JP2000192018A - Antistatic agent and antistatic acrylic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic agent which imparts excellent weatherability, antistatic effects, and persistence thereof to an acrylic resin without detriment to the clarity by using, as the agent, a polyether ester which is prepared by using, as diol components, an alkylene diol and a dihydric phenol in a specified ratio. SOLUTION: This composition is a polyether ester which is prepared from an aromatic polycarboxylic acid or its alkyl ester, a polyalkylene glycol, an alkylene diol, and a dihydric phenol as essential raw materials. In the polyether ester, the ratio (x/y) of the number (x) of alkylene groups derived from the alkylene diol to the number (y) of aromatic rings derived from the dihydric phenol is in the range of 2-3,000. Preferably, the aromatic polycarboxylic acid or its alkyl ester contains a sulfonate-group-containing dicarboxylic acid component in an amount of 0.1-15 mol% based on the total acid component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent excellent in antistatic effect, durability of antistatic effect, transparency and weather resistance, and an antistatic acrylic resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, acrylic resins have been used for a wide range of applications, such as signs, lighting covers, store displays, exteriors, vending machine front panels, and materials used in clean rooms, utilizing their excellent appearance and light resistance. ing.

However, ordinary acrylic resins are:
It is easy to be charged and tends to adhere to dust and the like, and in order to prevent this, antistatic performance is required. In particular, a high level of antistatic performance is required for use in clean room materials.

[0004] As a method of imparting antistatic properties to an acrylic resin, for example, a method of kneading a surfactant or applying it to a surface is well known. The antistatic agent is easily removed by washing with water or the like, losing the antistatic performance, and making it impossible to provide continuous antistatic performance.

[0005] The method of applying a surfactant to the surface has a problem of a solvent at the time of application, and has problems such as cracking of the material or peeling of the applied layer.

Therefore, conventionally, as a technique for effectively imparting an antistatic property to an acrylic resin, for example, Japanese Unexamined Patent Application Publication No.
Japanese Patent No. 59601 discloses an antistatic acrylic resin composition containing an acrylic resin, a polyetherester containing a specific amount of an aromatic dicarboxylic acid component nucleus-substituted with a sulfonate group, and a surfactant as essential components. It has been disclosed.

[0007]

However, when the polyetherester-based antistatic agent described in JP-A-9-59601 is used, the antistatic effect is reduced due to light irradiation or the like. In addition, there is a problem that the transparency of the acrylic resin is reduced.

An object of the present invention is to provide an antistatic agent excellent in weather resistance, antistatic effect and sustainability without deteriorating transparency with respect to an acrylic resin, and their performance. An object of the present invention is to provide an acrylic resin composition having both of the above.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have identified an alkylene diol and a bifunctional phenol compound as diol components used as a raw material of a polyetherester used as an antistatic agent. The inventors have found that the above-mentioned problems can be solved by using them together in proportions, and have completed the present invention.

That is, the present invention relates to an aromatic polycarboxylic acid or an alkyl ester thereof, a polyalkylene glycol,
A polyether ester (A) containing an alkylene diol and a bifunctional phenol compound as essential raw material components, and the number (x) of alkylene groups derived from the alkylene diol in the polyether ester; 2
An antistatic agent characterized in that the ratio to the number (y) of aromatic nuclei caused by the functional phenol compound is in the range of (x) / (y) = 2 to 3000, and an acrylic containing the same. It relates to a resin composition.

The antistatic agent of the present invention is a polyether ester (A) containing an aromatic dicarboxylic acid or an alkyl ester thereof, a polyalkylene glycol, an alkylene diol, and a bifunctional phenol compound as essential raw materials, As described above, the ratio of the number of alkylene groups (x) caused by the alkylene diol in the polyetherester (A) to the number of aromatic nuclei (y) caused by the bifunctional phenol compound is (x). / (Y) = 2-3
000 range. That is, (x) /
In a region where the ratio of (y) is lower than 2, the compatibility with the acrylic resin is reduced, and the transparency and the mechanical strength as well as the antistatic effect are reduced. For example, a conventional antistatic agent composed of a conventional ethylene-ethylene oxide adduct of bisphenol A, ethylene glycol, and terephthalic acid cannot be used because the amount of aromatic nuclei caused by bisphenol A is excessive compared to the present invention. Poor compatibility with resin, resulting in poor transparency and mechanical strength. On the other hand, in a region where the ratio of (x) / (y) exceeds 3000, although the compatibility with the acrylic resin is improved,
It becomes inferior in weather resistance.

In order to adjust the (x) / (y) ratio in the polyetherester (A), it is possible to select the reaction ratio of each raw material component as appropriate and produce it by a conventional method. An aromatic dicarboxylic acid or an alkyl ester thereof,
Polyetherester (a1) containing alkylene diol and polyalkylene glycol as essential raw material components,
And an aromatic dicarboxylic acid, an alkylene diol and 2
It is preferable to produce each of the polyesters (a2) containing a functional phenol compound as an essential raw material component and to react them to produce (A), because the (x) / (y) ratio can be easily adjusted.

The polyetherester (A) can exhibit an unprecedentedly superior antistatic effect by introducing a metal sulfonic acid salt into the molecular structure. Specific examples of such a sulfonic acid metal salt include those represented by the following general formula 2.

[0014]

## STR1 ## where M is an alkali metal or an alkaline earth metal, particularly preferably Na, K, Li, Mg, Ca or the like.

Although the content of the sulfonate is not particularly limited, the content of the sulfonate group present in the polyetherester (A) in terms of the weight of the raw material monomer is not limited. From the viewpoint of the effect of improving the antistatic property, the ratio is preferably from 0.1 to 10% by weight based on the weight of the polyetherester. Here, as the aromatic polycarboxylic acid or its alkyl ester used in (a1) and (a2), divalent, trivalent and tetravalent or higher valent aromatic carboxylic acids, their acid anhydrides, or their aromatics It is an ester of a polycarboxylic acid. Also,
The polyvalent carboxylic acid preferably has 4 to 20 carbon atoms.

Here, the divalent carboxylic acid and its anhydride are not particularly restricted but include, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, Diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, indene-4,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, azulene-2,5-dicarboxylic Acid, heptalene-1,7-dicarboxylic acid, biphenylene-1,5-dicarboxylic acid, as-indacene-2,6-dicarboxylic acid, s-
Indacene-1,7-dicarboxylic acid, acenaphthylene-
3,8-dicarboxylic acid, fluorene-1,8-dicarboxylic acid, phenalene-4,8-dicarboxylic acid, phenanthrene-1,6-dicarboxylic acid, anthracene-1,8-
Dicarboxylic acid, fluoranthene-6,7-dicarboxylic acid, acephenanthrylene-3,8-dicarboxylic acid, aceanthrylene-3,7-dicarboxylic acid, triphenylene-2,10-dicarboxylic acid, pyrene-1,6- Dicarboxylic acid, chrysene 1,7-dicarboxylic acid, naphthacene-
1,5-dicarboxylic acid, preyandene 2,5-dicarboxylic acid, picene-2,8-dicarboxylic acid, perylene-
Aromatic dicarboxylic acids such as 2,8-dicarboxylic acid, pentaphen-5,11-dicarboxylic acid, pentacene 2,6-dicarboxylic acid, their alkyl nucleus-substituted carboxylic acids, their halogen nucleus-substituted carboxylic acids, and phthalic anhydride An anhydride of each of the above-mentioned dicarboxylic acids such as an acid and the like can be mentioned.

The trivalent carboxylic acids include 1,2,4-trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, 2,6,7-naphthalene tricarboxylic acid, 3,3
', 4-diphenyltricarboxylic acid, benzophenone 3,3', 4-tricarboxylic acid, diphenylether-
3,3 ', 4-tricarboxylic acid, indene-3,4,7
-Tricarboxylic acid, naphthalene-2,5,7-tricarboxylic acid, naphthalene-2,4,6-tricarboxylic acid, azulene-2,5,7-tricarboxylic acid, heptalene-
1,3,7-tricarboxylic acid, biphenylene-1,3,3
5-tricarboxylic acid, as-indacene-2,4,6-tricarboxylic acid, s-indacene-1,3,7-tricarboxylic acid, acenaphthylene-3,6,8-tricarboxylic acid,
Fluorene-1,5,8-tricarboxylic acid, phenalene-2,4,8-tricarboxylic acid, phenanthrene-1,
6,8-tricarboxylic acid, anthracene-1,5,8-
Tricarboxylic acid, fluoranthene-4,6,7-tricarboxylic acid, acephenanthrylene-3,6,8-tricarboxylic acid, aceanthrylene-3,5,7-tricarboxylic acid, triphenylene-2,6,10-tricarboxylic acid Acid, pyrene-1,3,6-tricarboxylic acid, chrysene 1,4,7-tricarboxylic acid, naphthacene-1,3,5
-Tricarboxylic acid, preyandene 2,5,8-tricarboxylic acid, picene-2,5,8-tricarboxylic acid, perylene-2,4,8-tricarboxylic acid, pentaphen-
5,11,14-tricarboxylic acid, pentacene 2,6
Examples thereof include aromatic tricarboxylic acids such as 14-tricarboxylic acids and substituted alkyl nuclei and substituted halogen nuclei thereof, and anhydrides of the above tricarboxylic acids.

Examples of tetravalent carboxylic acids include pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid and diphenylsulfone-2. , 2 ', 3,3'-tetracarboxylic acid, diphenyl ether-2,2', 3
3'-tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, indene-2,3,4,7-tetracarboxylic acid, naphthalene-2,3,5,7-tetracarboxylic acid, naphthalene- 2,4,6,7-tetracarboxylic acid, azulene-2,3,5,7-tetracarboxylic acid, heptalene-1,3,4,7-tetracarboxylic acid, biphenylene-1,3,5,7- Tetracarboxylic acid, as-indacene-2,4,6,7-tetracarboxylic acid, s-indacene-1,2,3,7-tetracarboxylic acid, acenaphthylene-3,4,6,8-tetracarboxylic acid, Fluorene-1,2,5,8-tetracarboxylic acid, phenalene-
2,3,4,8-tetracarboxylic acid, phenanthrene-
1,2,6,8-tetracarboxylic acid, anthracene-
1,5,6,8-tetracarboxylic acid, fluoranthene-
4,5,6,7-tetracarboxylic acid, acephenanthrylene-2,3,6,8-tetracarboxylic acid, acetantetralen-3,4,5,7-tetracarboxylic acid, tetraphenylene-2 , 3,6,10-tetracarboxylic acid,
Pyrene-1,3,6,7-tetracarboxylic acid, chrysene 1,4,7,8-tetracarboxylic acid, naphthacene-1,
2,5,7-tetracarboxylic acid, preyandene 2,
5,8,9-tetracarboxylic acid, picene-2,5,7,
8-tetracarboxylic acid, perylene-2,4,5,8-tetracarboxylic acid, pentaphen-5,11,12,14
And aromatic tetracarboxylic acids such as tetracarboxylic acid and pentacene 2,3,6,14-tetracarboxylic acid, and the tetracarboxylic acid monoanhydrides and tetracarboxylic dianhydrides of the above compounds. These can be used alone or in combination of two or more.

Among them, terephthalic acid, isophthalic acid, naphthalene-2,
5-Dicarboxylic acid and naphthalene-2,6-dicarboxylic acid are preferred, and terephthalic acid, isophthalic acid and naphthalene-2,6-dicarboxylic acid are particularly preferred. Further, it is preferable to use a trivalent or higher polycarboxylic acid in combination, since the molecular weight of the target polyether ester can be easily increased.

The alkyl esters of aromatic polycarboxylic acids are defined as mono-, di-, and tri- and tetra-esters of the above-mentioned aromatic polycarboxylic acids in which some or all of the polycarboxylic acids are esterified. Any of the compounds can be used.

These aromatic polycarboxylic acids or their alkyl esters can be used alone or as a mixture of two or more.

The amount of the aromatic polycarboxylic acid used is as follows:
For example, it is preferable from the viewpoint of the antistatic effect and the weather resistance that the polyetherester is incorporated in the range of 10 to 60% by weight in terms of the charged ratio of each raw material constituting the finally obtained polyetherester.

As described above, in the present invention, the antistatic effect can be further improved by introducing a metal sulfonate group into the polyetherester (A). As the polyvalent carboxylic acid or its alkyl ester, it is preferable to use a partially sulfonated phthalate or its alkyl ester in combination.

The structure of the sulfonated phthalate or its alkyl ester is not particularly limited. Examples thereof include metal sulfonated phthalates, sulfonated phosphonium phthalates, and sulfonated ammonium phthalates. Salts or compounds in which a part or all of sulfonated phthalates such as monoesters and diesters thereof are esterified, specifically, sodium sulfoterephthalate, potassium sulfoterephthalate , Magnesium sulfoterephthalate, calcium sulfoterephthalate, zinc sulfoterephthalate, phosphonium sulfoterephthalate, ammonium sulfoterephthalate, ammonium sulfoterephthalate, sodium sulfoisophthalate, potassium sulfoisophthalate, Magnesium rufoisophthalate, calcium sulfoisophthalate, zinc sulfoisophthalate, phosphonium sulfoisophthalate, ammonium sulfoisophthalate, monomethyl sodium sulfoterephthalate, monomethyl potassium sulfoterephthalate, monomethylmagnesium sulfoterephthalate, Monomethyl calcium sulfoterephthalate, monomethyl zinc sulfoterephthalate, monomethyl phosphonium sulfoterephthalate, monomethylammonium sulfoterephthalate, dimethyl sodium sulfoterephthalate, dimethyl potassium sulfoterephthalate,
Dimethylmagnesium sulfoterephthalate, dimethylcalcium sulfoterephthalate, dimethylzinc sulfoterephthalate, dimethylphosphonium sulfoterephthalate, dimethylammonium sulfoterephthalate,
Monomethyl sulfoisophthalate, monomethyl potassium sulfoisophthalate, monomethylmagnesium sulfoisophthalate, monomethylcalcium sulfoisophthalate, monomethylzinc sulfoisophthalate, monomethylphosphonium sulfoisophthalate, monomethylammonium sulfoisophthalate, sulfoisophthalate monomethylammonium salt, sulfo Dimethyl isophthalate, dimethyl potassium sulfoisophthalate, dimethylmagnesium sulfoisophthalate, dimethylcalcium sulfoisophthalate, dimethylzinc sulfoisophthalate, dimethylphosphonium sulfoisophthalate, dimethylammonium sulfoisophthalate, etc. Can be

Of these, alkali metal salts and alkaline earth metal salts such as sodium salt, potassium salt, magnesium salt and calcium salt are preferable, and these sulfonated phthalates are partially or partially. Compounds which are all esterified are preferred. In particular, lower alkyl esters having 6 or less carbon atoms, such as methyl esters and ethyl esters, are preferred. These may be used alone or in combination of two or more.

The amount of the sulfonated phthalate or the alkyl ester thereof is not particularly limited, but is preferably used in a proportion of 0.1 to 15 mol% of the total raw acid components. When the amount is 0.1 mol% or more, the antistatic effect of the polyether ester is remarkably improved. On the other hand, when the amount is 15 mol% or less, the mechanical properties of the obtained polyether ester and the durability of the antistatic effect are improved.

Next, as the alkylene diol used in (a1) and (a2), for example, ethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,2-butylene glycol, trimethylene glycol, neopentyl glycol, diethylene glycol, 2-methyl-1,3-propylene glycol, triethylene glycol, octamethylene glycol, 1,4-cyclohexanedimethanol And alkylene glycols such as 1,4-cyclohexanediol, 1,6-hexaneglycol, and 3-methyl-1,5-pentanediol. These may be used alone or in combination of two or more. Among these, glycols having 2 to 8 carbon atoms are preferable because of excellent mechanical strength, and ethylene glycol is particularly preferable.

Next, the poly (alkylene oxide) glycol used in (a1) includes poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide)
Examples include glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. These may be used alone or in combination of two or more.

The bisphenols in the poly (alkylene oxide) glycol adduct of bisphenols are not particularly restricted but include, for example, bisphenol A, bisphenol S, fluorinated bisphenol A, chlorinated bisphenol A, and brominated bisphenol. A, 4,4-bis (hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methane, bis (4
Examples thereof include -hydroxyphenyl) ether and bis (4-hydroxyphenyl) amine, and among them, a compound having a bisphenol A skeleton is preferable.

Among these poly (alkylene oxide) glycols, those having 2 to 4 carbon atoms in the alkylene oxide structural unit constituting the glycol are preferred because of their excellent antistatic effect. Ethylene oxide, propylene oxide, 1,2
-It is preferable to have butylene oxide, tetramethylene oxide or the like as an alkylene oxide structural unit.

The alkylene oxide structural unit may be composed of a single component, or may be composed of a plurality of different components as in the above-mentioned exemplified compounds. It is preferable to contain ethylene oxide as a constituent component from the viewpoint of being excellent. Specifically, those having an ethylene oxide chain content (ratio of the molecular weight of the ethylene oxide group portion to the molecular weight of the poly (alkylene oxide) glycol) of 10% by weight or more are preferable from the viewpoint of the antistatic effect, and in particular, poly (ethylene oxide) Glycols are preferred.

Such a poly (alkylene oxide) glycol is not particularly limited in its molecular weight and the like, but preferably has a number average molecular weight of 300 to 50,000 from the viewpoint of antistatic effect.

When a poly (alkylene oxide) glycol adduct of bisphenol is used as the poly (alkylene oxide) glycol, the number average molecular weight is preferably 40 from the viewpoint of antistatic effect, mechanical properties and weather resistance.
Those having 0 to 200,000 are preferred. That is, when the number average molecular weight is 400 or more, the antistatic effect is more remarkably improved, and when the number average molecular weight is 200,000 or less, the obtained polyetherester has good mechanical properties. Become. The number average molecular weight is particularly preferably in the range of 500 to 9,000 from the viewpoint of excellent balance between these. In the polyetherester (a1), when a poly (alkylene oxide) glycol adduct of bisphenols is used as a raw material, the number (x) of the aromatic nuclei caused by the bisphenols is also included in the number of the aromatic nuclei. Of course.

The poly (alkylene oxide) glycol adduct of bisphenols is preferably used in a ratio of 10 to 90% by weight of the raw materials constituting the polyetherester. When the content is 10% by weight or more, the antistatic effect of the polyether ester is remarkably improved. On the other hand, when the content is 90% by weight or less, the obtained polyether ester has good mechanical properties and heat resistance. In particular, the range of 40 to 80% by weight is preferable from the viewpoint of excellent balance between them.

Next, the bifunctional phenol used in the polyester (a2) is not particularly limited.
For example, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, naphthalene-2,6-diol, naphthalene-2,7-diol, diphenyl-4,4'-diol, diphenoxy Ethanediol, indene-4,7-diol, naphthalene-2,5-diol, naphthalene-2,6-diol, azulene-2,5-diol, heptalen-1,
7-diol, biphenylene-1,5-diol, as-
Indacene-2,6-diol, s-indacene-1,7
-Diol, acenaphthylene-3,8-diol, fluorene-1,8-diol, phenalene-4,8-diol, phenanthrene-1,6-diol, anthracene-1,8-diol, fluoranthene-6,7-diol , Acephenanthrylene-3,8-diol, aceanthrylene-3,7-diol, triphenylene-
2,10-diol, pyrene-1,6-diol, chrysene 1,7-diol, naphthacene-1,5-diol, preyandene 2,5-diol, picene-2,8
-Diol, perylene-2,8-diol, pentaphen-5,11-diol, pentacene 2,6-diol, and other bisphenols such as bisphenol A, bisphenol F and bisphenol S. As these bifunctional phenols, 1,4-dihydroxybenzene, naphthalene-2,6-diol, and bisphenols are preferable because the effect of weather resistance is particularly remarkable.

As the bisphenols, a block copolymer or a random copolymer of ethylene oxide and propylene oxide of bisphenol A, an ethylene oxide adduct of bisphenol F, and an ethylene oxide of bisphenol F and propylene oxide are particularly preferred from the viewpoint of compatibility with the acrylic resin. Block or random copolymers, bisphenol S ethylene oxide adducts, bisphenol S ethylene oxide and propylene oxide block or random copolymers, their alkyl nuclei substituted products, and these halogen nucleated products such as alkylene oxides of bisphenols It is preferably used as an adduct.

The method for producing the polyester (a1), polyetherester (a2) and polyetherester (A), which is the final product, used in the present invention is not particularly limited, but (a1) and (a2) May be produced separately, and then both may be reacted. However, in order to make the effect of the present invention remarkable, (a2) is produced first, and then (a2) is produced during the reaction of (a1). The method of introducing into a system and making it react is preferable.

The latter method will be described in detail below.

First, in order to produce the polyester (a2), each component including the aromatic polycarboxylic acid or its alkyl ester, alkylene diol, and bifunctional phenol compound is subjected to 100 to 200 ° C. under normal pressure. A method for carrying out the reaction may be mentioned. Here, as the catalyst used, a very large number of compounds are effective, but an alkali metal or alkaline earth metal acetate, in the second stage, zinc, manganese, cobalt, antimony, germanium,
Compounds of titanium, tin, and zirconium are mentioned.

The polyester (a) thus obtained
2) is not particularly limited, but preferably has a number average molecular weight of 1,000 to 1,000,000 from the viewpoint of weather resistance.

Next, in order to produce the polyetherester (a1), the raw materials containing the aromatic polycarboxylic acid or its alkyl ester, alkylene diol and polyalkylene glycol are used as a first step under normal pressure at 100.degree.
The reaction is carried out at a temperature of from 200 ° C. to 200 ° C., and it is confirmed that the ester is formed quantitatively. No. At this time, the desired polyetherester (A) can be obtained by introducing the polyester (a2) previously produced into the system at an arbitrary stage and conducting the reaction.

At this time, the polyether ester (a1) produced is not particularly limited, but preferably has a number average molecular weight of 1,000 to 1,000,000 from the viewpoint of the antistatic effect.

In the production of (a1), when an aromatic polycarboxylic acid or an alkyl ester thereof is used in combination with a sulfonated phthalate or an alkyl ester thereof, the aromatic polycarboxylic acid or an alkyl ester thereof is used. The ester and the alkylene glycol are reacted under normal pressure for 100 to 2
The reaction was carried out at 00 ° C., and it was confirmed that an ester was formed quantitatively. Then, poly (alkylene oxide) glycol was further added, and as a second step, the temperature was raised to 200 to 300 ° C., and the reaction was carried out under reduced pressure. To obtain the desired polyetherester. The desired polyetherester (A) can be obtained by introducing the previously produced polyester (a2) into the system at an arbitrary stage of the reaction and conducting the reaction.

The catalyst used in the above production method includes
A very large number of compounds are effective, especially in the first stage alkali metal or alkaline earth metal acetates and in the second stage zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium compounds. Can be Particularly, a tetraalkyl titanate or tin oxalate is preferably used as a catalyst effective for all of the transesterification reaction and the polycondensation reaction. The catalyst is preferably used usually in an amount of 0.005 to 1.0% by weight based on the total amount of the raw materials for the polyetherester.

The above polyetherester (a1)
In the production method of the above, an antioxidant can be added during the reaction or at any time after the completion of the reaction.
In particular, it is effective to add an antioxidant that does not inhibit the polycondensation reaction in order to prevent the polyester elastomer from being oxidized and deteriorated at the time of entering the second stage polycondensation step.

Examples of these antioxidants include aliphatic and aromatic esters of phosphoric acid and phosphorous acid or phenolic derivatives, particularly so-called hindered phenols having highly sterically hindered groups. It is also preferable to use several kinds of stabilizers such as antioxidants and ultraviolet absorbers.

The amount of modification of the polyester (a2) with respect to the polyetherester (a1) is not particularly limited, but the content in the polyetherester (A) is 2 to 98% by weight, preferably The range of 5 to 90% by weight is preferable from the viewpoint that the effects of the present invention such as antistatic property, transparency, weather resistance and the like become remarkable.

In the polyetherester (A) thus obtained, the content of the alkylene oxide structural site derived from the poly (alkylene oxide) glycol is 40 to 40 in terms of the weight of the monomer component constituting the structural unit. 8
Preferably it is 5% by weight. That is, when the content is 40% by weight or more, the antistatic effect of the polyetherester is remarkably improved, the compatibility with the acrylic resin is remarkably improved, and the molded product is excellent in transparency and mechanical strength. On the other hand, when the content is 85% by weight or less, the mechanical properties and the heat resistance become good, and the weather resistance becomes good.

The molecular weight of such a polyetherester polycondensate (A) is not particularly limited, but from the viewpoint of dispersibility as an antistatic agent, antistatic effect and transparency, a number average molecular weight is preferred. 1,000-1,000,000
0, particularly preferably 10,000 to 500,000.

The antistatic agent described in detail above can be used for various thermoplastic resins such as polystyrene resin, polycarbonate resin, polyester resin, polyamide resin and polyphenylene oxide resin. As described in detail above, the use as an antistatic acrylic resin composition is preferable because it has excellent compatibility and weather resistance.

The antistatic acrylic resin composition of the present invention is characterized by comprising the above-described antistatic agent of the present invention and an acrylic resin as essential components.

As the acrylic resin used in the present invention, a methyl methacrylate homopolymer or a copolymer of methyl methacrylate and another monomer is used. The copolymer preferably has 60% by weight or more 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. , Aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, maleic anhydride, and anhydride. Examples include unsaturated carboxylic anhydrides such as itaconic acid and unsaturated acids such as methacrylic acid, acrylic acid and maleic acid.

The methacrylic acid or acrylic acid copolymer also includes a polymer 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. When using as acrylic resin,
The above-mentioned methyl methacrylate homopolymer or copolymer can be used alone or in combination of two or more. Among these, a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate is excellent in thermal stability and the like, and has good processing stability, and is most preferable.

As a method for producing these acrylic resins, a known suspension polymerization method, emulsion polymerization method, bulk polymerization method, solution polymerization method and the like are used. For applications requiring impact resistance, a generally used impact-resistant acrylic resin reinforced with a multilayer acrylic rubber or the like may be used.

In the antistatic acrylic resin composition of the present invention, the mixing ratio of the acrylic resin and the antistatic agent is not particularly limited, but the antistatic agent may be contained in the composition in an amount of from 1 to 3.
Preferably, the ratio is 30% by weight. That is, 1
When the content is at least 30% by weight, the antistatic property of the antistatic resin composition and its durability will be good, and when it is at most 30% by weight, the mechanical properties of the resin composition will be good, which is preferable. Among these, it is 5
Preferably it is 25% by weight.

Although the antistatic acrylic resin composition of the present invention has a sufficient antistatic property, a known ionic antistatic agent may be mixed at any time depending on the use. Representative examples of these known ionic antistatic agents include:

[0057]

Embedded image R-SO ₃ M An organic sulfonic acid metal salt represented by the general formula 3 is exemplified.

Here, the metal organic sulfonic acid salt represented by the general formula 2 is a metal organic sulfonic acid salt in which R is an alkyl group or an alkylaryl or aryl group and M is an alkali metal or an alkaline earth metal. Any one may be used as long as R has 8 carbon atoms.
About 30 alkyl groups or alkylaryl groups, M
Is preferably selected from Na, K, Li, Mg, Ca and the like.

Specific examples of such organic metal sulfonic acid salts include sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium octadecyl sulfonate, sodium decyl benzene sulfonate, dodecyl benzene Sodium sulfonate, sodium stearylbenzenesulfonate, sodium octylbenzenesulfonate, sodium octylnaphthalenesulfonate, sodium dodecylnaphthalenesulfonate, potassium dodecylsulfonate, potassium dodecylbenzenesulfonate, potassium dodecylnaphthalenesulfonate, lithium dodecylsulfonate, Lithium dodecylbenzenesulfonate, magnesium dodecylsulfonate, calcium dodecylsulfonate And the like. Among them, sodium dodecylbenzenesulfonate and sodium dodecylsulfonate are preferably used.

A known ionic antistatic agent represented by the formula (2) is not always necessary for the antistatic resin composition of the present invention. Is preferable because the antistatic performance is remarkably improved due to the interaction between them. When the amount of addition is 5% by weight or less based on the whole antistatic resin composition of the present invention, the antistatic effect can be improved without deteriorating the appearance or physical properties of a molded article of the resin composition. From the viewpoint, it is preferably in the range of 0.1 to 3% by weight.

Further, in the present invention, other known antistatic agents may be used in combination.

The thermoplastic acrylic resin composition of the present invention may further contain known additives. Such known additives include, for example, 2,6-
Di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol,
2,2-methylenebis- (4-ethyl-6-t-methylphenol), 4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di- Nonylphenyl) phosphite and the like, and pt-butylphenyl salicylate, 2,2′-dihydroxy-4-methoxybenzophenone, 2- (2′-hydroxy-4′-n) as an ultraviolet absorber.
-Octoxyphenyl) benzotriazole and the like, and as a lubricant, paraffin wax, stearic acid, hydrogenated oil, stearamide, methylenebisstearamide,
Ethylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, etc., and as a flame retardant, antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris ( Dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A, etc .; coloring agents such as titanium oxide and carbon black; fillers such as calcium carbonate, clay, silica and glass Fibers, glass spheres, carbon fibers, and the like. Further, the thermoplastic acrylic resin composition of the present invention can be mixed with other thermoplastic resins such as polyamide, polybutylene terephthalate, polyphenylene oxide, polyoxymethylene, and chlorinated polyethylene, if necessary.

The thermoplastic acrylic resin composition of the present invention comprises:
Although the compatibility is remarkably improved as compared with the case where a conventional antistatic agent is used, a known compatibilizer may be used in combination. Examples of the known compatibilizer include styrene-ethylene-butadiene block copolymer, polyethylene-polymethyl methacrylate block copolymer, polyethylene-polystyrene graft copolymer, polyethylene-polymethyl methacrylate as a non-reactive compatibilizer. Graft copolymers, polypropylene-acrylonitrile graft copolymers and the like, as a reactive compatibilizer,
Maleic anhydride-grafted polypropylene, styrene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, styrene graft copolymer on ethylene-glycidyl methacrylate copolymer, methyl methacrylate graft on ethylene-glycidyl methacrylate copolymer Copolymers, polypropylene-β-hydroxyethyl methacrylate graft copolymers, polypropylene-glycidyl methacrylate graft copolymers, and the like.

The method of preparing the antistatic acrylic resin composition of the present invention is not particularly limited. For example, the antistatic agent of the present invention, a thermoplastic resin, and if necessary, a metal salt of sulfonic acid or the like. It can be easily manufactured by blending a predetermined amount with other additive components, preliminarily mixing with a mixer such as a Henschel mixer or a tumbler mixer, and then melt-mixing with an extruder, a kneader, a hot roll, a Banbury mixer or the like.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following examples,% and parts indicate% by weight and parts by weight, respectively.

Example 1 Synthesis of Polyester A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 308 parts of dimethyl terephthalate and ethylene glycol 10
100 parts, 300 parts of a bisphenol A / poly (ethylene oxide) glycol adduct having a number average molecular weight of 3000 and 2.0 parts of calcium acetate as a catalyst were charged, and the mixture was stirred at 200 ° C. for 2 hours under a nitrogen flow while removing water. Continued. Then, the reaction was allowed to proceed at 220 ° C. for 1.5 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. 1.5 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2.5 hours, taken out in a strand shape under nitrogen pressure, and pelletized to obtain a pellet-shaped modified polyester. Hereinafter, this is referred to as modified PET-1. [Synthesis of polyetherester] Next, 700 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2000, naphthalene-2,6 were placed in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
-375 parts of dimethyl dicarboxylate, 29 parts of dimethyl sodium 5-sulfoisophthalate, 295 parts of ethylene glycol and 2.0 parts of calcium acetate as a catalyst were charged, and the methanol was removed at 180 ° C for 2 hours under a nitrogen flow. Stirring was continued. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. To this, 140 parts of modified PET-1 and 1.5 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 250 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 3 hours, taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent A.

The melt viscosity of the antistatic agent A was measured with a rheometer RDS-II (manufactured by RHEOMETRIC INC.
235 ° C. under a nitrogen atmosphere,
When measured at 100 rpm, the measured value was 24
It was 9 Pa · s. The ratio (x) / (y) of the number of ethylene groups (x) derived from ethylene glycol to the number of aromatic nuclei (y) based on bisphenol A, which was measured from the results of ¹ H NMR (nuclear magnetic resonance) spectrum measurement, was 300. Met.

Example 2 [Synthesis of Polyester] A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 200 parts of an adduct of bisphenol A / poly (ethylene oxide) glycol having a number average molecular weight of 4500, and naphthalene. −2,
380 parts of dimethyl 6-dicarboxylate, 1200 parts of ethylene glycol and 2.0 parts of calcium acetate as a catalyst were charged, and stirring was continued at 180 ° C. for 2 hours under a nitrogen flow while removing methanol. Then 1330 Pa
The reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under reduced pressure. 2 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Then, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a modified polyethylene naphthalate pellet. Hereinafter, this is referred to as modified PEN-1.

[Synthesis of Polyetherester] In a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade), 620 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2000 and 377 parts of dimethyl terephthalate were added. , 34 parts of dimethylpotassium 5-sulfoisophthalate, 480 parts of ethylene glycol and 2.0 parts of calcium acetate as a catalyst were charged, and stirring was continued at 180 ° C. for 2 hours under a nitrogen flow while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Furthermore, modified PEN-1
15 parts and 2 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 250 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent B. For this antistatic agent B, the melt viscosity measured in the same manner as in Example 1 was 235 Pa · s. The ratio (x) / (y) of the number of ethylene groups (x) derived from ethylene glycol to the number of aromatic nuclei (y) based on bisphenol A, measured in the same manner as in Example 1, was 580.

Example 3 Synthesis of Polyether Ester 590 parts of a bisphenol A / poly (ethylene oxide) glycol adduct having a number average molecular weight of 1500 in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade). Dimethyl terephthalate 363 parts, dimethyl isophthalate 80
Part, dimethyl 5-sulfoisophthalic acid sodium salt 85
, 600 parts of ethylene glycol and 2.8 parts of calcium acetate as a catalyst.
Stirring was continued while removing methanol over time.
Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Further, 631 parts of modified PET-1 and 1.8 parts of tetrabutyl titanate as a catalyst were added, and 255 parts were added.
The temperature was raised to ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent C. For this antistatic agent C, the melt viscosity measured in the same manner as in Example 1 was 278 Pa · s. Further, the number of ethylene groups (x) caused by ethylene glycol and the number of aromatic nuclei based on bisphenol A (y) were measured in the same manner as in Example 1.
And the ratio (x) / (y) was 25.

Example 4 Synthesis of Polyester 100 parts of naphthalene-2,6-diol, 1200 parts of ethylene glycol and 380 dimethyl terephthalate were placed in a flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade). Parts and 3 parts of calcium acetate as a catalyst, and feed under nitrogen flow 18
Stirring was continued at 0 ° C. for 2 hours while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2.5 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. 2 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Then, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a modified polyethylene naphthalate pellet. Hereinafter, this is referred to as modified PET-2. [Polyetherester] 620 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2,000 and 394 of dimethyl naphthalene-2,6-dicarboxylate in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade). Parts, 30 parts of dimethyl potassium 5-sulfoisophthalate, 408 parts of ethylene glycol and 3.1 parts of calcium acetate as a catalyst, and the mixture was stirred at 180 ° C. for 2 hours under nitrogen flow while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2.8 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 650 Pa. Further, modified PET-2
300 parts, and tetrabutyl titanate 1.7 as a catalyst
And heated to 250 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 3 hours, taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent D. For this antistatic agent D, the melt viscosity measured in the same manner as in Example 1 was 201 Pa · s. The ratio (x) / (y) of the number of ethylene groups (x) derived from ethylene glycol and the number of aromatic nuclei (y) based on naphthalene-2,6-diol, measured in the same manner as in Example 1.
Was 5.

Example 5 [Synthesis of polyetherester] Poly (ethylene oxide) having a number average molecular weight of 6000 was placed in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
800 parts of a glycol adduct, 380 parts of dimethyl naphthalene-2,6-dicarboxylate, 34 parts of dimethyl potassium 5-sulfoterephthalate, 480 parts of ethylene glycol and 3 parts of calcium acetate as a catalyst were charged at 180 ° C. under a nitrogen flow. Stirring was continued while removing methanol over time. Then, while removing distillate such as excess ethylene glycol under a reduced pressure of 900 Pa,
The reaction was allowed to proceed for 2 hours. Further, 10 parts of modified PEN-1 and 1.8 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 250 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyether. Hereinafter, this is referred to as an antistatic agent E.
For this antistatic agent E, the melt viscosity measured in the same manner as in Example 1 was 195 Pa · s. The ratio (x) / (y) of the number of ethylene groups (x) derived from ethylene glycol to the number of aromatic nuclei (y) based on bisphenol A, which was measured in the same manner as in Example 1, was 2,000.

Example 6 [Synthesis of polyetherester] In a flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade), 630 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 600, naphthalene- 419 parts of dimethyl 2,6-dicarboxylate, 35.5 parts of dimethyl potassium 5-sulfoisophthalate, ethylene glycol 440
Parts and 0.8 parts of calcium acetate as a catalyst,
Stirring was continued at 180 ° C. for 2 hours while removing methanol while flowing nitrogen. Then, while removing distillates such as excess ethylene glycol under a reduced pressure of 1300 Pa,
The reaction was allowed to proceed at 210 ° C. for 2 hours. Furthermore, modified PE
15 parts of T-2 and 1.9 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 250 ° C. Then 13P
After reacting under reduced pressure of a for 2.8 hours, the reaction mixture was taken out into a strand under nitrogen pressure and pelletized,
A pellet-like polyetherester was obtained. Hereinafter, this is referred to as antistatic agent F. For this antistatic agent F, the melt viscosity measured in the same manner as in Example 1 was 194 Pa · s. Further, the number of ethylene groups (x) caused by ethylene glycol and naphthalene-
The ratio (x) / (y) to the number of aromatic nuclei (y) based on 2,6-diol was 45.

Example 7 [Synthesis of polyetherester] Poly (ethylene oxide) having a number average molecular weight of 3000 was placed in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
Glycol adduct 680 parts, naphthalene-2,6-dicarboxylic acid dimethyl 430 parts, 5-sulfoisophthalic acid dimethyl sodium salt 34 parts, ethylene glycol 510
Parts and 1.8 parts of calcium acetate as a catalyst,
Stirring was continued at 180 ° C. for 2 hours while removing methanol while flowing nitrogen. Then, while removing distillate such as excess ethylene glycol under a reduced pressure of 1330 Pa,
The reaction was allowed to proceed at 210 ° C. for 2 hours. Furthermore, modified PE
18 parts of T-1 and 1.9 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 250 ° C. Then 13P
After reacting under the reduced pressure of a for 3.9 hours, the reaction mixture was taken out into a strand under nitrogen pressure and pelletized,
A pellet-like polyetherester was obtained. Hereinafter, this is referred to as antistatic agent G. For this antistatic agent G, the melt viscosity measured in the same manner as in Example 1 was 227 Pa · s. The ratio (x) / (y) of the number of ethylene groups (x) due to ethylene glycol to the number of aromatic nuclei (y) based on bisphenol A, which was measured in the same manner as in Example 1, was 6
It was 10.

Comparative Example 1 [Synthesis of Polyetherester] Poly (ethylene oxide) having a number average molecular weight of 1010 was placed in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
Glycol 614 parts, dimethyl terephthalate 361 parts,
69 parts of dimethyl 5-sulfoisophthalic acid sodium salt,
390 parts of ethylene glycol and 2.7 parts of calcium acetate as a catalyst were charged, and stirring was continued while removing methanol at 180 ° C. for 2 hours under a flow of nitrogen. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Further, 1.5 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Then 35P
The mixture was reacted under the reduced pressure of a for 2 hours and taken out into a cooling pan.
After cooling, cutting was performed to obtain a pellet-like polyetherester. Hereinafter, this is called an antistatic agent H
Called.

The melt viscosity of the antistatic agent H was measured by using a rheometer RDS-II (manufactured by RHEOMETRIC INC.
(Hereinafter referred to as RDS) using a nitrogen atmosphere at 250 ° C.
When measured at 100 rpm, the measured value was 84
Pa · s.

Comparative Example 2 [Synthesis of Polyether Ester] A poly (ethylene oxide) having a number average molecular weight of 4000 was placed in a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade).
618 parts of glycol adduct, dimethyl terephthalate 36
1 part, dimethyl sodium 5-sulfoisophthalate 3
0 parts, 410 parts of ethylene glycol and 2.5 parts of calcium acetate as a catalyst were charged, and stirring was continued for 2 hours at 180 ° C. while flowing methanol while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Further, 3 parts of modified PET-1 and 1.5 parts of tetrabutyl titanate as a catalyst were added, and 250 parts were added.
The temperature was raised to ° C. Then, the mixture was reacted under a reduced pressure of 35 Pa for 2 hours, and taken out to a cooling pan. After cooling, cutting was performed to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent I. For this antistatic agent I, the melt viscosity measured in the same manner as in Example 1 was as follows:
It was 158 Pa · s. Further, the ratio (x) / (y) of the number of ethylene groups (x) derived from ethylene glycol to the number of aromatic nuclei (y) based on bisphenol A, measured in the same manner as in Example 1, was 3,600.

Examples 8 to 23 and Comparative Examples 3 to 5 The components were mixed at the ratios shown in Tables 1 to 3 below.
Using a 25 mm twin screw extruder manufactured by Toyo Seiki Seisaku-sho, Ltd.
It was kneaded and extruded at 220 ° C. Each test piece was prepared from the obtained pellet using a 1 oz. Injection molding machine manufactured by Yamashiro Seiki Co., Ltd. at a cylinder temperature of 220 ° C., and the following evaluations were performed. The evaluation results are shown in Tables 1 to 7. (1) Drop weight impact test According to ASTM D-3763, an instrumented drop weight impact tester Dynatup (GRC manufactured by General Research Corporation)
730-I) using a flat plate of 80 × 80 × 3 mm as a test plate. (2) Antistatic performance test After adjusting the condition of a 80 × 80 × 3 mm flat plate at 23 ° C. and 50% relative humidity for 24 hours, use a SM-8210 super-insulation meter (manufactured by Toa Denpa Kogyo Co., Ltd.) The resistance was measured.
The unit of the measured value is Ω / □. (3) Transparency test According to JIS K7105, the total light transmittance (%) was measured using a haze meter (Model ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.) with a 30 × 30 × 3 mm flat plate as a test plate. ) Was measured. (4) Weather resistance test Sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.)
Model: WEL-SUN-DCH-8) 80 × 80 × 3
A 300 mm thick flat plate was put therein, and after elapse of 300 hours at 63 ° C., the surface resistivity was measured by the same method as in the antistatic property test (2).

In the table, PMMA represents "Acrypet MD" manufactured by Mitsubishi Rayon Co., Ltd., and DBS represents sodium dodecylbenzenesulfonate manufactured by Takemoto Yushi Co., Ltd.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

The antistatic agent of the present invention can provide an acrylic resin with excellent weather resistance, antistatic effect and its durability without impairing transparency. Further, the antistatic acrylic resin composition of the present invention has excellent antistatic properties, transparency and weather resistance, and further has excellent mechanical strength and weather resistance. Useful for automotive parts, packaging materials, furniture, etc.

Claims (10)

[Claims] 1. A polyether ester (A) comprising an aromatic polycarboxylic acid or an alkyl ester thereof, a polyalkylene glycol, an alkylene diol, and a bifunctional phenol compound as essential raw material components, and
In the polyetherester (A), the ratio of the number of alkylene groups (x) caused by the alkylene diol to the number of aromatic nuclei (y) caused by the bifunctional phenol compound is (x) / (y). = 2 to 3,000. 2. The polyetherester (A) is a polyetherester (a1) containing an aromatic polycarboxylic acid or an alkyl ester thereof, an alkylene diol, and a polyalkylene glycol as essential raw materials. 2. The antistatic agent according to claim 1, which has a structure modified with a polyester (a2) containing a carboxylic acid or an alkyl ester thereof, an alkylene diol, and a bifunctional phenol compound as essential raw material components. 3. The polyester (a2) comprising an ethylene oxide adduct of a bifunctional phenol compound, an aromatic polycarboxylic acid or an alkyl ester thereof, and an alkylene diol as essential raw material components.
The antistatic agent according to the above. 4. The antistatic agent according to claim 1, wherein the aromatic polycarboxylic acid is terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid. 5. The weight of poly (alkylene oxide) glycol derived from poly (alkylene oxide) glycol in polyetherester (A) is such that the content of poly (alkylene oxide) glycol is based on the weight of all monomers constituting (A). The antistatic agent according to any one of claims 1 to 5, wherein the ratio is in a range of 40 to 85% by weight. 6. The antistatic agent according to claim 1, wherein the poly (alkylene oxide) glycol has a number average molecular weight of 300 to 50,000. 7. An aromatic polycarboxylic acid or an alkyl ester thereof containing a sulfonic acid group-containing dicarboxylic acid component in a proportion of 0.1 to 15 mol% based on all acid components. 7. The antistatic agent according to any one of 7. 8. The antistatic agent according to claim 1, wherein the polyetherester (a1) has a number average molecular weight of 1,000 to 1,000,000. 9. An antistatic acrylic resin composition comprising the antistatic agent according to any one of claims 1 to 8 and an acrylic resin as essential components. 10. The antistatic acrylic resin composition according to claim 10, wherein the content of the antistatic agent is 1 to 30% by weight.