JP2002060734A - Antistatic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic composition which has a high antistatic effect, excellent immediate effectivity and excellent persistence and is used for synthetic resins. SOLUTION: This antistatic composition comprising (A) a polymer containing polymer units represented by general formula (1) [R1 is an alkylene; R2 is H, a halogen and a hydrocarbon group; X is H, a hydrocarbon group, an isocyanate residue, an ester group-having hydrocarbon group, or an anionic hydrophilic group; (m) is the number of >=1] and (B) a low mol.wt. organic anion compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fast-acting, long-lasting antistatic composition for synthetic resins.

[0002]

2. Description of the Related Art Synthetic resins are lightweight and easy to process.
It is an important material that is indispensable in modern times because it has excellent properties such as the ability to design a base material according to the application. One of the characteristics of the synthetic resin is that it has excellent electrical insulation properties. Therefore, resin is frequently used as a component of electrical products. But,
Since the insulating property is too high, there is a problem that static electricity is charged due to friction or the like. The charged resin attracts dust and dirt around it, causing a problem that the appearance of the resin molded product is spoiled. Also, in electronic products, for example, precision equipment such as a computer, the circuit may not work properly due to charging. In addition, there is a problem due to electric shock.
When electric shock is generated from the resin to the human body, it may cause discomfort, and may cause an explosion accident where there is flammable gas or dust.

[0003] Therefore, in order to solve such a problem, the synthetic resin is usually treated to prevent electrification.
The most popular method is to add an antistatic agent to the synthetic resin. The antistatic agent, a permanent antistatic agent copolymerizing the antistatic unit in the molecules constituting the resin,
It can be broadly classified into a kneading type antistatic agent which is added when processing and molding a resin.

[0004]

Among these, the kneading type antistatic agent, which bleeds on the surface of the resin and exerts an antistatic effect, is removed from the surface of the resin by friction or washing with water. Therefore, there is a problem in that the antistatic effect is persistent. In addition, when the compatibility with the resin is not good, there is a problem that the internal antistatic agent bleeds immediately on the resin surface, and the effect is lost in several days to several weeks. In contrast, Japanese Patent Application Laid-Open
JP-A-2-34330 describes that a polyalkylene glycol derivative having a structure similar to that of a phenol resin is excellent in persistence of an antistatic agent effect and in compatibility with a resin. Otherwise, there is a problem that a sufficient antistatic effect cannot be obtained, and that it takes time to develop the antistatic effect. In recent years, applications requiring a short time until the antistatic effect is realized, that is, a so-called fast effect, are increasing. In view of such a situation, the present inventors have made intensive studies and as a result, by combining a high molecular weight compound having a polyalkylene glycol monophenol ether structure and an organic anion compound, the quick-acting effect as an antistatic agent is improved. That is, the present invention has been reached. Accordingly, an object of the present invention is to provide an antistatic composition having a high antistatic effect, and having an excellent quick action and durability.

[0005]

That is, the present invention provides the following general formula (1):

[0006]

Embedded image

[0007] (In the formula, R ¹ represents an alkylene group, R ²
Represents a hydrogen atom, a halogen atom or a hydrocarbon group;
Represents a hydrogen atom, a hydrocarbon group, a hydrocarbon group having an isocyanate residue or an ester group, or an anionic hydrophilic group, and m represents a number of 1 or more. )) And a low molecular weight organic anion compound (B).

The present invention is also an antistatic composition in which the above (A) and (B) are impregnated in a carrier. Further, the present invention provides the resin base material having the above (A) and (B)
And an antistatic composition comprising: and the following general formula (2)

[0009]

Embedded image

(Wherein R ^{3 to} R ⁶ represent an aryl group, Y represents an arylene group, and ad represents 0 or 1)
And s represents a number from 1 to 5. This is a resin composition to which the phosphorus compound (C) represented by the formula (1) is added.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer (A) containing a monomer unit represented by the general formula (1) of the present invention is specifically a dehydration condensate of phenol or a substituted phenol with formaldehyde. An alkylene oxide adduct of this compound; a compound in which the terminal of the alkylene oxide chain of this compound is etherified with a hydrocarbon group or substituted with a hydrocarbon group having an isocyanate group or an ester group; or an anion at the terminal of the alkylene oxide chain of the compound. It is a polymer containing, as a monomer unit, a compound into which a hydrophilic group such as a sulfonic acid group, a sulfate group, a phosphate group or a carboxylate group is introduced.

The polymer (A) will be described in more detail. In the general formula (1), the portion of (R ¹ —O) _m is phenol or a phenol having a substituent, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide), long chain α -It can be obtained by addition polymerization of an alkylene oxide such as olefin oxide and styrene oxide. When the (R ¹ -O) _m portion is formed by addition polymerization of this alkylene oxide or the like, the type of (R ¹ -O) is determined by the type of the alkylene oxide or the like to be added. The polymerization form of the added alkylene oxide or the like is not limited, and may be any of homopolymerization of one kind of alkylene oxide or the like, random copolymerization of two or more kinds of alkylene oxides or the like, block copolymerization, and random / block copolymerization. You may. When the moiety of (R ¹ -O) _m is a polyalkylene oxide, R ¹ is an alkylene group, but has 2 carbon atoms.
Preferred are alkylene groups of 4 to 4, and most preferred is an ethylene group. When the (R ¹ -O) _m portion is formed by copolymerization of two or more types of alkylene oxides, one of them is preferably ethylene oxide. The polymerization degree m is a number of 1 or more, preferably 1 to 30.
0, more preferably 1 to 200, and most preferably 5 to 100.

R ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group. Examples of the alkyl group include:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl,
Isopentyl, secondary pentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl,
Grade nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triaconsil , 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2
-Decyltetradecyl, 2-dodecylhexadecyl, 2
-Hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like.

Examples of the alkenyl group include vinyl,
Allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

As the aryl group, for example, phenyl,
Toluyl, xylyl, cumenyl, mesityl, benzyl,
Phenethyl, styryl, cinnamyl, benzhydryl,
Trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, Dinonylphenyl, α
-Naphthyl, β-naphthyl group and the like.

Examples of the cycloalkyl group and cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclohexenyl And a heptenyl group.

Among them, R ² is preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 36 carbon atoms in view of miscibility and compatibility with the resin.
A chlorine atom, a bromine atom or an alkyl or aryl group having 1 to 24 carbon atoms is more preferred.

X represents a hydrogen atom, a hydrocarbon group, a hydrocarbon group having an isocyanate residue or an ester group, or an anionic hydrophilic group. Examples of the hydrocarbon group include the same as the alkyl group, alkenyl group, aryl group, cycloalkyl group, cycloalkenyl group and the like described in the case of R ² above, and among these, an alkyl group having 1 to 6 carbon atoms. Is preferred.

Examples of the isocyanate residue include monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolylene isocyanate and oleyl isocyanate. Isocyanate residues.

Examples of the ester group include acetyl,
Examples include propionyl, butyryl, isobutylyl, valeryl, isovaleryl, pivalyl, lauroyl, myristoyl, palmitoyl, stearoyl, behenyl, acroyl, propioloyl, methacryloyl, crotonoyl, oleiroyl, benzoyl, phthaloyl, succinyl, and the like.

When X is an anionic hydrophilic group, specifically, for example, in the general formula (1), X is-(R
¹ O) _m X portions _{^{- (R 1 O) m -C}} A H 2A SO 3 M ( alkylsulfonic acid group wherein A represented by the number of 2-4),
A sulfate group represented by — (R ¹ O) _m SO ₃ M;
(R ¹ O) _m PO ₃ phosphate groups represented by M _2, or - (R ¹ O) methyl carboxylate group represented by _m CH ₂ COOM and the like.

In the above general formula representing an anionic hydrophilic group, M represents a hydrogen atom, a metal atom or ammonium. Examples of the metal atom include an alkali metal atom such as lithium, sodium, and potassium, and an alkaline earth metal atom such as magnesium and calcium (however, since the alkaline earth metal atom is usually divalent, 1/2). Examples of ammonium include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N-methylmonoethanolamine, N-ethylethanolamine, Diethanolamine, triethanolamine, morpholine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediopear, aminoethylethanolamine, N,
Ammonium such as N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.
M is preferably sodium or potassium.

These anionic hydrophilic groups can be used to form a part or all of the terminal hydroxyl groups of a compound obtained by adding an alkylene oxide or the like to phenol or a phenol having a substituent, if necessary, by a known method. It can be obtained by introducing a hydrophilic group. By introducing an anionic hydrophilic group, the antistatic effect is further improved.

The polymer (A) containing a monomer unit represented by the general formula (1) is prepared by condensing a phenol with formaldehyde by a known method and then adding an alkylene oxide or the like, or further adding a terminal. Can be etherified with a hydrocarbon or substituted with a hydrocarbon group having an isocyanate group or an ester group, and further, if necessary, X can be substituted with an anionic hydrophilic group. Also,
The polymer (A) is a polymer containing at least two, preferably 3 to 30, monomer units represented by the general formula (1). When phenols and formaldehyde are condensed, they can be condensed with other condensable compounds. Other compounds that can be co-condensed with phenols include, for example, xylene,
Resorcin, catechol, hydroquinone, anisole and the like can be mentioned.

The proportion of the monomer unit represented by the general formula (1) in the polymer (A) containing the monomer unit represented by the general formula (1) is not particularly limited. But,
When this ratio is small, the obtained antistatic agent composition is unlikely to exhibit a sufficient effect, and in order to obtain a sufficient effect, it is necessary to add a large amount to the resin base material, and the strength of the resin base material, etc. May lead to a decrease in the physical properties of the material. For this reason, the proportion of the monomer unit represented by the general formula (1) in the polymer (A) is preferably 10% by weight or more, and more preferably 30% by weight or more based on the total amount of the polymer (A). Is more preferable.

The low molecular weight organic anion compound (B) used in the present invention is an organic compound having an acidic group or a neutralized product thereof with a basic compound. Examples of the organic compound having an acidic group include fatty acids, alkenyl succinic acids, (alkyl-substituted) benzoic acids, (alkyl-substituted) salicylic acids, polyacrylic acids, N-acylmethylamino acetates, acylated amino acids, polyoxyalkylenes Organic carboxylic acids such as alkyl ether carboxylic acids; alkyl sulfonic acid, (alkyl-substituted) benzene sulfonic acid, (alkyl-substituted) phenyl ether disulfonic acid, naphthalene sulfonic acid, formaldehyde condensate of naphthalene sulfonic acid, isethionic acid, isethionic acid fatty acid ester ,
Organic sulfonic acids such as isethionic acid alkyl ether, α-olefin sulfonic acid, α-sulfofatty acid methyl ester, and sulfosuccinic acid diester; alkyl sulfate, alkenyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate Organic sulfates such as esters, polyoxyalkylene fatty acid alkanolamide sulfates, and sulfo fatty acid esters; organic phosphoric acids such as acidic alkyl phosphates, acidic alkyl phosphites, acidic polyoxyalkylene alkyl phosphates, and alkyl phosphonic acids And the like. Of these, organic sulfonic acids are particularly preferred.

When these organic compounds having an acidic group have a large molecular weight, the antistatic composition of the present invention may not exhibit the fast-acting effect in some cases. Therefore, the average molecular weight of the organic compound having an acidic group is preferably from 100 to 500, and more preferably from 100 to 400.

The organic compound having an acidic group exhibits an antistatic effect even in the form of a free acid, but is preferably used as a neutralized product with a basic compound.
Such basic compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide,
Metal hydroxides or metal oxides such as calcium hydroxide, magnesium oxide and calcium oxide; examples of ammonium include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine and di (iso) propylamine , Monoethanolamine, N-methylmonoethanolamine, N-ethylethanolamine, diethanolamine, triethanolamine, morpholine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3- Ammonium such as propane diopear, aminoethylethanolamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine; and tetraphenylphosphonium, tetrabutylphosphonium Machine phosphonium, and the like.
Among them, a neutralized product of an alkali metal such as sodium hydroxide and potassium hydroxide is more preferable. Among them, a neutralized product of a metal hydroxide or a metal oxide of an alkali metal or an alkaline earth metal is preferable.

Examples of such particularly preferred neutralized organic sulfonic acids include, for example, Na, C9 decyl sulfonic acid.
-C13 Na alkyl sulfonate, Na octadecyl sulfonate, Na p-toluene sulfonate, Li dodecylbenzene sulfonate, N dodecylbenzene sulfonate
a, dodecylbenzenesulfonic acid K, naphthalenesulfonic acid Na, nonylnaphthalenesulfonic acid Na, isethionate Na, isethionate lauryl ester Na, isethionate lauryl ether Na, sulfurized C12-C14 olefin Na, sulfurized C16-C18 olefin Na, α -Sulfostearic acid methyl ester Na, sulfosuccinic acid dibutyl ester Na, sulfosuccinic acid di-2-ethylhexyl ester Na and the like. Among these neutralized organic sulfonic acids, Na decyl sulfonic acid,
Particularly preferred are C9 to C13 sodium alkylsulfonate, sodium octadecylsulfonate, and sodium dodecylbenzenesulfonate.

In the antistatic composition of the present invention, the weight ratio of the polymer (A) having the monomer unit represented by the general formula (1) to the organic anion compound (B) is (A) / weight ratio. (B) is preferably 10/90 to 99.5 / 0.5, and more preferably (A) / (B) is 15/90.
/ 85 to 99/1.

The antistatic composition of the present invention may be added to the resin as it is, or may be added after impregnating the carrier, if necessary. When impregnating the carrier, the mixture may be heated and mixed as it is, or if necessary, a method of diluting with an organic solvent, impregnating the carrier, and then removing the solvent may be used. As such a carrier, those known as resin fillers and fillers can be used. For example, calcium silicate powder, silica powder, talc powder, alumina powder,
Titanium oxide powder and the like can be mentioned, and silica powder is particularly preferable.

In the present invention, such an antistatic composition is added to and blended with various resin base materials to form a resin composition. As such a resin substrate, for example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene,
Polyolefin resins such as polypropylene, polymethylpentene, ethylene-propylene copolymer, polybutadiene, polyisoprene; polystyrene; polyvinyl chloride;
Polyvinylidene chloride, polychloroprene, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer,
Polyhaloolefin resins such as vinyl chloride-vinylidene chloride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polyvinyl acetate, ethylene-vinyl acetate copolymer (EVA) ), Polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl formal,
Polyvinyl butyral, polymethyl methacrylate, acrylic resin, ketone resin, norbornene resin, polyacetal resin, polyamide resin, polyamideimide resin,
Polyarylate resin, polyimide resin, polyetherimide resin, polyetheretherketone, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester resin such as polyhexamethylene terephthalate, polycarbonate, polysulfone resin, polyphenylene ether resin, polyphenylene sulfide resin Thermoplastic resins such as epoxy resin, polyurethane resin, phenol resin, unsaturated polyester resin, polylactic acid resin, polyimide resin, urea resin, melamine resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, furan resin, Thermosetting resins such as rosin-modified maleic resin; silicone resins; fluororesins such as polyvinyl fluoride and polyvinylidene fluoride; natural rubber (N ), Polyisoprene rubber (I
R), styrene butadiene rubber (SBR), polybutadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber, acrylonitrile butadiene rubber (NBR), rubber-based polymer compounds such as silicone rubber, etc. Is mentioned. Moreover, what is called a polymer alloy combining these resins may be used.

The amount of the antistatic composition of the present invention to be added to the resin substrate is not particularly limited. However, if the amount is too large, the physical properties such as the mechanical strength of the resin of the base material may be reduced, or the compounding may be difficult.If the amount is too small, the antistatic effect becomes insufficient. In some cases, the preferred compounding amount is 0.01 to the resin base material.
-20% by weight, more preferably 0.05-15% by weight,
Most preferably, it is 1 to 10% by weight. The blending method is not particularly limited, and any commonly used method can be used. For example, roll kneading, bumper kneading,
What is necessary is just to mix and knead with an extruder, a kneader, etc. and to mix.

The antistatic composition of the present invention is added to and blended with a resin base together with a flame retardant to form a resin composition, whereby the durability of the antistatic effect of the resin composition can be improved. it can. Examples of the flame retardant that can be used in combination include, for example, tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) ) Halogen flame retardants such as propane, decabromodiphenyl oxide, hexabromocyclodecane, tetrabromophthalic anhydride, chlorinated polyethylene, chlorinated paraffin, perchlorocyclopentadecane, chlorendic acid, and tetrachlorophthalic anhydride; ammonium phosphate, Tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyldiphenyl phosphate, xylenyl Phenyl phosphate, phenylene bis (diphenyl phosphate), phenylene bis (phenyl cresyl phosphate), phenylene bis (dicresyl phosphate), phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), Phosphorus flame retardants such as bisphenol A bis (dicresyl phosphate); red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, zinc borate, aluminum hydroxide, magnesium hydroxide, guanidine nitride, etc. Inorganic flame retardants. Among the flame retardants, synthetic resins containing a halogen-containing flame retardant such as a halogen-based flame retardant or a halogen-containing phosphorus-based flame retardant may generate dioxins during combustion. Flame retardants contained tend to be avoided. Further, among the flame retardants, when used in combination with the antistatic composition of the present invention, depending on the resin base material, the resin may be colored by heat or the heat resistance may be reduced. As such a flame retardant that does not have a fear, a phosphorus compound represented by the following general formula (2) is preferable.

[0035]

Embedded image

(Wherein, R ^{3 to} R ⁶ represent an aryl group, Y represents an arylene group, ad represents a number of 0 or 1, and s represents a number of 1 to 5.) In the formula (2), R ^{3 to} R ⁶ represent an aryl group, which may be the same or different. Examples of the aryl group include the same aryl groups as those described for R ^{2 in} the general formula (1), and among them, phenyl, cresyl, and xyenyl are preferable. Y represents an arylene group. The arylene group is a residue obtained by removing a hydroxyl group from divalent phenols. Examples of such dihydric phenols include resorcin, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, and biphenol. ad represents a number of 0 or 1, and may be the same or different. s is the average value of the repeating unit, and represents the number of 1 to 5.

The phosphorus compound represented by the general formula (2) can be prepared by a known method (for example, see JP-A-59-20224).
No. 0). Specific examples of the phosphorus compound represented by the general formula (2) include:
For example, phenylene bis (diphenyl phosphate),
Phenylene bis (phenylcresyl phosphate),
Examples include phenylene bis (dicresyl phosphate), phenylene bis (dicylenyl phosphate), bisphenol A bis (diphenyl phosphate), and bisphenol A bis (dicresyl phosphate). The amount of these flame retardants varies depending on the type and use of the resin serving as the base material, and cannot be specified unconditionally, but is generally preferably 0.5 to 30% by weight based on the resin base material,
It is more preferably 25% by weight, most preferably 5 to 20% by weight.

In addition, the antistatic composition of the present invention comprises
Antioxidants, light stabilizers, ultraviolet absorbers, fluoroolefin resins, other antistatic agents, antifogging agents, lubricants, plasticizers, coloring agents, fungicides, crystal nucleating agents, compatibilizers, antiblocking agents, foaming Agents, inorganic electrolytes, fillers, fillers, pigments, fragrances and other resin additives. Among them, it is preferable to use an antioxidant, a fluoroolefin resin or a lubricant in combination.

Examples of such antioxidants include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples of phenolic antioxidants include 2,6-di-tert. -Butylphenol (hereinafter, tert.-butyl is abbreviated as t-butyl), 2,
6-di-t-butyl-4-methylphenol, 2,6-
Di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4 ′
-Bis (2,6-di-t-butylphenol), 4,
4'-bis (2-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-
Butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol),
4,4'-isopropylidenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6- Nonylphenol), 2,
2′-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2′-hydroxy-3′-tert-butyl-5′-methylbenzyl) 4-methylphenol,
3-t-butyl-4-hydroxyanisole, 2-t-
Butyl-4-hydroxyanisole, stearyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di-t-
Oleyl butylphenyl) propionate, dodecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di-t
-Butylphenyl) octyl propionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-
Glycerin monoester of hydroxy-3,5-di-t-butylphenyl) propionic acid, ester of 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid with glycerin monooleyl ether, 3- (4
-Hydroxy-3,5-di-t-butylphenyl) propionic acid butylene glycol ester, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4′- Thiobis (3
-Methyl-6-t-butylphenol), 4,4′-thiobis (2-methyl-6-t-butylphenol),
2,2′-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-4
(N, N'-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl)
Sulfide, tris (3,5-di-t-butyl-4
-Hydroxyphenyl) propionyl-oxyethyl
Isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1,
3,5-tris (3 ′, 5′-di-tert-butyl-4-hydroxybenzoyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl ) Sulfide, 1,
3,5-tris (4-di-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) Sulfide), 6- (4-
Hydroxy-3,5-di-t-butylanilino) -2,
4-bis (octylthio) -1,3,5-triazine,
2,2-thio- {diethyl-bis-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinamide), 3,5-
Di-t-butyl-4-hydroxy-benzyl-phosphoric acid diester, bis (3-methyl-4-hydroxy-5-t
-Butylbenzyl) sulfide, 3,9-bis [1,
1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,
5] undecane, 1,1,3-tris (2-methyl-4
-Hydroxy-5-t-butylphenyl) butane, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-t) −
(Butylphenyl) butyric acid glycol ester.

Examples of the phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and 4,4-butylidenebis (3-methyl-6-t-butylphenyldiisotridecyl) phosphite. Phyte, distearylpentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, tris (nonylphenyl)
Phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 1,1,3-butyridine tris (3
-Methyl-6-t-butylphenyldiisotridecyl)
Phosphite, 2,2-propylidenebis (3-methyl-6-t-butylphenyldiisotridecyl) phosphite, tetrakis (2,4-di-t-butylphenyl)
-4,4-biphenylene-diphosphonite, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9
-Oxa-10-phosphaphenanthrene and the like.

Examples of the sulfur-based antioxidants include dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and lauryl stearyl thiopionate. Dipropionate, distearyl-β, β′-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) Pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4, '- thiodi (3-methyl -5-t
-Butyl-4-phenol) ester, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amylthioglycol and the like.

The amount of these antioxidants varies depending on the resin used as the base material, and cannot be specified unconditionally, but is preferably 0.001 to 15% by weight based on the resin base material.
0.005 to 10% by weight is more preferred, and 0.01 to 5% by weight.
% Is most preferred.

The resin composition of the present invention preferably contains a fluoroolefin resin. The resin composition containing the fluoroolefin resin is less likely to ignite or burn when a fire occurs, by preventing dripping during melting. The fluoroolefin resin referred to here is a polymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer,
Examples thereof include a tetrafluoroethylene-hexafluoropropylene polymer and a copolymer of tetrafluoroethylene with an ethylene monomer containing no fluorine. Preferably, it is polytetrafluoroethylene (PTFE),
PTFE having an average molecular weight of 500,000 or more is more preferable.
0000-10,000,000 PTFE is particularly preferred. Specific examples thereof include, for example, Teflon (registered trademark) 6-J (manufactured by DuPont-Mitsui Fluorochemicals), polyflon D-1,
Examples include polyflon FA-100, polyflon F-103, polyflon F-201, polyflon MPA (manufactured by Daikin Industries, Ltd.) CD076 (manufactured by Asahi ICI Fluoropolymers), and Algoflon F5 (manufactured by Montefluos). The blending amount of the fluoroolefin resin cannot be unconditionally determined because it varies depending on the resin used as the base material and the application, but is generally preferably 0.05 to 5% by weight, and preferably 0.1 to 2% by weight based on the resin base. % Is more preferred, and 0.5 to
1.5% by weight is most preferred.

Examples of the lubricant usable in the present invention include hydrocarbon lubricants such as liquid paraffin, paraffin wax and polyethylene wax; aliphatic lubricants such as stearyl alcohol, stearic acid and 12-hydroxystearic acid; stearamide Amide lubricants such as amide, oleic acid amide, erucic acid amide, methylenebisstearic acid amide, ethylene stearic acid amide; calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate, stearic acid Metal soap-based lubricants such as barium / zinc stearate complex, zinc stearate / calcium stearate complex; hardened fats and oils, glycerin monostearate, butyl stearate, pentaerythritol stearate Rate, include ester lubricant such as stearyl stearate.

The amount of these lubricants varies depending on the resin used as the base material, and cannot be specified unconditionally, but is generally preferably 0.001 to 15% by weight based on the resin base material, and is preferably 0.001 to 15% by weight.
5 to 10% by weight is more preferable, and 0.01 to 5% by weight is most preferable.

Examples of the ultraviolet absorber that can be used in the present invention include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and other ultraviolet absorbers. Examples of the benzotriazole-based ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3 ', 5'-di-t-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-3'-
t-butyl-5'-methylphenyl) benzotriazole, 2- {2'-hydroxy-3 ', 5'-bis (α,
α-dimethylbenzyl) phenyl} benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5 ′
-Methylphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-
5′-t-ocrphenyl) benzotriazole, 2-
{2'-hydroxy-3 '-(3 ", 4", 5 ", 6"
-Tetrahydrophthalimidomethyl) -5'-methylphenyl {benzotriazole, 2,2-methylenebis} 4- (1,1,3,3-tetramethylbutyl) -6
(2H-benzotriazol-2-yl) phenol}, 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole and the like.

As the benzophenone-based ultraviolet absorber,
For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-
4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone,
Bis (5-benzoyl-4-hydroxy-2-methoxyphenylmethane) and the like.

Other ultraviolet absorbers include, for example,
Salicylates such as phenyl salicylate, 4-t-butylphenyl salicylate and 4-octylphenyl salicylate; ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3
-Cyanoacrylates such as diphenylacrylate;
Oxalic acid-based ultraviolet absorbers such as 2-ethoxy-2'-ethyloxalic acid bisanilide and the like can be mentioned.

Examples of the hindered amine light stabilizer usable in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6). -Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-butylmalonate, tetrakis (2,2,6,6-tetramethyl-4
-Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, ( Mixed-2, 2, 6, 6
-Tetramethyl-4-piperidyl / tridecyl) -1,
2,3,4-butanetetracarboxylate, (mixed-1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] Undecane) diethyl} -1,2,
3,4-butanetetracarboxylate, mixed
{1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- (2
4,8,10-tetraoxaspiro [5,5] undecane) diethyl {-1,2,3,4-butanetetracarboxylate, poly {6- (1,1,3,3-tetramethylbutyl) Imino-1,3,5-triazine-2,4
-Diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6
-Tetramethyl-4-piperidyl) imino}, dimethylsuccinate / 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2,2
6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, ethylenebis (2,2,6,6-tetramethyl-3-oxa-4-piperidine ) And the like.

Other light stabilizers usable in the present invention include, for example, {2,2′-thiobis (4-t-octylphenolate)}-2-ethylhexylamine nickel (II), nickel dibutyl dithiocarbamate,
{2,2′-thiobis (4-t-octylphenolate)}-2-butylamine nickel (II), nickel bis (octylphenyl) sulfide, 3,5-di-t
-Based light stabilizers such as -butyl-4-hydroxybenzylphosphate monoethylate nickel complex; 2,4-di-
t-butylphenyl-3,5'-di-t-butyl-4 '
-Hydroxybenzoate and the like.

Other antistatic agents usable in the present invention include, for example, glycerin monofatty acid ester, polyglycerin fatty acid ester, diethanolamine fatty acid amide, polyalkylene glycol alkyl ether,
N-alkyl ammonium chloride and the like can be mentioned.

Other additives that can be used in the present invention include, for example, dibenzylidene sorbitol, bis (p-
(Methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, aluminum hydroxy-di (t-butylbenzoate), sodium bis (4-t-butylphenyl) phosphate, 2,2-methylenebis (4,6 Nucleating agents such as -di-t-butylphenyl) sodium salt; plasticizers such as phthalic acid ester, dibasic acid ester, chlorinated paraffin, polyester, epoxidized ester, phosphoric acid ester, trimellitic acid ester; metal soap , Organic tin, organic lead, phosphite, epoxide, β-diketone, polyol, perchlorate, hydrotalcite, chlorinated PVC stabilizer such as zeolite, and the like.

The polymer (A) containing the monomer unit represented by the general formula (1) and the organic anion compound (B) are contained as essential components, and various additives may be added as necessary. The antistatic composition of the present invention obtained by the addition of, especially in the molding process of various synthetic resins, is added to the resin by kneading and exhibits excellent antistatic performance, and this antistatic effect is not It has the characteristic that it is maintained for a long time immediately after the addition processing to the steel.

[0054]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples, units such as "parts" and "%" are based on weight unless otherwise specified. Samples 1 to 15 described below were blended in the proportions shown in Tables 1 and 2 to prepare various antistatic compositions of the present invention and comparative products, which were subjected to evaluation tests. .

[0055]

Embedded image

[0056]

Embedded image

(EO) _10- (EO) ₁₀ / (PO) ₁₀ is obtained by adding 10 moles of ethylene oxide to nonylphenol and then adding 1 mole each of ethylene oxide and propylene oxide.
It means that 0 mol was randomly copolymerized.

[0058]

Embedded image

[0059]

Embedded image

Sample 5: Sodium dodecylbenzenesulfonate Sample 6: Calcium dodecylbenzenesulfonate Sample 7: Lithium C9-C13 alkyl sulfonate Sample 8: Sodium di-2-ethylhexylsulfosuccinate Sample 9: Polyoxyethylene (5) stearyl Sodium phosphate ester Sample 10: C12-C13 sodium polyoxyethylene (3) alkyl sulfate ester Sample 11: Silica powder (trade name: Tokusil NP manufactured by Tokuyama) Sample 12: Nonylphenol ethoxylate (average molecular weight 2,000) Sample 13: Polyethylene glycol (average molecular weight
6,000) Sample 14: Glycerin monostearate Sample 15: Sodium polyoxyethylene (30) nonylphenol ether sulfate

[0061]

Embedded image

Sample 17: triphenyl phosphate

[0063]

[Table 1]

[0064]

[Table 2]

Example 1 Invention Products 1 to 10 or Comparative Product 1
Using each of the antistatic agents No. to No. 6, polyethylene glycol terephthalate (PET-G) at the ratio shown in Table 3 below
280 ° C, 20r with an extruder
A pellet was prepared under the condition of pm. The pellets are processed at 280 ° C. with an injection molding machine at a diameter of 10 cm and a thickness of 1.5 mm.
Molded article. Using each of these molded articles as test pieces, their surface specific resistance was measured by the following method to evaluate the antistatic property.

[0066]

[Table 3]

Evaluation of antistatic property : Each test piece of a molded article of these PET resin compositions was subjected to a temperature of 23 ° C. and a humidity of 6
The specimen was stored under 0% conditions, and after 10 minutes and 7 days after the molding, the surface resistivity of these test pieces was measured under the following conditions. Measuring device: Digital ultra high resistance meter R8 manufactured by Advantest
340 Measurement temperature: 23 ° C. Measurement humidity: 55 to 65% Applied voltage: 500 V Application time: 1 minute Also, in order to evaluate the durability of the antistatic property, each test piece after storage for 7 days was put in running water for 30 minutes. After immersion and air drying, the surface specific resistance values were measured. Further, in order to evaluate the durability of the antistatic property at a high temperature on another test piece, 8
After standing at 0 ° C. for 14 days, their surface specific resistance values were measured. Table 4 shows the measurement results.

[0068]

[Table 4]

Example 2: Products 1, 2, 5, 6, 8, and 8 of the present invention
Using each of the antistatic agents of Comparative Examples 10, 11 or Comparative Products 1, 2, 4 to 6, polycarbonate / A in the ratio shown in Table 5 below
The BS resin composition was blended, and the extruder was used at 280.degree.
Pellets were prepared under the condition of 5 rpm. These pellets were processed by an injection molding machine at 280 ° C., with a diameter of 10 cm and a thickness of 3 cm.
mm. Using these molded products as test pieces,
Forming was carried out in the same manner as in Example 1, and after 10 minutes and 7 days (before rinsing) and after immersion in running water (after rinsing), the surface resistivity of these test pieces was measured. Table 6 shows the measurement results.

[0070]

[Table 5]

[0071]

[Table 6]

Example 3 Using the antistatic agent of the product 1, 2, 5, 6 of the present invention or the comparative product 5, and using the sample 16 or 17 as a phosphorus-based flame retardant, the following Table 7 was used. The polycarbonate / ABS resin composition was blended in the proportions shown, and the same operation as in Example 2 was performed to obtain a diameter of 10 cm and a thickness of 3 m.
m. In addition, only the antioxidant was compounded with the resin, and the resin without the flame retardant and the antistatic agent was used as a blank. Using these molded articles as test pieces, the surface resistivity values of these test pieces were measured 10 minutes and 7 days after the forming in the same manner as in Example 1.

Further, in order to evaluate the heat resistance and the thermal coloring property of each test piece, the heat deformation temperature (HD) was determined by the following method.
T) and the surface color difference were measured. Evaluation of heat resistance : length 110 mm, width 4 mm, height 12 m
m, according to JIS K720
7 and the heat distortion temperature (HD
T) was measured, and the change in heat resistance due to the addition of the antistatic agent was evaluated. The lower the heat distortion temperature, the lower the heat resistance. HDT measuring device: HDT measuring device 3A-2 manufactured by Toyo Seiki Seisaku-sho, Ltd. Load: 18.5 kgf / cm2 (A method)

Evaluation of thermal coloring property : A resin test piece formed into a sheet was evaluated using a tester described below and a blank (without adding an antistatic agent and a flame retardant). The color difference (ΔE) of the surface of the molded article was measured to evaluate the thermal coloring property during resin molding. The larger the value of the color difference, the larger the thermal coloring property, indicating that the color difference is not suitable as an antistatic agent. Color difference measuring device: Color difference meter CM-3700 manufactured by Minolta
d Table 8 shows the measurement results.

[0075]

[Table 7]

[0076]

[Table 8]

Example 4 A polypropylene / nylon resin composition was prepared using the antistatic agent of the product 1, 3, 4, 7 to 9 of the present invention or the comparative products 1 to 3 and 6 in the proportions shown in Table 9 below. And pellets were prepared with an extruder at 260 ° C. and 25 rpm. These pellets were formed into a molded product having a diameter of 10 cm and a thickness of 1.5 mm at 260 ° C. by an injection molding machine. Using these molded articles as test specimens, 10 minutes and 7 days after molding (before water washing) in the same manner as in Example 1.
The surface resistivity of these test pieces after immersion in running water (after washing with water) was measured. Table 10 shows the measurement results.

[0078]

[Table 9]

[0079]

[Table 10]

As is clear from the results of the above evaluation tests, for various resins, the resin molded product using the product of the present invention has a surface resistance value immediately after molding which is lower than that of the resin molded product using the comparative product. However, it can be seen that it is small and hardly changes even if it is stored for 7 days or washed with water thereafter, or the change width is small. For PET resin, 14 ° C at 80 ° C
Almost no change is seen even after storage for days. Therefore, it can be seen that the antistatic composition of the present invention has excellent antistatic performance, quick action, and durability for many types of resins.

[0081]

The effect of the present invention is that the antistatic effect is high,
It is an object of the present invention to provide a polymer type antistatic agent for a synthetic resin which is excellent in quick action and durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/521 C08K 5/521 C08L 61/14 C08L 61/14 101/00 101/00 C09K 21/12 C09K 21/12

Claims (6)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ represents an alkylene group, R ² represents a hydrogen atom,
X represents a halogen atom or a hydrocarbon group, X is a hydrogen atom,
Represents a hydrocarbon group, an isocyanate residue, a hydrocarbon group having an ester group, or an anionic hydrophilic group, and m represents a number of 1 or more. An antistatic composition comprising a polymer (A) containing a monomer unit represented by the formula (1) and a low molecular weight organic anion compound (B). 2. The antistatic composition according to claim 1, wherein R ¹ is an alkylene group having 2 to 4 carbon atoms. 3. The method according to claim 1, wherein the low molecular weight organic anion compound (B) is
Organic carboxylic acids, organic sulfonic acids, organic sulfates,
The antistatic composition according to claim 1 or 2, which is an organic compound having an acidic group selected from organic phosphates and having an average molecular weight of 500 or less, or a neutralized product of these and a basic compound. 4. The method according to claim 1, wherein the weight ratio of (A) and (B) is (A) / (B) = 10/90 to 99.5 / 0.5. 3. The antistatic composition according to item 1. 5. The antistatic composition according to claim 1, wherein (A) and (B) are impregnated in a carrier. 6. A resin substrate, wherein the antistatic composition according to claim 1 and the following general formula (2): (Wherein, R ^{3 to} R ⁶ represent an aryl group, Y represents an arylene group, ad represents a number of 0 or 1,
s represents the number of 1-5. A resin composition to which a phosphorus compound (C) represented by the formula (1) is added.