce a molded article with excellent appearance without surface stickiness etc. can do. Further, it has a feature of reducing contamination of a polishing roll and adhesion of a colored decomposition product to a die lip portion during extrusion molding.

[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 sheet, which is disadvantageous in terms of cost, and the obtained product lacks the sustainability of the 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 is liable to bleed out on the surface of the molded article, and has the disadvantages of impairing the surface appearance and causing stickiness. A method of kneading a polyalkylene glycol and a higher fatty acid monoglyceride (Japanese Patent Publication No. 53-36)
865) and a method of using a specific phosphorus compound in combination (JP-B-53-15896, JP-A-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). Further, an antistatic resin composition comprising a similar polyetherester and an optional thermoplastic resin has also been proposed (JP-A-6-57153).

[0008] However, although the composition of the polyetherester polycondensate and the acrylic resin has a permanent antistatic property, when an ionic antistatic agent is used in combination in order to further impart an effect, the composition may be washed by a water washing method. Had the disadvantage that the antistatic performance could be reduced. Further, in order to solve the above problem, a method has been proposed in which an aromatic dicarboxylic acid component substituted with a sulfonic acid group is contained in a polyetherester polycondensate (Japanese Patent Application Laid-Open No. 8-337702). As an antistatic agent for acrylic resin, the ratio of polyester segment to polyether segment is not optimized, and surfactants such as alkyl sulfonates and alkyl benzene sulfonates are required to continuously exhibit antistatic performance. Since the agent must be added as an essential component, the performance is insufficient as an antistatic agent that exhibits stable and continuous antistatic performance, and when the resin composition is molded, the appearance of a molded article However, at present, a resin composition which is always good and has excellent antistatic performance has not yet been obtained.

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to a method of mixing and forming a composition with an acrylic resin without adding a surfactant such as an anionic surfactant and / or a cationic surfactant, and forming an antistatic agent by extrusion molding. The object of the present invention is to provide a polyetherester polycondensate capable of achieving both antistatic performance and excellent appearance of a product when molding an sheet or producing an antistatic article by injection molding. .

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, a polyetherester polycondensate 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. That is, the present invention provides a polyoxyalkylene glycol having a number average molecular weight of 500 to 20,000, 20 to 75% by weight, dicarboxylic acid and / or
Or a polycondensate obtained by polycondensation of 10 to 70% by weight of an ester thereof with a dihydroxy compound, wherein the dicarboxylic acid and / or the ester thereof is represented by the following formula (1)

[0011]

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[In the formula (1), R ³ is an alkylene group having 2 or more carbon atoms and / or a trivalent aromatic group having 6 to 12 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, Number 1
Represents an alkyl group having from 6 to 6 or an aryl group having from 6 to 12 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. 0.1 to 80 mol% of a dicarboxylic acid substituted with a sulfonic acid group represented by the formula (1) and / or an ester thereof, and has a relative viscosity of 1.2 to 4.0 as measured in m-cresol at 30C. A polyether ester polycondensate characterized by the following. Hereinafter, the present invention will be described in more detail.

The dicarboxylic acid and / or its ester used in polymerizing the polyetherester polycondensate of the present invention may be an aromatic dicarboxylic acid and / or an ester thereof, and may be an aliphatic dicarboxylic acid and / or an ester thereof.
Or its ester may be sufficient. Further, an aromatic and an aliphatic may be used in combination as the dicarboxylic acid component. As the aromatic dicarboxylic acid component, for example, terephthalic acid,
Isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, and methyl, ethyl, propyl of these aromatic dicarboxylic acids;
Butyl ester and the like. These aromatic dicarboxylic acids or aromatic dicarboxylic esters may be used alone or in combination of two or more. Among them, the polyether ester polycondensate from which terephthalic acid or its ester is obtained has a particularly high melting point and is most preferable in handling.

The aliphatic dicarboxylic acid component can be used for adjusting the refractive index and the melting point of the polycondensate. At that time, the proportion of the aliphatic dicarboxylic acid and its ester is preferably in the range not exceeding 30% by weight. If the amount exceeds 30% by weight, the melting point of the polycondensate becomes extremely low, which makes it difficult to handle and degrades the antistatic performance of the resin composition.

Examples of the aliphatic dicarboxylic acid component include succinic acid, glutaric acid, adipic acid, pimelic acid,
Examples include azelaic acid, sebacic acid, dodecanedicarboxylic acid, and methyl, ethyl, propyl, and butyl esters of these aliphatic dicarboxylic acids. These aliphatic dicarboxylic acid or aliphatic dicarboxylic acid ester,
They may be used alone or in combination of two or more.

The amount of the dicarboxylic acid and / or its ester used in the present invention is 10 to 70% by weight, preferably 20 to 65% by weight. If the amount is less than 10% by weight, not only the melting point of the polyetherester obtained by polymerization becomes low and handling becomes difficult, but also when injection molding or sheet molding is carried out as an acrylic resin composition, since the hard segment is small, acryl is used. It does not form a suitable morphology because it is compatible with the base resin, and the antistatic performance is not stably exhibited. On the other hand, if it exceeds 70% by weight, the number of soft segments is reduced, and the refractive index and compatibility with the acrylic resin are largely separated. Will be enough.

The polyether ester sulfonate polycondensate of the present invention ^- dicarboxylic acid and / or its esters substituted with (-SO ₃ M ⁺⁾ is represented by the following formula (1).

[0018]

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In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, a methyl group, An alkyl group having 1 to 4 carbon atoms such as an ethyl group, a propyl group, and a butyl ester group. In the above formula (1), M ⁺ represents an ion selected from a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. For example, alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and magnesium ion, metal ions such as zinc ion, tetramethylphosphonium ion, tetrabutylphosphonium ion, tetramethylammonium ion, tetrabutyl Ammonium ion and the like. Among these ions, metal ions are preferred, and alkali metals are particularly preferred.

R ³ in the above formula (1) is an alkylene group having 2 or more carbon atoms and / or a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring. It may have a substituent such as an alkyl group, a phenyl group, a halogen and an alkoxy group. Examples of those having an alkylene group include dialkyl sulfosuccinates. Specific examples include sodium dioctyl sulfosuccinate, potassium dioctyl sulfosuccinate, sodium dibutyl sulfosuccinate, potassium dibutyl sulfosuccinate, and the like. Examples of those having an aromatic group include 4-sodium sulfo-isophthalic acid, 5-sodium sulfo-isophthalic acid,
Potassium sulfo-isophthalic acid, 5-potassium sulfo-
Isophthalic acid, 2-sodium sulfo-terephthalic acid,
2-potassium sulfo-terephthalic acid, zinc 4-sulfo-isophthalate, zinc 5-sulfo-isophthalate, zinc 2-sulfo-isophthalate, tetraalkylphosphonium 4-sulfo-isophthalate, tetrasulfo-isophthalate Alkyl phosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5-sulfo-isophthalic acid tetraalkylammonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt, 4
-Sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-sodium sulfo-2,7-naphthalenedicarboxylic acid, 4-potassium sulfo-2,6-naphthalenedicarboxylic acid, 4-sulfo-2,6-zinc naphthalenedicarboxylate And / or esters thereof, for example, dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester and the like. Among these dicarboxylic acid components, particularly preferably used are dimethyl 5-sodium sulfo-isophthalate, 4-sodium sulfo-
Dimethyl isophthalate.

The polyether ester sulfonate for use in the polymerization of polycondensate of the present invention (-SO ₃ ^- M
^The dicarboxylic acid and / or ester thereof substituted with ( ⁺ ) accounts for 0.1 to 80 mol% of the total amount of the dicarboxylic acid component used. If the amount is less than 0.1 mol%, the antistatic performance will not be sufficiently exhibited, and if it exceeds 80 mol%, the polymerization rate will be extremely slow, and as a result, the molecular weight will hardly increase, and the coloring of the polymer will be remarkable. And it is very difficult to produce industrially. Further, when injection molding or sheet molding is performed as an acrylic resin composition, it is not preferable because it causes clouding of a molding die and contamination of a polishing roll. For this reason, it is preferable that the amount of 0.1.
3 to 60 mol%, more preferably 0.5 to 50 mol%,
More preferably, it is 1 to 40 mol%. Further, sulfonate ^- by co-polycondensation of (-SO ₃ M ⁺⁾ with substituted dicarboxylic acids and / or esters thereof, there is an effect such that can control the crystallinity of the resulting polyetherester.

The polyoxyalkylene glycol used for polymerizing the polyetherester polycondensate of the present invention includes, for example, polyoxyethylene glycol,
Examples include polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and a polyoxyethylene / polyoxypropylene glycol block copolymer. These polyoxyalkylene glycol components may be used alone or in combination of two or more.
Among these, polyoxyethylene glycol is particularly excellent in terms of antistatic performance and is most preferable. The polyoxyalkylene glycol component has a number average molecular weight of 500 to 20,
000 is required. When two or more kinds 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. When the number average molecular weight is less than 500, the melting point of the polyetherester polycondensate is low, and it becomes difficult to handle the polycondensate, and at the same time, the antistatic performance of the acrylic resin composition becomes insufficient. On the other hand, when the number average molecular weight exceeds 20,000, the composition distribution tends to occur at the time of polycondensation, or the polymerization rate tends to be low, and the polymerizability problem such as not increasing the molecular weight of the polycondensate tends to occur. When the acrylic resin composition is used, the antistatic performance may not be sufficiently exhibited.

In addition to polyoxyethylene 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, even when used alone,
Two or more kinds may be used in combination.

The number average molecular weight of the polyoxyalkylene glycol is 2,000 to 8,000, preferably 3,000.
When it is in the range of 0 to 6,000, contamination with a polishing roll, adhesion to a die lip portion, thermo-oxidative coloring, and the like when mixing with an acrylic resin and performing extrusion molding can be significantly reduced. Examples of the dihydroxy compound used for polymerizing the polyetherester polycondensate of the present invention include ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol. Among them, ethylene glycol is particularly preferred in view of reactivity and antistatic performance.

The ratio of the dihydroxy compound used when polymerizing the polyetherester polycondensate of the present invention is as follows:
Polyoxyalkylene glycol and dicarboxylic acid and / or
Or a role as a linking agent with the ester thereof, and 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 is It is necessary to make the carboxylic acid groups of the dicarboxylic acid and its ester the same molar number. For this adjustment, a dihydroxy compound component is introduced. Therefore, the weight percent of the dihydroxy compound is automatically determined from the amount of polyoxyalkylene glycol, the amount of dicarboxylic acid and its ester.

In order to increase the molecular weight of the polyetherester polycondensate of the present invention in a short time, easily control the melt viscosity, and control the morphology of the resin composition and product, the number of carbon atoms is 3 to 30. It is possible to introduce a trivalent or higher valent polyhydroxy compound. In that case, the addition amount is 0.01 to 5% by weight, preferably 0.03 to 3% by weight, and more preferably 0.05 to 2% by weight. If the polyhydroxy compound is less than 0.01, the increase in molecular weight is insufficient, and if it exceeds 5 parts by weight, gelation of the polycondensate tends to occur, resulting in generation of foreign matter and poor appearance when molded. There is not preferred. The polyhydroxy compound having a valence of 3 or more must have a carbon number of 3 or more and 30 or less, preferably 3 or more and 25 or less. Compounds having less than 3 carbon atoms cannot exist stably and have 30 carbon atoms.
When the molecular weight exceeds the above range, the reactivity is lowered, so that the molecular weight cannot be effectively increased. Specific examples of the trivalent or higher polyhydroxy compound having 3 to 30 carbon atoms include pentaerythritol, trimethylolpropane, glycerin, erythritol,
Examples include natural sugars such as glucose, low molecular weight natural sugars having 30 or less carbon atoms, and oligomers of polyvinyl alcohol.

The polyetherester polycondensate of the present invention has a relative viscosity of 1. measured at 30 ° C. in m-cresol.
It is 2-4.0, preferably 1.5-3.5. When the relative viscosity is less than 1.2, the fluidity of the polymer itself increases, but when kneaded with an acrylic resin, the mechanical strength of the molded article is reduced, and the polyetherester-based polymer is finely dispersed in the resin. This is not preferable because the effect of imparting antistatic performance is reduced. On the other hand, when the relative viscosity is more than 4.0, the flowability of the polymer itself is reduced, making it difficult to discharge the polymer from the reactor, and when kneaded with an acrylic resin, the polyetherester-based polymer is difficult to disperse. However, the effect of imparting antistatic performance is also reduced, which is not preferable.

There is no particular limitation on the method for producing the polyetherester polycondensate of the present invention. For example, the above-mentioned polyalkylene glycol compound, dicarboxylic acid or its ester and a dihydroxy compound, and if necessary, a raw material mixture comprising a polyhydroxy compound are charged into a reactor, and are produced during the reaction in the presence or absence of a solvent. A method of polycondensing while removing water or alcohol to be removed from the reactor to increase the molecular weight is used. In order to remove water or alcohol from the reactor, it is preferable to flow nitrogen gas or to reduce the pressure inside the reactor to a high degree. The temperature during polycondensation is 150 to 300
C., preferably at 180-270.degree.

When the polycondensate is produced, the reaction time can be shortened 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) Stabilizers, sulfur-based stabilizers such as dilaurylthiodipropionate, or tris (2,
A phosphorus compound such as 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.

The acrylic resin capable of producing the antistatic resin composition by mixing the polyetherester polycondensate of the present invention includes methyl methacrylate homopolymer or methyl methacrylate and another monomer. Copolymers with the body are 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,
Examples include unsaturated carboxylic anhydrides such as itaconic anhydride 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.

When an antistatic resin composition is produced using the polyetherester polycondensate of the present invention, 30 to 2% by weight, preferably 25 to 5% by weight of the polycondensate and acrylic resin 70 ~ 98% by weight, preferably 75 ~ 9
It is preferable to use a mixture of 5% by weight. When the amount of the polycondensate is less than 2% by weight, the obtained resin composition has insufficient antistatic performance, while the amount of the polycondensate is 30% by weight.
If the ratio exceeds the above range, the mechanical strength of the obtained resin composition is lowered, which is not preferable. The mixing method for producing the antistatic resin composition is not particularly limited. There is a method of mixing with a drum blender or a Henschel mixer, a method of mixing with these methods and then granulating at a temperature of 200 to 280 ° C. using an extruder. 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, for example, various kinds of dyes,
Pigments, organic light diffusing agents such as methyl methacrylate / styrene copolymer beads, and inorganic light diffusing agents such as barium sulfate, titanium oxide, calcium carbonate, and talc.
Hindered phenols as heat stabilizers and antioxidants,
Phosphate-based, benzotriazole-based, 2-hydroxybenzophenone-based, salicylic acid-phenylester-based, etc. as ultraviolet absorbers, phthalate-based, fatty acid ester-based, trimellitate-based, phosphate ester-based, polyesters as plasticizers Higher fatty acid, higher fatty acid ester, higher fatty acid mono,
Di- or triglycerides, etc., higher fatty acid esters as lubricants, polyolefins, etc., phosphorus-based as flame retardants,
Glass fiber, carbon fiber, or the like may be mixed as a reinforcing agent such as phosphorus / chlorine or phosphorus / bromine.

The antistatic resin composition obtained by mixing the polyetherester polycondensate of the present invention can be used to produce an antistatic sheet or film by extrusion molding or various molded articles by injection molding. it can. These moldings have a resin temperature of 180 to prevent burning and deterioration of the resin.
It is preferable to carry out in the range of -280 ° C.

[0035]

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 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 m-cresol solution to the flowing time of m-cresol. 2. Copolycondensate composition ¹ H-NMR analysis is performed, and the composition is 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 type manufactured 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.

The following abbreviations were used. PEG (1500): polyoxyethylene glycol PEG (5000): polyoxyethylene glycol The numbers in parentheses indicate the molecular weight. DMT: dimethyl terephthalate DMA: dimethyl adipate SIPM: dimethyl 5-sodium sulfo-isophthalate EG: ethylene glycol Penta: pentaerythritol DBS: sodium dodecylbenzenesulfonate Unless otherwise specified, parts are by weight.

[0037]

Example 1 Production of polyetherester polycondensate (A-1). A reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube was charged with 33.2 parts by weight of dimethyl terephthalate and 5-sodium sulfo-
17.8 parts by weight of dimethyl isophthalate, 30 parts by weight of ethylene glycol, and manganese acetate tetrahydrate 0.02
Charge the parts by weight and heat at 180-230 ° C for 3 hours,
The transesterification reaction was performed while distilling off the generated methanol. Next, 50 parts by weight of polyoxyethylene glycol having a number average molecular weight of 5000, 0.03 parts by weight of antimony trioxide, and 0.1 part by weight of trimethyl phosphate were added to the reactor.
015 parts by weight was added, and the temperature was raised to 260 ° C. The pressure inside the reactor was gradually reduced, and the polycondensation reaction was carried out for 3.5 hours while maintaining the internal pressure at 1 Torr or less while distilling off excess ethylene glycol. The obtained polyetherester polycondensate (A-
The relative viscosity of 1) was 1.9. From the NMR analysis, the composition was found to be polyoxyethylene glycol component 5
0% by weight, 40.3% by weight of terephthalic acid and 5-sodium sulfo-isophthalic acid component, and 9.7% by weight of ethylene glycol component.

The results are summarized in Tables 1 and 2.

[0039]

Examples 2 to 8 and Comparative Examples 1 to 3 The same procedures as in Example 1 were carried out except that the charged compositions were changed as shown in Table 1.
The results are summarized in Tables 1 and 2.

[0040]

Reference Example 1 Polycondensate (A-1) 1 produced in Production Example 1
5 parts by weight, acrylic resin "Delpet LP" manufactured by Asahi Kasei Corporation
-1 (B-1) "with a drum blender, and using a 30 mm twin-screw extruder, a resin temperature of about 260 ° C.
And kneaded and granulated. The obtained pellets were subjected to a resin temperature of about 26 from a 50 mm single screw extruder equipped with a T die having a width of about 30 cm.
It was extruded at 0 ° C., and the interval between polishing rolls having a surface temperature of about 100 ° C. was adjusted to form a sheet having a thickness of 1.8 mm. The surface of the molded article had no white streak defects and no stickiness and had an excellent appearance. Also, no fogging on the polishing roll surface and no fouling on the lips of the T-die during molding were observed during the operation for 8 hours.

A test piece was cut out from this sheet and
After 24 hours in a constant temperature room at 50 ° C and 50% relative humidity
When the sheet resistance was measured, 7 × 10^TenΩ. Ma
Test specimens in running tap water 30 times a minute for 5 minutes.
Continue to rub with a cloth, wipe off any water droplets, and place in a constant temperature room.
24 hours later, the surface resistance was measured to be 7 × 10
^TenΩ, and no performance deterioration was observed.

[0042]

Reference Examples 2 to 13 The same procedure as in Example 1 was carried out except that the kind of the polycondensate was changed, and the fogging of the polishing roll surface, the presence or absence of attached matter on the eyes of the T-die lip, and the surface resistance of the sheet were evaluated. . The results are summarized in Table 3.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

When the polyetherester polycondensate of the present invention is mixed with an acrylic resin to produce an antistatic acrylic resin composition, an anionic surfactant such as an alkylbenzene sulfonate and / or Without mixing a surfactant such as a cationic surfactant, excellent long-lasting antistatic performance can be exhibited, and when an antistatic extruded plate or molded article is produced using the resin composition Almost no heat coloring and no burning gel is generated during molding, and the resulting molded product is free from appearance defects such as surface roughness and white streaks and surface stickiness, and has excellent durability of antistatic performance. In addition, a polishing roll for manufacturing an extruded plate and a mold for injection molding are less likely to be fogged, and a product having a good surface appearance can be stably obtained. Therefore, the polyetherester polycondensate of the present invention can be used in applications that dislike charging or dust adhesion of lighting fixture covers, transport containers for semiconductor components, fixtures used in clean rooms, front panels of projection televisions, optical lenses, and the like. It is suitable for producing an antistatic resin composition.

Claims (5)

[Claims] 1. A polycondensate obtained by polycondensing 20 to 75% by weight of a polyoxyalkylene glycol having a number average molecular weight of 500 to 20,000, 10 to 70% by weight of a dicarboxylic acid and / or an ester thereof, and a dihydroxy compound. Wherein the dicarboxylic acid and / or ester thereof is represented by the following formula (1): [In the formula (1), R ³ is an alkylene group having 2 or more carbon atoms and / or a trivalent aromatic group having 6 to 12 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom, Represents an alkyl group having 6 or an aryl group having 6 to 12 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. Containing 0.1 to 80 mol% of a dicarboxylic acid and / or an ester thereof substituted with a sulfonate group represented by the formula:
0 ° C., relative viscosity measured in m-cresol is 1.2 to
4.0, a polyetherester polycondensate. 2. The polyetherester polycondensate according to claim 1, wherein the polyoxyalkylene glycol is polyethylene glycol. 3. The polyetherester polycondensate according to claim 1, wherein the dicarboxylic acid and / or ester thereof has 4 to 20 carbon atoms. 4. The polyetherester polycondensate according to claim 1, wherein the dicarboxylic acid and / or its ester is aromatic and / or aliphatic. 5. The polyetherester polycondensate according to claim 1, wherein the dihydroxy compound has 2 to 3 carbon atoms.