JPH10273526A - Polyester antistatic agent and polymer composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester antistatic agent having excellent compatibility with a polymer component, and a polymer composition exhibiting satisfactory permanent antistatic effect. SOLUTION: This antistatic agent comprises, as an effective component, a polyester which is prepared by polycondensation of a polycarboxylic acid component and a polyhydric alcohol component, wherein the polyhydric alcohol component comprises at least one alkylene glycol condensate selected from the group consisting of an oligoalkylene glycol and a polyalkylene glycol and a hindered polyhydric alcohol, and has a weight average molecular weight(Mw) of 1,000 to 500,000. This polymer composition in the form of a resin or a rubber comprises the above-mentioned polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester-based antistatic agent, a polymer composition comprising the same and a molded article,
More specifically, the present invention relates to a polyester-based antistatic agent exhibiting excellent compatibility with a polymer component, and a polymer composition and a molded article having a sufficient permanent antistatic effect.

[0002]

2. Description of the Related Art As is well known, olefin resins such as polypropylene and olefin rubbers such as ethylene-propylene-diene copolymer rubber (EPDM) have been used widely because they have excellent properties and are relatively inexpensive. Has been
Since there was no polar group in the molecule, no practical antistatic effect was obtained. Therefore, various surfactants are added,
Although a method of enhancing the antistatic effect has been performed, the effect obtained by leaching the surfactant onto the polymer surface is temporary, and a more persistent antistatic agent has been demanded.

On the other hand, it is known that a polymer having a polyoxyalkylene chain exhibits an antistatic property (Plastic Age, Takai, 41 [3], 133 (199).
3)) For example, in US Pat. No. 4,165,303, polyesters of dimer acid and polyoxyalkylene glycol are known as antistatic agents for polyamides and polyesters. JP-A-6-322050 discloses a technique of grafting a polyoxyalkylene chain to polystyrene by an ester bond.
Japanese Patent Publication No. 209045 discloses a polyester comprising a carboxylic acid containing phosphonium sulfoisophthalic acid as a main component and a glycol containing polyoxyalkylene glycol as a main component.

[0004]

However, conventional polyesters have a serious problem in compatibility with polymers such as polyolefins, and as a result, the polymer composition containing these polyesters has a sufficient permanent antistatic property. I'm not satisfied with it. Accordingly, the present invention provides a polyester-based antistatic agent exhibiting excellent compatibility with a polymer component, a polymer composition containing the polyester-based antistatic agent and having a sufficient permanent antistatic effect, and a molded article thereof. It is intended for.

[0005]

That is, the present invention relates to a polyhydric carboxylic acid component and a polyhydric alcohol component which are obtained by polycondensation of a polyvalent carboxylic acid component and a polyhydric alcohol component. At least one selected from an alkylene glycol condensate and a hindered polyhydric alcohol,
Weight average molecular weight (Mw) of 1,000 to 500,000
And an antistatic agent containing the polyester as an active ingredient. The present invention also relates to a resinous or rubbery polymer composition and a molded article containing the polyester.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyvalent carboxylic acid component of the polyester used in the present invention is not particularly limited, as long as it is a divalent or higher carboxylic acid monomer and is used for ordinary polyester synthesis. Preferably, those containing a divalent carboxylic acid-based monomer as a main component are used. 2
There is no particular limitation on the monovalent carboxylic acid monomer, and linear, branched or cyclic aliphatic divalent carboxylic acids or aromatic or heterocyclic divalent carboxylic acids are preferably used. Acids and aromatic divalent carboxylic acids. Among these, those containing at least an aromatic divalent carboxylic acid monomer are suitable because they can raise the softening point of the polyester, and are usually 30% by weight or more, preferably 50% by weight or more of all divalent carboxylic acid type monomers, It is more preferably at least 70% by weight.

Examples of the aliphatic dicarboxylic acid include succinic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and the like.
Itaconic acid, pimelic acid, suberic acid, azelaic acid,
A lower aliphatic divalent carboxylic acid having 1 to 9 carbon atoms such as 1,2-cyclohexane diacid, 1,3-cyclohexane diacid, 1,4-cyclohexane diacid and the like and having 10 or more carbon atoms; Higher aliphatic dicarboxylic acids are used, with higher aliphatic carboxylic acids being preferred. The carbon number is usually 1
The range is from 0 to 200, preferably from 20 to 150, and more preferably from 20 to 100. Specific examples of such higher aliphatic divalent carboxylic acids include sebacic acid, brassic acid, polyalkenyl succinic acid, and dimer acids of polymerized fatty acids. Among them, polyalkenyl succinic acid and dimer acid of polymerized fatty acid are preferable, and dimer acid of polymerized fatty acid is more preferable.

The polyalkenyl succinic acid is represented by the following general formula (1).

Embedded image Here, R ¹ is a polymer chain of lower alkylene having 1 to 6 carbon atoms, and preferably, the lower alkylene is one selected from ethylene, propylene, and butylene. The degree of polymerization preferably ranges from 10 to 300.

As the dimer acid of the polymerized fatty acid, generally, a polymer obtained by polymerizing a fatty acid or a fatty acid ester by a known method is used, and is obtained by hydrogenating carbon-carbon unsaturated bonds remaining in the polymerized fatty acid. There may be. A dimer acid of a higher fatty acid obtained by polymerizing a higher fatty acid or a higher fatty acid ester is preferred. The fatty acid may be saturated or unsaturated, and usually has 8 to 3 carbon atoms.
0, preferably 12 to 24, more preferably 16 to 20
Range. As the fatty acid ester, an alkyl ester of the above fatty acid such as methyl, ethyl, propyl, butyl, amyl and cyclohexyl is used. Preferred polymerized fatty acids include, for example, those obtained by polymerizing unsaturated higher fatty acids such as oleic acid, linoleic acid, ricinoleic acid, and eleostearic acid, and those obtained by polymerizing natural fatty acids such as tall oil and tallow. The structural analysis of polymerized fatty acids is described in D.S. H. (J. Am. Oil. Chem. Soc., 5).
1, 522 (1974)). Polymerized fatty acids are also available as commercial products. A commercially available product is obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eriostearic acid, or the like, and has dimer acid as a main component, and a polymer acid and a monomer acid which are at least dimer acid as subcomponents. These can be purified by distillation or solvent extraction,
It may be used after purification or may be used as it is without purification.

As the aromatic divalent carboxylic acid, those having one aromatic ring as a basic skeleton are generally used, but they are independently used in the form of biphenyl, p-terphenyl, diphenylmethane, triphenylmethane, bibenzyl, stilbene and the like. Or two or three aromatic rings such as naphthalene, anthracene, and phenanthrene may be condensed. An aromatic ring such as indene or tetralin may have a condensed ring in which another 5- or 6-membered carbon ring is condensed. The number of carbon atoms is usually in the range of 8 to 30, preferably 8 to 20, and more preferably 8 to 15.

Preferred specific examples of the aromatic divalent carboxylic acid monomer include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-1,4-.
Examples thereof include dicarboxylic acid and naphthalene-2,3-dicarboxylic acid. Of these, terephthalic acid and isophthalic acid are preferred.

Heterocyclic divalent carboxylic acid refers to a 5- or 6-membered ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen as a heteroatom constituting the ring or a fused ring thereof. It refers to a compound in which two carboxyl groups are coordinated, and a compound commonly used in general polyester synthesis can be appropriately selected and used according to the purpose of use. As the heterocyclic ring, specifically, pyrrole, pyrazole, pyridine, pyrazine, quinoline, naphthyridine, quinoxaline; thiophene, benzothiophene; furan,
Pyran, isobenzofuran, chromene and the like,
Those containing a nitrogen atom as a hetero atom, such as pyrazole, pyridine and pyrazine, are preferred. The carbon number is usually 8
-30, preferably 8-20, more preferably 8-15
Range. Specific examples of the heterocyclic divalent carboxylic acid monomer include, for example, 2,5-pyrroledicarboxylic acid,
2,3-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, pyrazine-
Examples include 2,3-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2,4-quinolinedicarboxylic acid, 2,7-naphthyridinedicarboxylic acid, 2,3-quinoxalinedicarboxylic acid, and 2,5-thiophenedicarboxylic acid. . Among these, 2,3-pyridinecarboxylic acid, 2,2
Preferred are 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid and the like.

Here, the substitution positions of the two carboxyl groups of the dihydric carboxylic acid may be any positions as long as they do not inhibit the polycondensation reaction with the polyhydric alcohol component.
Further, the divalent carboxylic acid may have, in addition to the above two carboxyl groups, other substituents as long as they do not inhibit the polycondensation reaction with the polyhydric alcohol component. Tertiary amino groups substituted with lower alkyl such as propyl, butyl, amyl, hexyl, etc .; nitro groups; cyano groups; carbamoyl groups; halogen atoms such as fluorine and chlorine;
Lower alkyl groups such as isopropyl; lower alkoxy groups such as methoxy and ethoxy; and halogenated lower alkyl groups such as trifluoromethyl.

The divalent carboxylic acid may be a derivative thereof such as an acid halide, an acid anhydride and an ester compound. The ester compound is not particularly limited, but usually an alkyl ester is used. As the alkyl ester, for example, methyl ester, ethyl ester,
Lower alkyl esters such as propyl ester, isopropyl ester, butyl ester, amyl ester, and hexyl ester; octyl ester, decyl ester,
Higher alkyl esters such as dodecyl ester, pentadecyl ester and octadecyl ester are mentioned, preferably lower alkyl esters, more preferably methyl esters, ethyl esters, propyl esters, butyl esters and the like. The acid halide is not particularly limited, but usually an acid chloride is used.

The divalent carboxylic acid monomers can be used alone or in combination of two or more. The proportion is appropriately selected according to the purpose of use, but is usually in the range of 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight in the total polycarboxylic acid component. .

The balance other than the divalent carboxylic acid monomer is
Trivalent or higher carboxylic acids used in general polyester synthesis are used without any particular limitation. The trivalent or higher carboxylic acid may have a substituent similarly to the above divalent carboxylic acid-based monomer, or may be a carboxylic acid derivative. Examples of the trivalent or higher carboxylic acid include trivalent or higher carboxylic acids such as trimellitic acid, tricarballylic acid, camphoronic acid, trimesic acid, and trimer acid in polymerized fatty acids. More than one species can be used in combination.

In the present invention, as the carboxylic acid component, as long as the effects of the present invention are not impaired, formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, valeric acid, isooctylic acid, isononanoic acid, lauric acid , Myristic acid, palmitic acid, stearic acid, isostearic acid,
Monovalent carboxylic acids such as arachiic acid, linoleic acid, oleic acid and elaidic acid may be used in combination. These may have a substituent similarly to the above-mentioned divalent carboxylic acid, and may be carboxylic acid derivatives. Each of them can be used alone or in combination of two or more, and the allowable amount is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less in all carboxylic acid components.

The polyhydric alcohol component of the polyester used in the present invention is characterized by containing at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols and a hindered polyhydric alcohol. .

As at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols, for example, alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, alone or in a mixture, can be obtained by a known method. For example, those represented by the following general formula (2) can be used. _{HO - ((CH 2) a} -CHR 2 O) b -H (2) where, R ² is a lower alkyl group having 1 to 6 carbon atoms, such as hydrogen atom or a methyl group, an ethyl group, preferably It is a hydrogen atom or a methyl group. a represents an integer of 1 to 6, and is preferably an integer of 1 to 4. b is 2 to 1,0
It represents an integer of 00, preferably an integer of 5 to 500, more preferably an integer of 10 to 200. Specifically, oligooxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, and polybutylene glycol; No. The molecular weight of the oligooxyalkylene glycol and / or the polyoxyalkylene glycol can be appropriately selected according to the purpose of use, and is usually 100 to 10 based on the weight average molecular weight (Mw) measured by GPC.
It is in the range of 0000, preferably 200 to 20,000, more preferably 500 to 5,000.

These oligooxyalkylene glycols and / or polyoxyalkylene glycols can be used alone or in combination of two or more. The amount of at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols in the polyhydric alcohol component is appropriately selected according to the purpose of use, and is usually 10 to 95% by weight. Preferably it is 30 to 90% by weight, more preferably 50 to 85% by weight. If the polyhydric alcohol component does not contain at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols, the antistatic effect is poor, which is not preferred.

The hindered polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups in the molecule and the β-position carbon atom of the hydroxyl group does not have a hydrogen atom. Equation (3) or Equation (4)
Is used.

HOCH ₂ — (CR ³ R ⁴ ) —CH ₂ OH (3) R ³ and R ⁴ each independently represent an alkyl group or a methylol group. The carbon number of the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 20, and more preferably 2 to 10. Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, hexyl, heptyl, octyl,
Nonyl group, decyl group, dodecyl group, tridecyl group, pentadecyl group, octadecyl group, eicosyl group and the like, among them, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec
-Butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like are preferable, and ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl are preferable. Groups and the like are particularly preferred.

Specific examples of the hindered polyhydric glycol represented by the formula (3) include, for example, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2-dipropyl-
1,3-propanediol, 2,2-diisopropyl-
1,3-propanediol, 2,2-dibutyl-1,3
-Propanediol, 2,2-diisobutyl-1,3-
Propanediol, 2-methyl-2-dodecyl-1,3
-Propanediol, 2-butyl-2-ethyl-1,3
-Propanediol, 2-propyl-2-pentyl-
Examples thereof include 1,3-propanediol, trimethylolethane, trimethylolpropane, trimethylolbutane, and pentaerythritol.
2-diethyl-1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Diol, 2-propyl-2-pentyl-1,3-propanediol and the like are preferred.

[0024]

Embedded image R ⁵ and R ⁶ each independently represent an alkyl group or a methylol group. The carbon number of the alkyl group of R ⁵ or R ⁶ is
Although there is no particular limitation, it is usually 1 to 50, preferably 1 to 2
0, more preferably in the range of 2-10. Specific examples of the alkyl group are the same as those described in relation to the general formula (3).

The compounds included in the above general formula are preferably trimethylolethane, trimethylolpropane, trimethylolbutane, triethanolpropane,
Dehydration condensates of one or more compounds selected from the group consisting of triethanol butane and pentaerythritol (except when both are glycerin), such as ditrimethylolethane and ditrimethylolpropane , Ditrimethylolbutane, ditriethanolpropane, ditriethanolbutane, dipentaerythritol and the like are preferable, ditrimethylolpropane,
Dipentaerythritol is more preferred.

These hindered polyhydric alcohols can be used alone or in combination of two or more. The proportion of the hindered polyhydric alcohol in the polyhydric alcohol component may be appropriately selected according to the purpose of use, and is usually 5 to 90% by weight, preferably 10 to 70% by weight, more preferably 15 to 50% by weight. Range.
If the hindered polyhydric alcohol is not contained in the polyhydric alcohol component, the compatibility with a polymer such as polyolefin is poor, and the antistatic effect is not sufficient.

The proportion of at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols and the hindered polyhydric alcohol may be appropriately selected according to the purpose of use. The weight ratio of at least one alkylene glycol condensate selected from the group consisting of alkylene glycols and polyoxyalkylene glycols]: [hindered polyhydric alcohol] is usually 10:90 to 95: 5, preferably 30:70 to 9
0:10, more preferably in the range of 50:50 to 85:15. When the ratio of both is within this range, the compatibility with the polymer and the antistatic effect are highly balanced, which is preferable. Further, the total amount of at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycol and polyoxyalkylene glycol in the polyhydric alcohol component and the hindered polyhydric alcohol is appropriately selected depending on the intended use. Is usually 50% by weight or more, preferably 70% by weight or more, more preferably 9% by weight.
0% by weight or more. When the total amount of both is within this range, the compatibility with the polymer and the antistatic effect are highly balanced, which is preferable.

Other polyhydric alcohols are used for the remainder other than the hindered polyhydric alcohol and at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols in the polyhydric alcohol component. The other polyhydric alcohol is not particularly limited, and dihydric diols and trihydric or higher polyols used in ordinary polyester synthesis are used.

Examples of the divalent diol include alkane diol, cycloalkane diol, aromatic diol and the like. Specifically, as the alkanediols, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 Examples of cycloalkanediols such as -hexanediol, 1,8-octanediol, and 1,9-nonanediol include, for example, cyclopentane-1,
2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-
Examples of aromatic diols such as 1,4-diol, cyclooctane-1,4-diol and 2,5-norbornanediol include, for example, p-xylene diol,
4'-methylenediphenol, 4,4'-dihydroxybiphenyl, 2,5-naphthalenediol and the like can be mentioned.

The trivalent or higher alcoholic monomer is not particularly limited as long as it has three or more hydroxyl groups. Examples thereof include glycerol compounds such as glycerol, diglycerol and polyglycerol;
In addition to saccharides such as sorbitol, glucose, mannitol, sucrose, glucose, and the like, an epoxy compound having two or more epoxy groups in a molecule can also be used.

In the present invention, the alcohol component may be, for example, methanol, ethanol, isopropanol, butanol or t-sodium as long as the effects of the present invention are not impaired.
-Butanol, neopentyl alcohol, 3-methyl-
3-pentanol, 3-ethyl-3-pentanol,
Monohydric alcohols such as 2,3,3-trimethyl-2-butanol, 1-decanol and nonyl alcohol may be used in combination. These may have a substituent similarly to the above-mentioned polyhydric alcohol. Each of them can be used alone or in combination of two or more. The allowable amount thereof is usually 20% by weight or less, preferably 15% by weight of the total alcohol component.
% By weight, more preferably 10% by weight or less.

In the condensation polymerization of the above monomer components,
Polyester can be obtained under the condition that the total number [X] of alcoholic reactive groups in all monomers obtained by adding the polyvalent carboxylic acid component and the polyhydric alcohol component is larger than the total number [Y] of the carboxylic acid reactive groups. Is suitable for increasing the molecular weight and increasing the hydroxyl value. The ratio of the total number of alcoholic reactive groups [X] to the total number of carboxylic acidic reactive groups [Y] is usually 1.02 or more, preferably 1.03 to 1.0, in an equivalent ratio of [X] / [Y]. 5, more preferably 1.04
-3, most preferably in the range of 1.05-2.5.
Here, the alcoholic reactive group refers to an alcoholic functional group that forms an ester bond, and typically includes a hydroxyl group, and the carboxylic acid reactive group includes a carboxylic acid group that forms an ester bond. And generally includes a carboxyl group and an ester group.

The polycondensation reaction may be carried out according to a conventional method. For example, the reaction temperature is 100 to 300 ° C., preferably 150 to 28
It is carried out at 0 ° C., particularly preferably in the presence of an inert gas such as nitrogen gas. If necessary, a water-insoluble organic solvent azeotropic with water, such as toluene or xylene, may be used, and the reaction is carried out under reduced pressure (usually 0.1 to 500 mmH).
g, preferably 1 to 200 mmHg, more preferably 1
0-100 mmHg).

In the polycondensation reaction, an esterification catalyst is usually used. Examples of the esterification catalyst include Bronsted acids such as paratoluenesulfonic acid, sulfuric acid, and phosphoric acid; Lewis acids such as boron trifluoride complex, titanium tetrachloride, and tin tetrachloride; calcium acetate, zinc acetate;
Organic metal compounds such as manganese acetate, zinc stearate, alkyltin oxide, and titanium alkoxide; metal oxides such as tin oxide, antimony oxide, titanium oxide, and vanadium oxide; and the oxidation stability of the obtained polyester. In terms of properties, organometallic compounds belonging to Group IV of the periodic table are preferable, and monobutyltin oxide and tetra-n-butyl-ortho titanate are particularly preferable.

The molecular weight of the polyester used in the present invention can be determined by gel permeation chromatography (GP).
C) The weight average molecular weight in terms of polystyrene (M
w) from 1,000 to 500,000, preferably 3,0
00 to 100,000, more preferably 6,000 to 6
It is in the range of 0000. If the molecular weight of the polyester is excessively small, the softening point is inferior. On the other hand, if the molecular weight is excessively large, the polyester molecule hardly migrates to the surface of the resin or rubber molded article, so that the antistatic effect is inferior.

The hydroxyl value of the polyester is not particularly limited and may be appropriately selected depending on the purpose of use.
OH / g or more, preferably 10 to 250 mgKOH /
g, more preferably in the range of 15 to 200 mg KOH / g. When the hydroxyl value is in this range, the compatibility with the polymer and the antistatic effect are highly balanced, which is preferable.

The softening point of the polyester is usually 30 ° C. or higher, preferably 30 to 300 ° C., more preferably 40 to 300 ° C.
250 ° C, most preferably 50-150 ° C. When the softening point is in this range, the operability is excellent and suitable.

When the polyester is oil-soluble, the compatibility with the resinous or rubbery polymer is further improved and is preferable.
Here, “oil-soluble” means that the polyester solution has a light transmittance of 70% or more measured as described below. The preferred light transmittance is 80% or more. Light transmittance was measured by dissolving 5 g of polyester in 95 g of toluene while stirring at 80 ° C. for 1 hour in a nitrogen atmosphere, and then stirring at room temperature (20 ° C.).
C). The diluted toluene solution is allowed to stand in a constant temperature room at 20 ° C. for 24 hours, then stirred again, and measured with a turbidity meter (“ANA-14S” manufactured by Tokyo Koden Co., Ltd.). Using a tungsten incandescent lamp (6V, 6A) as a light source,
A 20 mm square glass cell is used as the cell. The light transmittance is 0% when the shutter is closed, and the light transmittance of toluene used for dilution is 100%.

Examples of the polymer used as the base in the polymer composition of the present invention include resinous or rubbery polymers such as synthetic resin, rubber, and urethane foam. Although there is no particular limitation on the synthetic resin, a thermosetting resin or a thermoplastic resin is preferably used, and a thermoplastic resin is more preferably used. As a thermosetting resin, for example,
Phenol resin, cresol resin, urea resin, methamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin, polyurethane resin and the like are preferable, and unsaturated polyester resin, epoxy resin and polyurethane resin are preferable. As a thermoplastic resin,
For example, olefin-based resins, styrene-based resins, acrylate-based resins, phenylene ether-based resins, ester-based resins, carbonate-based resins, general-purpose engineering plastics, and the like, among which hydrocarbon-based resins such as olefin-based resins and styrene-based resins When a thermoplastic resin, especially an olefin resin, is used, the effect of improvement is high, which is preferable.

Examples of the olefin resin include homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1; ethylene and propylene or other α-olefins. −
And copolymers of two or more types of α-olefins, such as copolymers with olefins. Among these,
A (co) polymer containing polyethylene or propylene as a main component is preferable, and a (co) polymer containing propylene as a main component is particularly preferable. Examples of the (co) polymer containing propylene as a main component include a copolymer comprising polypropylene and propylene in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more and another α-olefin. And as the α-olefin to be copolymerized,
Particularly, ethylene is preferred.

Other olefin resins include, for example, graft copolymerized modified olefin resins obtained by graft copolymerizing the above olefin resin with an α, β-unsaturated carboxylic acid such as acrylic acid, maleic acid and anhydride thereof. A block copolymerized modified olefin resin obtained by block copolymerizing the olefin resin with an α, β-unsaturated carboxylic acid such as acrylic acid, maleic acid and anhydride; ethylene / acrylic acid copolymer, ethylene / methacrylic Α-olefins such as acid copolymer, ethylene / crotonic acid copolymer, ethylene / maleic acid copolymer, ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / vinyl acetate copolymer And other copolymerizable monomers; and the like.

Examples of the styrene resin include polystyrene, impact-resistant polystyrene, styrene-acrylonitrile copolymer, styrene-alkyl (meth) acrylate copolymer, ABS resin, MBS resin, AAS resin,
Examples include styrene-modified polyphenylene ether, styrene-butadiene block copolymer resin, styrene-isoprene block copolymer resin, and hydrides thereof.

The rubber is not particularly limited and includes, for example, natural rubber; conjugated diene polymer rubber such as polyisoprene rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, chloroprene rubber; styrene-butadiene random copolymer rubber; Aromatic vinyl-conjugated diene random copolymer rubber such as styrene-isoprene random copolymer rubber, styrene-isoprene-butadiene random copolymer rubber; aromatic vinyl-conjugated diene block copolymer rubber and its hydrogenated product; acrylonitrile A copolymer rubber of a conjugated diene such as a butadiene copolymer rubber and another copolymerizable monomer; a chlorinated polyethylene rubber,
Modified polyethylene rubber such as chlorosulfonated polyethylene rubber; olefin-based copolymer rubber and its modified products;
And silicone rubber. Among them, aromatic vinyl-conjugated diene block copolymer rubber and hydrogenated product, modified polyethylene rubber, olefin-based copolymer rubber and its modified product, silicone rubber and the like are preferable, and olefin-based copolymer rubber is preferred. Particularly preferred.

Examples of the olefin copolymer rubber include, for example, a copolymer rubber obtained by copolymerizing two or more α-olefins exemplified as the olefin resin, and an α-olefin and other copolymerizable monomers. And a copolymer rubber obtained by copolymerizing the above. Specifically, for example, ethylene / propylene copolymer rubber, ethylene / butene-1
Copolymer rubber of ethylene and other α-olefin such as copolymer rubber; isobutene (90 to 99.5% by weight)
Α such as isoprene (10-0.5% by weight) copolymer rubber
-Copolymer rubber of olefin and diene monomer; ethylene and other α-olefin and diene monomer such as ethylene / propylene / dicyclopentadiene copolymer rubber, ethylene / propylene / ethylidene norbornene copolymer rubber Copolymer rubber; and the like.

Examples of the modified olefin copolymer rubber include those obtained by modifying the olefin copolymer rubber with a polar compound. Specifically, for example, a chlorinated olefin copolymer rubber, a chlorosulfonated olefin copolymer rubber, a polar vinyl compound adduct obtained by adding a polar vinyl compound to an olefin copolymer rubber,
Examples include a polar compound graft polymer obtained by graft-polymerizing a polar vinyl compound to an olefin copolymer rubber,
Preferred are chlorinated olefin copolymer rubbers, chlorosulfonated olefin copolymer rubbers, and polar vinyl compound adducts of olefin copolymer rubbers. Examples of the polar vinyl compound include acrylic acid, methacrylic acid, crotonic acid, maleic acid, methyl acrylate, and vinyl acetate.

These resinous or rubbery polymers can be used alone or in combination of two or more. The blending amount of the polyester with respect to the resinous or rubbery polymer is appropriately selected depending on the purpose of use, but is usually 0.01 to 20% by weight, preferably 0.1% by weight, based on the total amount of the resinous or rubbery polymer. It is in the range of 1 to 15% by weight, more preferably 1 to 10% by weight. When the amount of the polyester relative to the resinous or rubbery polymer is in this range, the antistatic effect can be improved to a high degree without deteriorating the physical properties of the polymer.

The polymer composition of the present invention may contain other additives as required below the above components. The other compounding agents are not particularly specified, and are appropriately selected from various compounding agents used in ordinary polymer compositions, and include, for example, inorganic fillers; activators such as diethyl glycol, polyethylene glycol, and silicone oil; Fillers such as calcium carbonate, talc and clay; process oils and waxes.

As the inorganic filler to be compounded, for example,
Calcium oxide, magnesium oxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium carbonate, calcium titanate, barium sulfate, magnesium sulfate, calcium sulfite, talc, clay,
Glass, mica, dolomite, basic calcium carbonate,
Zinc oxide, silica, carbon black, glass fiber and the like, calcium carbonate, barium sulfate, mica,
Talc, carbon black and the like are particularly preferred. These inorganic fillers may be surface-treated with, for example, a silane-based or titanium-based coupling agent, an acid such as a higher fatty acid or an unsaturated organic acid.

These other compounding agents can be used alone or in combination of two or more. The amount of the other compounding agents is appropriately selected within a range that does not impair the purpose of the present invention.

The polymer composition of the present invention can be obtained by mixing the above components. The mixing method may be performed according to a conventional method.For example, after mixing using a Henschel mixer or the like, a single-screw extruder, an extruder such as a twin-screw extruder, Banbury, Brabender, plastmill, kneader, roll, Kneading is performed using an extruder, a multi-axis kneader, a double helical ribbon stirrer, or the like. The kneaded polymer composition is usually handled in a pellet form.

By molding the polymer composition according to a conventional method, a polymer molded article having an excellent antistatic effect can be obtained. As a molding method, for example, injection molding,
Any known method such as hollow molding, extrusion molding, compression molding, and rotational molding may be used, and an arbitrary molded body can be obtained.

The molded article of the obtained polymer composition can be used as a material for molded articles such as covers and parts for lighting fixtures, electric instruments, electronic devices, home appliances, automobiles, meter covers, films, sheets, panels, fibers and the like. It is suitably used as a material for daily goods such as clothes trays.

[0053]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in these examples are on a weight basis unless otherwise specified.

(1) Weight average molecular weight The weight average molecular weight of the polyester was determined according to the GPC method.
It was calculated as a standard polystyrene equivalent. (2) Hydroxyl value and acid value The hydroxyl value and acid value of the polyester were measured according to the following described in “Standard Fat and Oil Analysis Test Method” (Japan Oil Chemical Association). Hydroxyl value 2,4,9,2-83 Acid value 2,4,1-83 (3) Softening point The softening point of polyester was measured according to JIS-K2531.

Production Example 1 332,000 g of terephthalic acid and polyethylene glycol (Mw = 6) were placed in a 2000-cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube.
00) 481.5 g, 2-butyl-2-ethyl-1,3
-257.1 g of propanediol and 0.26 g of monobutyltin oxide as catalyst were charged. (OH / COOH equivalent ratio = 1.20) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester A had a weight average molecular weight of 13,300, an acid value of 0.2 mgKOH / g, a hydroxyl value of 18 mgKOH / g, a softening point of 112 ° C., and a light transmittance of 9%.
It was 0%.

Production Example 2 332,000 g of terephthalic acid and polyethylene glycol (Mw = 4) were placed in a 2000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube.
00) · polypropylene glycol (Mw = 200) ·
Polyethylene glycol (Mw = 400) 768.8
g, 2-butyl-2-ethyl-1,3-propanediol 246.4 g and monobutyltin oxide 0.26 g as a catalyst were charged. (OH / COOH equivalent ratio = 1.15) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester B had a weight average molecular weight of 26,100, an acid value of 0.2 mg KOH / g, a hydroxyl value of 16 mg KOH / g, a softening point of 121 ° C, and a light transmittance of 8
8%.

Production Example 3 332,000 g of terephthalic acid and polyethylene glycol (Mw = 1) were placed in a 2000-cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube.
000) 646.7 g, 2-butyl-2-ethyl-1,
155.9 g of 3-propanediol, 61.8 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.26) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester C had a weight average molecular weight of 31,400, an acid value of 0.2 mg KOH / g, a hydroxyl value of 77 mg KOH / g, a softening point of 109 ° C, and a light transmittance of 8
7%.

Production Example 4 332.2 g of terephthalic acid and polyethylene glycol (Mw = 1) were placed in a 2000-cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube.
000) 832.9 g, 2-butyl-2-ethyl-1,
200.8 g of 3-propanediol, glycerin / EO
69.6 g of an adduct (AM300, OHV = 530) and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.20) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester D had a weight average molecular weight of 27,600, an acid value of 0.2 mg KOH / g, a hydroxyl value of 53 mg KOH / g, a softening point of 93 ° C., and a light transmittance of 92.
%Met.

Production Example 5 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and a nitrogen gas inlet tube was charged with dimer acid (Halidimer 300; acid value 195, monomeric acid 0.1).
58.0%, 97.0% of dimer acid, 2.5% of trimer acid, 348.0 g of Harima Chemicals, 262.5 g of polyethylene glycol (Mw = 1000), 2-butyl-2-ethyl-1,3-propane 63.3 g of a diol, 9.92 g of pentaerythritol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.32) The mixture was stirred while introducing nitrogen gas, and the temperature was increased to 100 ° C. Subsequently, the temperature was raised from 100 ° C to 200 ° C over 6 hours while removing water and unreacted diol generated during the reaction. Then, while dehydrating at 200 ° C, 1
The reaction was continued for 0 hours. The obtained polyester E had a weight average molecular weight of 21,400, an acid value of 0.9 mg KOH / g, a hydroxyl value of 56.8 mg KOH / g, a softening point of 63 ° C, and a light transmittance of 95%.

Production Example 6 A 2000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube was charged with dimer acid (Halidimer 300; acid value 195, monomeric acid 0. 1).
5%, 97.0% of dimer acid, 2.5% of trimer acid, 1152 g of Harima Chemicals, 481.5 g of polyethylene glycol (Mw = 600), 2-butyl-2-ethyl-1,3-propanediol 257 .1 g and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.20) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester F had a weight average molecular weight of 14,900, an acid value of 0.2 mg KOH / g, a hydroxyl value of 19 mg KOH / g, a softening point of 43 ° C, and a light transmittance of 96.
%Met.

Production Example 7 Polymerized fatty acid (Halidimer 250; acid value 193, monomeric acid 3.) was placed in a 2000-cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube.
0%, 79.0% of dimer acid, 18.0% of trimer acid,
1163.6 g of Harima Chemicals, polyethylene glycol (Mw = 400), polypropylene glycol (M
w = 200) ・ Polyethylene glycol (Mw = 40)
0) 768.8 g, 2-butyl-2-ethyl-1,3-
246.4 g of propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.15) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester G had a weight average molecular weight of 27,800, an acid value of 0.2 mg KOH / g, a hydroxyl value of 15 mg KOH / g, a softening point of 71 ° C, and a light transmittance of 97.
%Met.

Production Example 8 A 2000-cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube was charged with hydrogenated dimer acid (Pripol 1009; acid value 196, monomeric acid 1.0). %, Dimer acid 98.0%, trimer acid 1.0
%, Manufactured by Unichema) 1145.8 g, polyethylene glycol (Mw = 1000) 646.7 g, 2-butyl-
155.9 g of 2-ethyl-1,3-propanediol,
61.8 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.26) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester H had a weight average molecular weight of 33,100, an acid value of 0.2 mg KOH / g, a hydroxyl value of 69 mg KOH / g, a softening point of 81 ° C, and a light transmittance of 94.
%Met.

Production Example 9 A 2000-cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and a nitrogen gas inlet tube was charged with dimer acid (Halidimer 300; acid value 195;
5%, 97.0% of dimer acid, 2.5% of trimer acid, 1152 g of Harima Chemicals, 832.9 g of polyethylene glycol (Mw = 1000), and 2-butyl-2-ethyl-1,3-propanediol 200 .80 g, glycerin / EO adduct (AM300, OHV = 530) 6
9.6 g and monobutyltin oxide as a catalyst 0.1.
26 g were charged. (OH / COOH equivalent ratio = 1.20) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C. to 240 ° C. over 3 hours while removing water and unreacted diol generated during the reaction. Thereafter, while dehydrating at 260 ° C., 6
The reaction was continued for hours. The obtained polyester I had a weight average molecular weight of 29,800, an acid value of 0.2 mg KOH / g, a hydroxyl value of 48 mg KOH / g, a softening point of 69 ° C, and a light transmittance of 91.
%Met.

Reference Production Example 1 (US Pat. No. 4,165,303)
Example 1) In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, dimer acid (Halidimer 300; acid value 195, monomeric acid 0.
58.0%, 97.0% of dimer acid, 2.5% of trimer acid, 348.0 g of Harima Chemicals, 960.0 g of polyethylene glycol (Mw = 1000) and 0.26 g of p-toluenesulfonic acid as a catalyst. . (OH / COOH equivalent ratio = 1.6) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, while removing the water generated during the reaction, 10
The temperature was raised from 0 ° C to 200 ° C over 6 hours. Thereafter, the reaction was continued for 10 hours while dehydrating at 200 ° C.
The obtained polyester X had a weight average molecular weight of 17,40.
0, acid value 6.4 mgKOH / g, hydroxyl value 7.8 mgK
OH / g, softening point 68 ° C., light transmittance 78%.

Examples 1 to 9 and Comparative Examples 1 to 2 Resinous and rubbery polymers shown in Table 1 and Production Examples 1 to 9
The polyesters A to I (antistatic agent of the present invention) or the resinous and rubbery polymers obtained in Example 1 and the polyester X obtained in Reference Production Example 1 were mixed in a twin-screw extruder at a compounding ratio shown in Table 1. And pelletized. After the pellets were dried with hot air, a test piece was molded at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C. using an injection molding machine, and the surface resistivity was measured. The surface resistance value of the test piece was 25.
After standing overnight in a constant temperature / humidity room at a temperature of 65 ° C. × 65% RH, the measurement was performed using an insulation resistance meter (manufactured by Toa Denpa Kogyo). Next, the test piece was washed in running water for 10 hours, and then at 20 ° C. × 65% RH.
After being left overnight in a constant temperature and humidity room, the measurement was performed in the same manner. Moreover, the layered peeling prevention property was determined as follows by observing the fractured surface of a test piece which was obtained by bending a molded product and performing a tensile test. ：: good △: cracks are partially formed ×: delamination clearly occurs

[0066]

[Table 1]

From the above results, all of the polymer compositions (Examples 1 to 9) to which the antistatic agent of the present invention was added had excellent appearance of molded articles, low surface resistivity, and excellent delamination prevention properties. It is understood to have On the other hand, the polymer compositions (Comparative Examples 1 and 2) in which an antistatic agent containing no polyhydric alcohol component was added to the polyester had low surface resistivity, but were inferior in anti-lamellar properties.

[0068]

According to the present invention, there is provided a novel polyester-based antistatic agent capable of sufficiently improving the antistatic properties of a resin having a small polarity such as polyolefin or EPDM or a highly saturated hydrocarbon rubber. . Further, the antistatic agent of the present invention has an effect of improving delamination prevention and the like in addition to the above-mentioned application for improving the permanent antistatic property, and can broadly improve the properties of resinous or rubbery polymers.

Claims (3)

[Claims] Claims: 1. A polyhydric carboxylic acid component and a polyhydric alcohol are polycondensed, and at least one alkylene glycol condensate selected from the group consisting of oligooxyalkylene glycols and polyoxyalkylene glycols as a polyhydric alcohol component and a hindered material. At least a polyhydric alcohol, and has a weight average molecular weight (Mw) of 1,000.
An antistatic agent comprising as an active ingredient a polyester having a molecular weight of up to 500,000. 2. A resinous or rubbery polymer composition comprising the polyester according to claim 1. 3. A molded article obtained by molding the resinous or rubbery polymer composition according to claim 2.