JPH1060238A - Photostabilized polyether-ester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in light stability and useful for producing antistatic molded products suitable as e.g. projection television front panels and optical lens for which electrification and dust adherence are unfavorable, by incorporating a polyether-ester-based polycondensate with a specific photostabilizer. SOLUTION: This composition is obtained by incorporating (A) 100 pts.wt. of a polyether-ester-based polycondensate with (B) 0.05-5 pts.wt. of a photostabilizer bearing at least one triazine ring in one molecule. This composition is slight in molecular weight drop and acid value increase due to ultraviolet light. A molded product obtained by blending a noncrystalline resin with this composition is slight in antistaticity drop due to ultraviolet light, having stable antistaticity over a long period. Optionally, this composition may be further incorporated with (C) 0.01-5 pts.wt. of a phenolic antioxidant bearing two or more hydroxyphenyl groups in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-stabilized polyetherester composition, and more particularly, to a long-term stable antistatic property by being blended with an amorphous resin such as an acrylic resin. The present invention relates to a polyetherester composition having improved light stability to give a molded article.

[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 lenses, optical parts such as lenses, light guide plates, video discs, projection TV screens, vending machine front panels, outdoor signs, stores Widely used for applications such as instrument display.

[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 generated on the product. Adhesion tends to impair transparency and surface appearance, and also has the disadvantage 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 impart good antistatic properties to these resins.

As methods for imparting antistatic properties to such acrylic resins and the like, a method of applying a silicon compound to the resin surface, a method of adding and mixing a surfactant to the resin, a method of imparting hydrophilicity, A method of copolymerizing a monomer having a group or an ionic group and chemically modifying the resin has been proposed.

However, the method of applying a silicon-based compound requires an application step for a molded article or a sheet, which is disadvantageous in terms of cost, and the obtained product has poor durability of the antistatic effect and has a low rainfall. There is a disadvantage that the effect is easily lost by running water. Examples of the method of adding a surfactant include a method of kneading a compound having a sulfonic acid group or a polyether with a compound having a sulfonic acid group (Japanese Patent Application Laid-Open Nos. 47-26438 and 3-434).
No. 40), 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) has been proposed. Since it is added, the antistatic agent tends to bleed out on the surface of the molded article, impairing the surface appearance, and has the disadvantage that stickiness tends to occur. Also, a method of kneading a polyalkylene glycol and a higher fatty acid monoglyceride (Japanese Patent Publication No. Sho 53-3)
No. 6865) and a method in which a specific phosphorus compound is used in combination (Japanese Patent Publication No. Sho 53-15896, Japanese Patent Application Laid-Open No. Sho 54-7).
No. 4849) has also 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, it is difficult to impart sufficient antistatic properties, and When a large amount of monoglyceride is added to impart antistatic properties, 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 (JP-A-64-24845)
Japanese Patent Application Laid-Open No. H10-279, but has a drawback that the surface appearance of the resin is impaired because it is necessary to add a relatively large amount of an alkyl sulfonate or the like. Further, a disadvantage common to these methods is that it is difficult to maintain the antistatic property for a long period of time because the added surfactant is easily lost from the surface of the molded article due to running water or the like.

Further, as a method of copolymerizing a monomer having a hydrophilic group or an ionic group, for example, a copolymer of a sulfosuccinate ester monomer and an acrylate monomer and an acid phosphate ester Alternatively, compositions comprising 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 copolymerize a relatively large number of special monomers, which is disadvantageous not only in terms of cost but also in that the composition is inevitably reduced in weather resistance and heat resistance.

On the other hand, in order to improve the durability of the antistatic effect, a polymer type antistatic agent such as a vinyl copolymer containing hydrophilic and ionic groups and a polyetheramide polymer is kneaded. Methods are known.

As a method of kneading a vinyl copolymer containing hydrophilic and ionic groups, for example, a vinyl copolymer having a polyoxyethylene chain and a sulfonate or quaternary ammonium salt structure is used. To an acrylic resin (JP-A-55-36237,
JP-A-63-63739) has been proposed,
This method is not only disadvantageous in terms of cost, since expensive special monomers must be used for the production of the copolymer,
There is a disadvantage that the heat resistance of the acrylic resin is reduced. As a method of kneading a polyetheramide polymer, a method of kneading a polyetheramide polycondensate composed of a polyamide segment and a polyether segment as an antistatic component in an acrylic resin (Japanese Patent Application Laid-Open No. Sho 64)
-90246, JP-A-1-308444)
In these methods, even if the durability of the antistatic property is good in these methods, the polycondensate itself containing the polyamide segment tends to be thermally colored when it comes into contact with air at a high temperature, and it also has an acrylic resin. Since the polycondensate containing a polyamide segment easily undergoes a crosslinking reaction under heating to form an insoluble and infusible gel, the composition retained in the extruder becomes a colored gel to form a molded product or sheet. There is a drawback that they may be mixed and significantly impair the appearance of the product.

In order to remedy such drawbacks of gelation and coloring, a polyether ester 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).
The polyetherester polycondensate has poor light stability and is liable to be decomposed by irradiation with ultraviolet light, resulting in a decrease in molecular weight and an increase in acid value. As a result, the polycondensate is kneaded with an amorphous resin, and is extruded. Alternatively, a molded article obtained by injection molding has a drawback that the antistatic property is remarkably reduced by irradiation with ultraviolet rays.

[0010]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a molding agent which is stable in antistatic properties for a long time by blending it with an amorphous resin such as an acrylic resin. It is an object of the present invention to provide a light-stabilized polyetherester composition capable of giving a molded article, that is, a molded article having a small decrease in antistatic property even when irradiated with ultraviolet rays.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a light-stabilized polyetherester composition, and as a result, a polyetherester-based polycondensate has a specific structure of a stabilizer. And optionally, by adding a phenolic antioxidant of a specific structure in a predetermined ratio,
The light stability of the polyetherester-based polycondensate is remarkably improved, and a decrease in the molecular weight and an increase in the acid value due to ultraviolet light can be suppressed. It has been found that the molded article obtained can suppress a decrease in the antistatic property due to ultraviolet rays and can maintain a stable antistatic property for a long period of time, and have completed the present invention based on this finding.

That is, the present invention relates to (B) a stabilizer containing at least one triazine ring in one molecule per 100 parts by weight of a polyetherester polycondensate (A).
005 to 5 parts by weight and optionally (C) a polyetherester composition comprising 0.01 to 5 parts by weight of a phenolic antioxidant having two or more hydroxyphenyl groups in one molecule. is there.

[0013]

DETAILED DESCRIPTION OF THE INVENTION In the composition of the present invention, examples of the polyetherester polycondensate used as the component (A) include (a) a polyoxyalkylene glycol component, (b) a dicarboxylic acid component and (c) Examples thereof include those composed of a dihydroxy compound component, but are not limited thereto, and can be arbitrarily selected from conventionally known polyetherester-based polycondensates.

Here, (a) the polyoxyalkylene glycol component includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, ethylene glycol / propylene glycol block copolymer, etc. Is mentioned. Among these, use of polyoxyethylene glycol or polyoxypropylene glycol is advantageous because a polycondensate having good antistatic properties can be obtained. These polyoxyalkylene glycols may be used alone or in combination of two or more. In particular, it is preferable to use a combination of polyoxyethylene glycol and polyoxytetramethylene glycol because a polycondensate having good antistatic properties and excellent mechanical strength can be obtained.

Further, (b) the dicarboxylic acid component includes:
For example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid and their alicyclic dicarboxylic acids such as methyl, ethyl, propyl, butyl ester, and 1,4-cyclohexyldicarboxylic acid Acids and their methyl, ethyl, propyl, butyl esters, etc., phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, aromatic dicarboxylic acids such as diphenyl-4,4'-dicarboxylic acid and their methyl , Ethyl, propyl, butyl ester and the like. These may be used alone or in combination of two or more.

Further, (c) the dihydroxy compound component includes, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and the like. Examples include aliphatic dihydroxy compounds, alicyclic dihydroxy compounds such as cyclohexanediol, and aromatic dihydroxy compounds such as hydroquinone, resorcin, dihydroxydiphenyl ether, and bisphenol A. These dihydroxy compounds may be used alone or in combination of two or more.

The polyetherester polycondensate of the component (A) is prepared by, for example, charging the above-mentioned polyoxyalkylene glycol, dicarboxylic acid or its ester and a dihydroxy compound in a reactor at a predetermined ratio, and reacting the mixture in the presence of a solvent. Alternatively, a method in which polycondensation is carried out in the absence of water or alcohol generated during the reaction while removing the water or alcohol outside the reactor to increase the molecular weight is preferably used. To remove water or alcohol out of the reactor, flow nitrogen gas or
Alternatively, it is advantageous to carry out the reaction at a high pressure in the reactor. The polycondensation temperature is usually 150 to 300 ° C,
Preferably, it is selected in the range of 180 to 270 ° C.

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.

In the composition of the present invention, the stabilizer used as the component (B) must contain at least one triazine ring in one molecule. Such materials include, for example, 2- (4,6-diphenyl-1,3,5-
Triazin-2-yl) -5-[(hexyl) oxy]
-Phenol, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6
6-tetramethyl-4-piperidyl) imino]], N,
N'-bis (3-aminopropyl) ethylenediamine
2,4-bis [N-butyl-N- (1,2,2,6,6
-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.
Stabilizers having four or more triazine rings are difficult to synthesize and obtain, and also increase the colorability of the stabilizer itself. Therefore, those having one to three triazine rings are preferable. Among these stabilizers, 2- (4,6-diphenyl-
1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, poly [[6- (1,1,
3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-tetramethyl-4-piperidyl)
Imino]] is preferred, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol is particularly preferred.

The stabilizer of component (B) may be used alone or in combination of two or more.
The compounding amount is selected in the range of 0.005 to 5 parts by weight based on 100 parts by weight of the polyetherester polycondensate of the component (A). When the amount is less than 0.005 parts by weight, the effect of improving the light stability of the polyetherester polycondensate is not sufficiently exhibited. When the amount exceeds 5 parts by weight, the effect is not much improved for the amount. On the contrary, it is economically disadvantageous, and the color of the compound itself causes an undesirable situation such as coloring of the composition. From the viewpoints of improving the light stability, economy, and preventing the coloring of the composition, the preferred amount of the component (B) is 0.01 to 3 parts by weight based on 100 parts by weight of the component (A). The range is particularly preferable in the range of 0.05 to 2.0 parts by weight.

In the composition of the present invention, in order to further improve the light stability, it is preferable to use a phenolic antioxidant as the component (C) in combination with the stabilizer of the component (B). This phenolic antioxidant contains 1
It has two or more hydroxyphenyl groups in the molecule. These include one-sided hindered phenolic antioxidants, ie, those having a hindered group on one side of a hydroxyl group, and both hindered phenolic antioxidants, ie, those having a hindered group on both sides of a hydroxyl group. Examples of such phenolic antioxidants include triethylene glycol-bis [3-
(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane, , 6-Hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), bis ( Ethyl 3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,2'-methylene-bis -
(4-methyl-6-t-butyl-phenol), 4,
4'-butylidene-bis- (3-methyl-6-t-butyl-phenol), 4,4'-thio-bis- (3-methyl-6-t-butyl-phenol), 1,3,5- Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxy-phenyl) propionate ] -Methane, 3,9-
Bis [2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane. A phenolic antioxidant having four or more phenol groups in one molecule preferably has two to three phenol groups because the coloring property of the antioxidant itself increases.

Among the phenolic antioxidants, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane, 1,6-
Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferred, and triethylene glycol-bis [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 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-butyl-phenyl) butane is preferred.

The phenolic antioxidant of the component (C) may be used alone or in combination of two or more. For 100 parts by weight of the system polycondensate,
It is selected in the range of 0.01 to 5 parts by weight. If this amount is 0.0
If the amount is less than 1 part by weight, the effect of the combined use with the stabilizer is not sufficiently exerted. If the amount exceeds 5 parts by weight, the effect is not so much improved for the amount, and it is economically disadvantageous.
Undesirable situations such as coloring of the composition are caused.
From the viewpoints of the combined effect with the stabilizer, economical efficiency and prevention of coloring of the composition, the preferred amount of the component (C) is (A)
It is preferably in the range of 0.05 to 3 parts by weight, particularly preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the component.

The method of adding the stabilizer of the component (B) and the phenolic antioxidant of the component (C), which is optionally used, are not particularly limited. You may. In any case, it is important that they are substantially homogeneously incorporated into the composition. Further, the stabilizer and the phenolic antioxidant are not limited by the melting point and the vapor pressure.

In the composition of the present invention, if necessary, other additives such as known stabilizers such as N, N'-bis (β-
Naphthyl) -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, poly (2,2,4-
Amine stabilizers such as trimethyl-1,2-dihydroquinoline), sulfur stabilizers such as dilauryl thiodipropionate, and phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite May be contained.

The polyetherester composition of the present invention comprises:
It is possible to produce an antistatic resin composition by mixing with an amorphous resin such as an acrylic resin or a polycarbonate resin. 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 viewpoint of thermal decomposition resistance and fluidity of the copolymer. Acrylate, ethyl acrylate, n-butyl acrylate are preferred.

This acrylic resin is used in chloroform.
It is preferred to use one having a reduced viscosity at 5 ° C. of 30 to 90 ml / g. 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 It is not preferable because the fluidity is reduced and extrusion molding and injection molding become difficult.

The acrylic resin may be produced by any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization. As the polymerization initiator at this time, an ordinary peroxide-based or azo-based radical polymerization initiator can be used, and this can be used in combination with a reducing agent as a redox-based initiator. An acrylic resin produced 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 can also 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, an alkyl mercaptan or the like can be used 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.

The amorphous resin into which the polyetherester composition of the present invention can be mixed is not limited to the above-mentioned acrylic resin, but can be selected from a wide range of general resins. Examples of such resins include polycarbonate resin, polystyrene, high impact polystyrene, ABS resin, MBS resin, amorphous copolyester, and the like, and these can be used alone or in combination of two or more. You can also.

To prepare an antistatic resin composition from the polyetherester composition of the present invention and an acrylic resin, the polyetherester composition is added with 30 to 2% by weight, preferably 25 to 5% by weight, of acrylic resin. 70 to 98% by weight, preferably 75 to 95% by weight of the system resin. When the polyetherester composition is less than 2% by weight, the obtained resin composition has insufficient antistatic properties. On the other hand, when the polyetherester composition exceeds 30% by weight,
It is not preferable because the mechanical strength of the obtained resin composition decreases. There is no particular limitation on the mixing method when producing the antistatic resin composition, and 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, 180 to 280 ° C. A method of granulating at about the temperature is used.

When a polyetherester composition of the present invention is mixed with an acrylic resin to produce an antistatic resin composition, an organic sulfonate and an organic phosphate are used to further improve the antistatic property. At least one selected from
Seed compounds 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 present invention, when producing the polyetherester polycondensate of the component (A), a compound containing a sulfonate or a phosphate in the molecule, for example, isophthalic acid containing a sulfonate is used. Alternatively, the alkyl ester can be copolycondensed and introduced into a polyetherester polycondensate.

When an antistatic resin composition is produced by mixing the polyetherester composition of the present invention and an acrylic resin, for example, various dyes, pigments, Methyl methacrylate / styrene copolymer beads as an organic light diffusing agent, barium sulfate, titanium oxide, calcium carbonate, talc, etc. as inorganic light diffusing agents, phthalic acid ester type, fatty acid ester type, trimellitic acid ester as plasticizer -Based, phosphate ester-based, polyester-based, etc., higher fatty acids as release agents, higher fatty acid esters, mono-, di-, or triglycerides of higher fatty acids, higher fatty acid esters as lubricants,
For example, polyolefins, phosphorus-based, phosphorus / chlorine-based, and phosphorus / bromine-based flame retardants, and glass fibers, carbon fibers, and the like may be mixed as reinforcing agents.

The antistatic resin composition obtained by mixing the polyetherester composition of the present invention and an acrylic resin can be prepared by extrusion molding to produce an antistatic sheet or film, or by injection molding. Various molded products can be manufactured. These moldings are advantageously performed at a temperature of about 180 to 280 ° C. in order to prevent burning and deterioration of the resin.

[0036]

The polyetherester composition of the present invention is obtained by mixing this with an amorphous resin such as an acrylic resin by suppressing a decrease in molecular weight and an increase in acid value due to ultraviolet rays. When the pellets are formed into a molded article by extrusion molding or injection molding, the molded article has a small decrease in antistatic properties even when irradiated with ultraviolet rays, and can maintain stable antistatic properties for a long period of time. Therefore, the polyetherester composition of the present invention, a lighting fixture cover,
It is suitable for producing an antistatic resin composition that can be used in applications that do not want to be charged or adhered to dust, such as a container for transporting semiconductor parts, equipment used in a clean room, a front plate of a projection television, and an optical lens.

[0037]

EXAMPLES 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 for the physical properties shown in each example are shown below. (1) Ultraviolet irradiation test method A 0.3 mm thick film was formed from the polyetherester composition at a molding temperature of 240 ° C. using a compression molding machine, and exposed to a high-pressure transparent mercury lamp for 48 hours. The changes in relative viscosity and acid value before and after that were measured.

(2) Measurement method of relative viscosity 0.25 g of the polyetherester composition was precisely weighed and dissolved in 50 ml of meta-cresol, and the flow time at 30 ° C. was measured with an Ostwald viscometer No. 3. The same measurement was carried out for the meta-cresol used for dissolution, and the relative viscosity was calculated by the ratio of the flowing time of the polyether ester composition to the meta-cresol solution and the flowing time of the meta-cresol solution.

(3) Method of Measuring Acid Value 0.1 g of the polyetherester composition was precisely weighed and dissolved in benzyl alcohol, and subjected to neutralization titration with a 0.1 N sodium hydroxide / benzyl alcohol solution.

The abbreviations of the stabilizers and phenolic antioxidants used in the respective examples have the following meanings. B-1: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol B-2: Poly [[6- (1,1, 3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2 , 6,6-Tetramethyl-4-piperidyl) imino]] B-3: 2- (5-methyl-2-hydroxyphenyl)
Benzotriazole B-4: 2- [2-hydroxy-3,5-bis (α, α
-Dimethylbenzyl) phenyl] -2H-benzotriazole C-1: triethylene glycol-bis [3- (3-t
-Butyl-5-methyl-4-hydroxyphenyl) propionate] C-2: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene C-3: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane C-4: pentaerythrityl-tetrakis [3- (3
5-Di-t-butyl-4-hydroxyphenyl) propionate] C-5: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate C-6: 3,5-di- t-butyl-4-hydroxy-benzylphosphonate-diethyl ester

EXAMPLE 1 51 parts by weight of dimethyl terephthalate and ethylene glycol 33 were placed in a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube.
Parts by weight and 0.02 parts by weight of manganese acetate tetrahydrate were charged and heated at 180 to 230 ° C. for 3 hours to carry out a transesterification reaction while distilling off generated methanol. Next, 16 parts by weight of polyoxyethylene glycol having a number average molecular weight of 1500, 0.03 parts by weight of antimony trioxide, 0.015 parts by weight of trimethyl phosphate, and 0.3 parts by weight of a stabilizer "B-1" were added to the reactor. Additional temperature was raised to 260 ° C. The pressure inside the reactor was gradually reduced, and a polycondensation reaction was carried out for 3 hours while maintaining the internal pressure at 1 Torr or less while removing excess ethylene glycol, thereby obtaining a polyetherester composition.

Next, the change in the relative viscosity and the change in the acid value of the polyetherester composition before and after the ultraviolet irradiation test were measured. Table 2 shows the results.

Examples 2 and 3 and Comparative Examples 1 to 5 In Example 1, instead of 0.3 parts by weight of the stabilizer "B-1", stabilizers or stabilizers of the types and amounts shown in Table 1 were oxidized. A polyetherester composition was prepared and evaluated in the same manner as in Example 1 except that an inhibitor was used. Table 2 shows the results.

[0045]

[Table 1]

[0046]

[Table 2]

Examples 4 to 11 and Comparative Example 6 51 parts by weight of dimethyl terephthalate, ethylene glycol 33 were placed in a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube.
Parts by weight and 0.02 parts by weight of manganese acetate tetrahydrate were charged and heated at 180 to 230 ° C. for 3 hours to carry out a transesterification reaction while distilling off generated methanol. Next, 16 parts by weight of polyoxyethylene glycol having a number average molecular weight of 1500, 0.03 parts by weight of antimony trioxide, and 0.015 parts by weight of trimethyl phosphate were added to the reactor together with the stabilizer “B-1” in the amount shown in Table 3 and Antioxidants of the type and amount shown in Table 3 were added, and the temperature was raised to 260 ° C. The pressure inside the reactor was gradually reduced, and a polycondensation reaction was carried out for 3 hours while maintaining the internal pressure at 1 Torr or less while removing excess ethylene glycol, thereby obtaining a polyetherester composition.

Next, the relative viscosity change and the acid value change of the polyetherester composition before and after the ultraviolet irradiation test were measured. Table 4 shows the results.

[0049]

[Table 3]

[0050]

[Table 4]

As can be seen from this table, even when an antioxidant is used in combination, the use of 0.005 parts by weight or more of a stabilizer can suppress a decrease in molecular weight and an increase in acid value due to ultraviolet irradiation, When a phenolic antioxidant having two or more hydroxyphenyl groups in one molecule is used as the antioxidant, the above-described inhibitory effect can be further enhanced.

Claims (3)

[Claims] 1. A method according to claim 1, wherein (B) at least 1 part per molecule per 100 parts by weight of the polyetherester polycondensate.
A polyetherester composition comprising 0.005 to 5 parts by weight of a stabilizer containing one triazine ring. 2. A method according to claim 1, wherein (B) at least 1 part per molecule per 100 parts by weight of the polyetherester polycondensate.
Polyether comprising 0.005 to 5 parts by weight of a stabilizer containing one triazine ring and 0.01 to 5 parts by weight of a phenolic antioxidant having two or more hydroxyphenyl groups per molecule. Ester composition. 3. The polyetherester polycondensate of component (A) comprises (a) a polyoxyalkylene glycol component, (b) a dicarboxylic acid component, and (c) a dihydroxy compound component. Item 3. The polyetherester composition according to Item 1 or 2.