JPH1060213A - Thermally stabilized antistatic acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition useful for an illuminator cover, etc., excellent in moldability free from defective appearance caused by discoloration by heat and gelatinization, by mixing a specific resin composition with a prescribed phenolic antioxidant in a specified ratio. SOLUTION: This thermally stabilized antistatic acrylic resin composition is obtained by blending 100 pts.wt. of a resin component composed of (A) 70-98wt.% of an acrylic resin and (B) 30-2wt.% of a polyether-ester-based polycondensate constituted of a polyoxyalkylene glycol component, a dicarboxylic acid component such as terephthalic acid and a dihydroxy compound component such as ethylene glycol with (C) 0.01-5 pts.wt. of a phenolic antioxidant containing two or more hydroxyphenyl groups in one molecule such as triethylene glycolbis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-stabilized antistatic acrylic resin composition, and more particularly, it does not cause appearance defects due to heat coloring or gelling during granulation or molding. The present invention relates to a heat-stabilized antistatic acrylic resin composition that hardly causes fogging of a polishing roll or a mold during molding and gives a molded article having a good surface appearance and excellent antistatic properties. .

[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).
Since this composition is unstable to heat and easily undergoes oxidative decomposition, for example, when extruded from an extruder and formed into an extruded plate with a polishing roll, clouding occurs on the roll surface,
In addition, when used as an injection molding material, there is a drawback that fogging occurs in a mold and as a result, the surface of a molded product is damaged. Furthermore, even though the generation of gel is considerably smaller than the case where the polyamide-based elastomer is used as an antistatic agent, it cannot be completely suppressed. Alternatively, the composition staying in the molding machine gels and impairs the appearance of the molded article.

[0010]

SUMMARY OF THE INVENTION Under such circumstances, the present invention does not involve appearance defects due to heat coloring or gelling at the time of granulation or molding, An object of the present invention is to provide a heat-stabilized antistatic acrylic resin composition which does not cause polishing of a polishing roll or a mold and gives a molded article having a good surface appearance and an excellent antistatic property. Things.

[0011]

The present inventors have conducted intensive studies to develop an acrylic resin composition having good antistatic properties. As a result, the present inventors have found that an acrylic resin and a polyetherester polycondensate are obtained. By blending a certain phenolic antioxidant into the resin mixture, they have found that an acrylic resin composition that gives a molded article having antistatic properties without poor appearance can be obtained. The present invention has been made.

That is, according to the present invention, 100 parts by weight of a resin component composed of (A) 70 to 98% by weight of an acrylic resin and (B) 30 to 2% by weight of a polyetherester polycondensate are added to (C) A) a phenolic antioxidant having at least two hydroxyphenyl groups in one molecule;
An object of the present invention is to provide an antistatic acrylic resin composition containing 5 parts by weight.

[0013]

DETAILED DESCRIPTION OF THE INVENTION In the composition of the present invention, the acrylic resin used as the component (A) can be arbitrarily selected from those conventionally used in general, and in particular, 50 to 99% by weight of methyl methacrylate unit. It is preferable to use one comprising 1 to 50% by weight of other monomer units copolymerizable therewith. Other copolymerizable monomers include, for example, alkyl methacrylate having an alkyl group having 2 to 18 carbon atoms, and alkyl group having 1 to 18 carbon atoms.
In addition to the alkyl acrylates, α, β-unsaturated acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid,
Examples include unsaturated group-containing divalent carboxylic acids such as itaconic acid, aromatic vinyl compounds such as styrene, α-methylstyrene, and nuclear-substituted styrene, maleic anhydride, maleimide, and N-substituted maleimide. These may be used alone or in combination of two or more. In addition, a copolymer of methyl methacrylate and methacrylic acid or acrylic acid, a polymer obtained by heat-treating it to perform a dealcoholization reaction or a dehydration reaction to form a six-membered cyclic anhydride unit,
And a polymer obtained by an imidization reaction with ammonia or an amine to form a 6-membered imide unit. Among them, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are advantageous from the viewpoint of the thermal decomposition resistance and fluidity of the copolymer. Particularly, methyl acrylate, ethyl acrylate and n-butyl acrylate are preferred.

This acrylic resin is prepared by adding 2
Those having a reduced viscosity at 5 ° C. of 30 to 90 ml / g are preferred. 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 Fluidity is reduced, making extrusion and injection molding difficult.

Such an acrylic resin is prepared by suspension polymerization,
It may be produced by any known method such as emulsion polymerization, bulk polymerization, or solution polymerization. As the polymerization initiator at this time, a normal peroxide-based or azo-based radical polymerization initiator, or a redox-based initiator obtained by combining this with a reducing agent can be used. An acrylic resin obtained by an anionic polymerization method using an alkyl lithium, 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 from 30 to 10 for suspension or emulsion polymerization.
For 0 ° C., bulk or solution polymerization, a range of 80-170 ° C. is used. 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.

Further, a part of the acrylic resin may be replaced with another amorphous resin if necessary, as long as the desired performance is not impaired. Examples of the amorphous resin include polycarbonate resin, polystyrene, impact-resistant polystyrene, ABS resin, MBS resin, and amorphous copolyester. These may be used alone or in combination of two or more. They may be used in combination.

In the composition of the present invention, the polyetherester-based polycondensate used as the component (B) is a polycondensate comprising a polyether segment and a polyester segment, for example, (a) a polyoxyalkylene glycol and (b) And (c) a dihydroxy compound obtained by polycondensation of a dihydroxy compound.

Here, (a) the polyoxyalkylene glycol component includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, ethylene glycol / propylene glycol block copolymer and the like. 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
More than one species may be used in combination. 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. 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.

In order to produce the polyetherester polycondensate of the component (B), for example, the above-mentioned polyoxyalkylene glycol, dicarboxylic acid or its ester and dihydroxy compound are charged into a reactor at a predetermined ratio, respectively. In the presence or absence of a solvent, polycondensation is carried out while removing water or alcohol generated during the reaction out of the reactor to increase the molecular weight. To remove water or alcohol from the reactor, nitrogen gas is flown or the inside of the reactor is highly depressurized. The temperature at the time of the polycondensation is selected in the range of usually 150 to 300 ° C, preferably 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, the coloring and deterioration of the polymer during the reaction can be prevented.

In the composition of the present invention, the blending ratio of the acrylic resin (A) and the polyetherester polycondensate (B) is the total weight of the components (A) and (B). (A) 70-98% by weight based on
It is necessary that the component (B) be in the range of 30 to 2% by weight. When the amount of the component (B) is less than 2% by weight, the obtained resin composition does not sufficiently exhibit antistatic properties,
If it exceeds 30% by weight, the mechanical strength of a molded article obtained from the resin composition will be reduced. From the viewpoints of the antistatic property and mechanical strength of the resin composition, the preferred compounding ratio is such that the component (A) is 75 to 95% by weight and the component (B) is 25 to 5% by weight.
Range.

In the composition of the present invention, the phenolic antioxidant used as the component (C) has at least two hydroxyphenyl groups in one molecule.
Such substances include one-sided hindered phenolic antioxidants, i.e., those having a hindered group on one side of a hydroxyl group, and both hindered phenolic antioxidants, i.e., those having hindered groups on both sides of a hydroxyl group. Examples of such phenolic antioxidants include 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, 1,6-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 (3,5-di-t-butyl- 4
-Ethyl-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-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,
1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane. As this phenolic antioxidant, those having 2 to 4 hydroxyphenyl groups in one molecule are preferable, but the phenolic antioxidant having 4 or more hydroxyphenyl groups in one molecule is the antioxidant itself. Is more preferably one having 2 to 3 hydroxyphenyl groups, since the coloring property of the compound becomes larger.

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 and 1,1,3-tris (2-methyl-4-hydroxy-5-t-butyl-phenyl) butane are preferred .

The component (C) phenolic antioxidant may be used alone or in combination of two or more. The compounding amount is 0.01 to 5 parts by weight per 100 parts by weight of the resin component composed of the acrylic resin (A) and the polyetherester polycondensate (B).
It is selected in the range of parts by weight. When the amount is less than 0.01 part by weight, the effect of improving the thermal stability of the resin composition is not sufficiently exhibited. When the amount is more than 5 parts by weight, the effect is not improved for the amount, and the economical efficiency is rather low. In addition to this, unfavorable situations such as coloring of the resin composition and fogging of the polishing roll and the mold are caused. From the viewpoints of improving heat resistance stability, economy, preventing coloration of the composition, and preventing clouding of the polishing roll and the mold, the preferred amounts of the component (C) are the components (A) and (B). With respect to 100 parts by weight of the resin component
To 3 parts by weight, and particularly preferably 0.1 to 2.0 parts by weight.

The phenolic antioxidant is not limited based on the melting point and vapor pressure. The phenolic antioxidant contains two or more hydroxyphenyl groups in one molecule, and has tert-terminal on one or both sides of the hydroxyl group. It is preferable that a bulky group such as -butyl group is introduced and the hydroxyl group is hindered.

The acrylic resin composition of the present invention may optionally contain additives such as N, N'-bis (β-naphthyl) -p-phenylenediamine, N , N'-Diphenyl-p-phenylenediamine, poly (2,2,4-trimethyl-1,2-
Amine-based stabilizers such as dihydroquinoline), sulfur-based stabilizers such as dilaurylthiodipropionate, phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, and known pigments, Titanium and a fluorescent whitening agent may be added.

In order to prepare the acrylic resin composition of the present invention, for example, (1) the components (A), (B) and (C) are mixed by a drum blender or a Henschel mixer and then extruded. (2) The component (C) is added to the polyetherester polycondensate of the component (B) in advance during polymerization or after polymerization using a polymer kneader or the like. And (A) a mixture of component (A) and granulation. (3) Component (C) is added to acrylic resin (A) and polyetherester polycondensate (B) in suitable amounts in advance. A method of adding the mixture using a polymer kneader or the like, mixing them, and granulating them can be used, but other methods may be used. In any case, it is important that the components are substantially homogeneously mixed. The kneading temperature is usually 18
It is selected in the range of 0 to 280 ° C.

In preparing the acrylic resin composition of the present invention, at least one compound selected from organic sulfonates and organic phosphates may be used in combination to further improve the antistatic property. . Examples of these compounds include aromatic sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid,
Examples thereof include alkali metal salts and alkaline earth metal salts such as alkylsulfonic acids such as laurylsulfonic acid and stearylsulfonic acid, and organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate. Sodium salts and potassium salts are preferred from the viewpoint of the antistatic effect of the resin composition. The compounding amount of the organic sulfonate or the organic phosphate is 10%.
It is preferably 5 parts by weight or less based on 0 parts by weight. 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 (B), a compound containing a sulfonate or a phosphate in the molecule, for example, isophthalic acid containing a sulfonate is used. And its alkyl ester can be copolymerized and introduced into a polyetherester-based polycondensate.

When the acrylic resin composition of the present invention is produced, an antistatic property and other physical properties are not impaired.
For example, various dyes, pigments, methyl methacrylate / styrene copolymer beads as an organic light diffusing agent, barium sulfate, titanium oxide, calcium carbonate, talc and the like as inorganic light diffusing agents, phthalate ester as a plasticizer, Fatty acid ester type, trimellitate type, phosphate type, polyester type, etc., higher fatty acid, higher fatty acid ester, higher fatty acid mono as release agent,
Di- or triglycerides, etc., higher fatty acid esters and polyolefins as lubricants, phosphorus-based, phosphorus / chlorine-based, phosphorus / bromine-based as flame retardants, and glass fibers and carbon fibers as reinforcing agents can be mixed.

The acrylic resin composition of the present invention can be used to produce an antistatic sheet or film by extrusion or various molded articles by injection molding. These moldings are performed at a temperature of 1 to prevent burning and deterioration of the resin.
It is preferable to carry out in the range of 80 to 280 ° C.

[0034]

The acrylic resin composition of the present invention can be used for producing an extruded plate or various molded articles having a long antistatic property.
It does not cause appearance defects due to heat coloring or gelling, hardly causes fogging of the polishing roll for extrusion plate production and the mold for injection molding, and provides a molded article with good surface appearance and excellent antistatic properties. it can. Therefore, the acrylic resin composition of the present invention is suitable for use in applications that dislike charging or dust adhesion such as lighting equipment covers, transport containers for semiconductor components, equipment used in clean rooms, front panels of projection televisions, and optical lenses. ing.

[0035]

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 in each example are shown below. (1) Method of Measuring Surface Resistance Using an insulation resistance meter Ultra Megohmmeter SM-8200 series SME8311 manufactured by Toa Denpa Kogyo Co., Ltd., 500 V was applied to the laminated sheet at 23 ° C. and 50% relative humidity for 45 seconds, and 15 After 2 seconds, the surface resistance was measured.

(2) Gelation test of the composition 0.2 g of the composition is placed in a glass ampoule having a capacity of 5 ml, and the tube is sealed at normal pressure. The sealed ampule is heated in an oven at 250 ° C. for a predetermined time, and after completion, the composition is taken out. The removed composition was placed in a 25 ml screw bottle, 5 g of hexafluoroisopropanol was added, and the solubility was visually observed, and evaluated according to the following criteria. ○: No gel-like substance, △: Slightly gel-like insoluble matter

The meanings of the abbreviations of the starting compounds used in the respective examples are as follows. 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-t-butyl-phenyl) butane C-4: Octadecyl-3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate C-5: 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester

Reference Example Production of Polyetherester Polycondensate 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, and 0.015 parts by weight of trimethyl phosphate were added to the reactor, and the temperature was raised to 260 ° C. The pressure inside the reactor was gradually reduced, and polycondensation reaction was performed for 3 hours while maintaining the internal pressure at 1 Torr or less while distilling off excess ethylene glycol to obtain a polyetherester polycondensate.

Example 1 85 parts by weight of an acrylic resin "Delpet LP-1" (manufactured by Asahi Kasei Kogyo Co., Ltd.), 15 parts by weight of a polyetherester polycondensate obtained in Production Example, sodium dodecylbenzenesulfonate 0.5 parts by weight and 0.3 parts by weight of the phenolic antioxidant "C-1" are kneaded at an extrusion temperature of 250 ° C. using a twin-screw extruder equipped with a 30 mm vent. An acrylic resin composition was prepared by pelletizing with a cutter. The pellets were subjected to a gelation test.

Next, the pellets were used as a laminated portion, while the acrylic resin "Delpet LP-1" was used as a substrate portion.
Co-extrusion was performed using an extruder having a diameter of 30 mm and L / D = 24 for the laminated portion and an extruder having a diameter of 90 mm and L / D = 32 for the substrate portion. The die was of a feed block type, and the lip opening and the clearance of the polishing roll were adjusted so that the laminated sheet had a thickness of 3 mm. Extruder temperature is 250
° C, the thickness of the laminated portion was adjusted to 20 µm by the discharge amount of the extruder, and a laminated sheet having a sheet width of 60 cm was prepared. At this time, the degree of haze of the polishing roll was visually observed.
Thereafter, a test piece was cut out from the obtained sheet,
Conditioning in a constant temperature room with a relative humidity of 50% for 24 hours,
The initial surface resistance was measured. Further, the appearance of the obtained laminated sheet was visually observed. Table 2 shows the results.

Examples 2-7, Comparative Examples 1-8 In Example 1, the phenolic antioxidant "C-1" was used.
Instead of using the types and amounts of phenolic antioxidants shown in Table 1, an acrylic resin composition was prepared in the same manner as in Example 1, and a laminated sheet was further prepared using the same. Was evaluated. Table 2 shows the results.

[0043]

[Table 1]

[0044]

[Table 2]

Claims (5)

[Claims] 1. (A) 70 to 98% by weight of an acrylic resin
And (B) 30 to 2% by weight of a polyetherester-based polycondensate, and (C) 1
An antistatic acrylic resin composition comprising 0.01 to 5 parts by weight of a phenolic antioxidant having at least two hydroxyphenyl groups in the molecule. 2. The polyetherester-based polycondensate of component (B) comprises (a) a polyoxyalkylene glycol component, (b) a dicarboxylic acid component, and (c) a dihydroxy compound component. Item 4. An antistatic acrylic resin composition according to Item 1. 3. The antistatic acrylic resin composition according to claim 1, wherein the phenolic antioxidant (C) has two hydroxyphenyl groups in one molecule. 4. The antistatic acrylic resin composition according to claim 1, wherein the phenolic antioxidant (C) has three hydroxyphenyl groups in one molecule. 5. The antistatic acrylic resin composition according to claim 1, wherein the phenolic antioxidant (C) has four hydroxyphenyl groups in one molecule.