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WO2016084954A1 - Agent antistatique pour une résine thermoplastique et composition de résine thermoplastique - Google Patents

Agent antistatique pour une résine thermoplastique et composition de résine thermoplastique Download PDF

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Publication number
WO2016084954A1
WO2016084954A1 PCT/JP2015/083470 JP2015083470W WO2016084954A1 WO 2016084954 A1 WO2016084954 A1 WO 2016084954A1 JP 2015083470 W JP2015083470 W JP 2015083470W WO 2016084954 A1 WO2016084954 A1 WO 2016084954A1
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group
substituted
antistatic agent
chemical formula
carbon atoms
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Japanese (ja)
Inventor
雄太 斉藤
義高 神田
航 加賀山
潤 福嶋
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Nippon Nyukazai Co Ltd
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Nippon Nyukazai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials

Definitions

  • the present invention relates to an antistatic agent for thermoplastic resins and a thermoplastic resin composition.
  • Thermoplastic resin is one of the materials widely used from miscellaneous goods to household appliances, OA equipment, and automobile parts.
  • ABS resin has a high surface resistivity, and static electricity induced by contact or friction is not easily dissipated or lost. Therefore, it is easy for dust to adhere to the molded product surface during use. Has the disadvantage of detracting from.
  • Japanese Patent Application Laid-Open No. 10-36629 discloses a technique in which alkane sulfonate or alkylbenzene sulfonate is added to an ABS resin as an antistatic agent.
  • Japanese Patent Application Laid-Open No. 2009-249407 discloses a technique of adding an ionic liquid as an antistatic agent to a transparent styrenic thermoplastic resin such as an ABS resin.
  • JP-A-2009-249407 discloses trifluoromethanesulfonic acid, bistrifluoromethanesulfonic acid imide, 1-butyl-3-methylimidazolium methane as anions constituting an ionic liquid added as an antistatic agent.
  • Anions such as sulfonic acid and 1-ethyl-3-methylimidazolium methanesulfonic acid are disclosed.
  • imidazolium, pyridinium, ammonium, phosphonium, and sulfonium are disclosed as cations constituting the ionic liquid.
  • Specific examples of the ammonium cation include trimethylpentylammonium and trimethylhexylammonium. Only quaternary ammonium cations are disclosed.
  • an antistatic agent other than those described above there are known those using a polymer antistatic agent and a conductive material such as metal or carbon.
  • Japanese Patent Application Laid-Open No. 2013-253225 discloses a polymer antistatic agent made of a polymer having a polyether chain such as polyether ester, polyether amide, or polyether ester amide.
  • the present inventors have examined the effectiveness of the conventional technology as described above. As a result, it is possible to prevent an ionic liquid containing an alkylbenzene sulfonate as disclosed in JP-A-10-36629 or a quaternary ammonium cation as disclosed in JP-A-2009-249407. It has been found that even when added to a thermoplastic resin such as ABS resin as an agent, sufficient antistatic performance may not always be obtained.
  • the antistatic performance of conventional polymer antistatic agents is not sufficient. Specifically, to add anti-static performance by adding a conventional polymer antistatic agent to a thermoplastic resin, an addition amount of about 10 to 20 parts by weight per 100 parts by weight of the resin is required. In addition, it has been found that the antistatic effect obtained thereby is limited. In particular, when a conventional polymer-type antistatic agent is used, even if the initial antistatic performance is excellent, the performance deteriorates with time, or the water resistance against operations such as washing with water is low. It turns out that there is a problem.
  • the present invention provides an antistatic agent that can impart excellent antistatic properties even when added in a small amount to a thermoplastic resin, has high water resistance to operations such as washing with water, and is inexpensive.
  • the purpose is to provide.
  • an antistatic material for a thermoplastic resin comprising a mixture of an ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2) and a polymer-type antistatic agent. Agents are provided:
  • R 1 is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6
  • A is a linear or branched alkylene group having 2 to 4 carbon atoms
  • n is an integer from 0 to 50
  • Q1 + is a secondary ammonium ion or a tertiary ammonium ion.
  • R 2 is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6
  • Q2 + is a secondary ammonium ion or a tertiary ammonium ion.
  • thermoplastic resin composition comprising a thermoplastic resin and the above-described antistatic agent for thermoplastic resin.
  • One embodiment of the present invention is an antistatic agent for a thermoplastic resin including a mixture of an ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2) and a polymer antistatic agent.
  • a thermoplastic resin including a mixture of an ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2) and a polymer antistatic agent.
  • the antistatic agent for thermoplastic resins according to the present embodiment it is possible to impart excellent antistatic properties even when added in a small amount to the thermoplastic resin, and water resistance against operations such as washing with water is also possible.
  • a high and inexpensive antistatic agent is provided. For example, even if a conventional polymer type antistatic agent is added in an amount of about 10% by weight relative to the total amount of the resin, 10 11 to 10 12 ⁇ / sq.
  • the antistatic agent for thermoplastic resins according to this embodiment can exhibit a sufficient antistatic effect even when added in a small amount. Therefore, the content of the thermoplastic resin in the thermoplastic resin composition can be increased as compared with the conventional polymer antistatic agent, which required a large amount of addition for the expression of sufficient effects, There is also an advantage that the possibility of impairing the original performance of the resin is minimized. In addition, although the mechanism by which such an effect appears is not completely clear, the following mechanism has been estimated.
  • the predetermined ion-binding salt functions as a conductive path between the molecular chains, thereby It is considered that a synergistically excellent antistatic effect that cannot be achieved by the addition of each of the inhibitor or the above-mentioned predetermined ion-binding salt and high water resistance against operations such as washing with water.
  • the mechanism is based on estimation and does not affect the technical scope of the present invention.
  • one of the chemical formula (1) may be used singly or in combination of two or more, or the chemical formula (2 ) May be used alone or in combination of two or more, one or more of the chemical formula (1) and one or more of the chemical formula (2) And may be used in combination.
  • R 1 and R 2 are each independently a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.
  • Examples of substituted or unsubstituted linear, branched, or cyclic alkyl groups having 1 to 30 carbon atoms used as R 1 and R 2 in the chemical formulas (1) and (2) are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, tert-pentyl, neopentyl Group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl Group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group,
  • a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and 2-ethylhexyl group, dodecyl group, tridecyl group, 1,2-bis ( 2-ethylhexyloxycarbonyl) ethyl group is more preferable, and 2-ethylhexyl group is particularly preferable.
  • Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms used as R 1 and R 2 in the chemical formulas (1) and (2) include, for example, a phenyl group, a dimethylphenyl group ( 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, etc.), isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group), dodecyl Phenyl group (2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group), biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group,
  • a substituted or unsubstituted aryl group having 8 to 18 carbon atoms is preferable, and a dimethylphenyl group (2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4- Dimethylphenyl group, etc.), isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group), dodecylphenyl group (2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group) ) Is more preferable, and an isopropylphenyl group is particularly preferable.
  • Examples of the substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms used as R 1 and R 2 in the chemical formulas (1) and (2) include, for example, benzyl group, phenylethyl group 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) propyl group, or And 3- (2-naphthyl) propyl group.
  • Preferred examples of the anion in the chemical formula (1) include those having a chemical structure represented by the following chemical formulas (3) to (6).
  • preferable examples of the anion in the chemical formula (2) include those having the chemical structures of the following chemical formulas (7) to (10), and among them, those having the chemical structure of the following chemical formula (9) are preferable. .
  • A is a linear or branched alkylene group having 2 to 4 carbon atoms.
  • Examples of the linear or branched alkylene group having 2 to 4 carbon atoms used as A in the chemical formula (1) include an ethylene group, a propylene group, a butylene group, and the like. From the viewpoint of availability, an ethylene group and a propylene group are particularly preferable.
  • the hydrogen atom in the chain or branched alkylene group may be substituted with another substituent.
  • substituents include halogens such as fluorine, chlorine, bromine and iodine, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, phenyl group, p-tolyl group, xylyl group, Aryl groups such as cumenyl group, naphthyl group, anthryl group, phenanthryl group, alkoxy groups such as methoxy group, ethoxy group, tert-butoxy group, aryloxy groups such as phenoxy group, p-tolyloxy group, methoxycarbonyl group, butoxycarbonyl Groups, alkoxycarbonyl groups such as 2-ethylhexyloxycarbonyl group and phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryl
  • N in the chemical formula (1) is an integer of 0 to 50.
  • n is preferably an integer of 1 to 50, more preferably an integer of 1 to 30, and particularly preferably an integer of 1 to 10.
  • Q 1 + and Q 2 + are each independently a secondary ammonium ion or a tertiary ammonium ion.
  • the secondary ammonium ion and the tertiary ammonium ion representing Q1 + and Q2 + can be collectively represented by the following chemical formula.
  • R 3 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.
  • R 4 and R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may be substituted with a hydroxy group or an alkoxy group.
  • R 3 is a hydrogen atom
  • the ammonium ion represented by the chemical formula is secondary
  • R 3 is the predetermined alkyl group
  • the ammonium ion represented by the chemical formula is a third ion.
  • R 3 is preferably a hydrogen atom (that is, Q 1 + and Q 2 + are secondary ammonium ions).
  • R 4 and R 5 are a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms that is substituted with a hydroxy group or an alkoxy group.
  • the substituted alkyl group is more preferably an alkyl group substituted with a hydroxy group, and particularly preferably a hydroxyethyl group.
  • a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms those listed above can be used in the same manner, and detailed description thereof is omitted here. .
  • R 4 and / or R 5 is an alkyl group substituted with an alkoxy group
  • examples of the alkoxy group as the substituent include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and 2-ethylhexene.
  • examples thereof include an alkoxy group having 1 to 8 carbon atoms such as a xyloxy group.
  • secondary ammonium ions include dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, Di-n-butylamine, di-2-butylamine, di-1-pentylamine, di-2-pentylamine, di-3-pentylamine, dineopentylamine, dicyclopentylamine, di-1-hexylamine, di Examples include ions of protonated -2-hexylamine, di-3-hexylamine, dicyclohexylamine, methylethanolamine, and ethylethanolamine.
  • Tertiary ammonium ions include trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentyl.
  • methylethanolamine, ethylethanolamine, diethylethanolamine, or lauryldiethanolamine is more preferably a protonated ion
  • methylethanolamine, ethylethanolamine, or lauryldiethanolamine is a protonated ion.
  • methylethanolamine or ethylethanolamine is particularly preferably a protonated ion
  • ethylethanolamine is most preferably a protonated ion.
  • More preferable compounds of the ion binding salt represented by the chemical formula (1) include ion binding salts represented by the following chemical formulas (11) to (19).
  • more preferable compounds of the ion-binding salt represented by the chemical formula (2) include ion-binding salts represented by the following chemical formulas (20) to (26).
  • ion-binding salts represented by the following chemical formulas (23) to (26) are particularly preferable in terms of high antistatic performance, and ion-binding salts represented by the following chemical formula (23) are most preferable.
  • the production method of the ion-binding salt is not particularly limited, and examples thereof include an anion exchange method, a neutralization method, and an acid ester method.
  • a deammonia method in which an ammonium salt of a sulfate ester or an ammonium salt of a sulfonate ester and a nitrogen-containing compound are reacted to distill off ammonia to obtain an ion-binding salt is also preferably used.
  • the chemical formulas (4), (6), (7) and (10) and the chemical formulas (15), (16), (19), (20), (25) and (26) described in the chemical formulas are described.
  • 8 H 17- , C 12 H 25 -and C 13 H 27 - may each be linear or branched.
  • C 8 H 17 — can be 2-ethylhexyl.
  • any conventionally known polymeric antistatic agent (antistatic agent having a polymer structure) can be suitably used as the polymeric antistatic agent.
  • the “ion-binding salt represented by the chemical formula (1) or the chemical formula (2)” described above is not included in the concept of the “polymer-type antistatic agent” in the present invention even if it has a polymer structure. Shall not be included.
  • polyethers having a hydrophilic group and block copolymerization examples include polyethers having a hydrophilic group and block copolymerization (polyetheresteramides, ethylene oxide-epichlorohydrins, polyetheresters, etc., nonionic types; polystyrene sulfonic acids, etc.
  • a block copolymer having a structure in which it is repeatedly bonded alternately through at least one bond selected from As an example, a block copolymer having a structure in which a polyether block, which is a hydrophilic block having a volume resistivity of 10 5 to 10 11 ⁇ ⁇ cm, and a polyolefin block are bonded alternately and repeatedly can be mentioned.
  • the number average molecular weight (Mn) of the block copolymer is preferably 2000 to 60000.
  • polymer-type antistatic agents available on the market include “Pelestat (registered trademark)” (“Pelestat 300”, “Pelestat 230”, “Pelestat NC6321”, “Pelestat NC6322” manufactured by Sanyo Chemical Industries, Ltd. ”,“ Pelestat NC7350 ”,“ Pelestat HC250 ”, etc.),“ Peletron (registered trademark) ”(“ Peletron PVH ”,“ Peletron PVL ”,“ Peletron HS ”, etc.), Sanko Chemical Co., Ltd.
  • the above-described ion-binding salt and polymer type antistatic agent may be used as they are, or the above-mentioned antistatic agent at a concentration higher than the use concentration is blended in the thermoplastic resin. It may be in the form of a masterbatch.
  • the antistatic agent for thermoplastic resins according to the present embodiment contains the above-described ion-binding salt and polymer-type antistatic agent as essential components, but there is no particular limitation on the content ratio of these components, It can be appropriately determined with reference to a preferable addition amount based on the weight of the thermoplastic resin described later.
  • the antistatic agent for thermoplastic resins according to this embodiment may further contain various additives as required.
  • additives include antistatic agents other than the antistatic agent according to the present invention (for example, metal salts or quaternary ammonium salts, surfactants, ionic liquids, etc.); compatibilizers; glass fibers, metals Fibrous reinforcing agents such as fiber, aramid fiber, ceramic fiber, potassium titanate, carbon fiber; talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, glass flake, milled fiber, metal flake, metal powder Various kinds of fillers; thermal stabilizers or catalyst deactivators represented by phosphate esters and phosphites; oxidation stabilizers; light stabilizers; ultraviolet absorbers; lubricants; pigments; dyes; Examples include flame retardants; plasticizers; mold release agents; ultraviolet absorbers; and antibacterial agents.
  • the content of these additives is not particularly limited, but is usually about 0.1 to 20% by weight with respect to 100% by weight of the
  • metal salt or quaternary ammonium salt metal [alkali metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, etc.)] or quaternary ammonium [amidinium (1-ethyl- 3-methylimidazolium etc.) or guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium etc.)] of organic acids (C1-7 mono- and di-carboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-7 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid)
  • a salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.
  • halides lithium fluoride, -sodium, -potassium, -magnesium, -calcium, -1-ethyl-3-methylimidazolium, etc.
  • a salt is constituted.
  • the cation moiety is the same.), Chloride, bromide, iodide, etc.], perchlorate, fluorinated sulfonate, methanesulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfone Acid salts, undecafluoropentane sulfonates, tridecafluorohexane sulfonates, bistrifluoromethanesulfonimide salts, acetates, sulfates, phosphates, thiocyanates and the like.
  • halide, perchlorate, trifluoromethanesulfonate, bistrifluoromethanesulfonimide salt and acetate are preferred from the viewpoint of antistatic properties, and lithium chloride, potassium and sodium are preferred.
  • Nonionic surfactants include nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
  • Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines (C8-24).
  • EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18-2) EO adducts of higher fatty acid esters (molecular weight of 250 or more and Mn of 30,000 or less); higher fatty acid amide EO adducts (molecular weight of 200 or more and more than 8 to 8 or more, such as EG, PG, glycerin, pentaerythritol and sorbitan) Mn 30,000 or less); and polyhydric alcohols (as described above) EO adducts of alkyl (C3-60) ether (molecular weight of 120 or more and Mn 30,000 or less)], and polyhydric alcohols (above) (C3-60) type nonionic surfactants [for example, polyvalent Fatty acid
  • anionic surfactant examples include those excluding (C11) and those having an anionic group portion of C8-30, such as sodium dodecylbenzenesulfonate.
  • cationic surfactant examples include quaternary ammonium salts such as alkyltrimethylammonium salts excluding (C11).
  • amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. These surfactants may be used alone or in combination of two or more.
  • Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; amine salts [alkylamine (C1-720) salts and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts, etc.]; amidinium salts (1-ethyl-3-methylimidazolium salts) And the like, and quaternary ammonium salts such as guanidinium salts (such as 2-dimethylamino-1,3,4-trimethylimidazolinium salt); and quaternary ammonium salts other than the quaternary ammonium salts. .
  • metal salts such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc
  • the ionic liquid is a compound excluding the above-mentioned metal salt or quaternary ammonium salt and a surfactant, has a melting point of room temperature or lower, and at least one of the cation or anion constituting the organic ion is an organic ion.
  • a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group can be used.
  • polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group
  • polymers described in JP-A-3-258850 for example, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
  • pigments examples include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (chromium oxide, chromium, etc.) Lead acid, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lake, monoazo, disazo, chelate azo, etc.), polycyclic pigments (benzimidazolone, phthalocyanine] , Isoindolinone, anthraquinone, etc.); dyes such as azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, aniline, etc .; 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-
  • Lubricants include waxes (carnauba wax, paraffin wax, polyolefin wax, etc.), higher fatty acids (C8-24, eg stearic acid, oleic acid), higher alcohols (C8-18, eg stearyl alcohol, lauryl alcohol) and higher fatty acid amides. (C8-24, such as stearamide, oleamide) and the like.
  • the flame retardant includes one or more flame retardants selected from the group consisting of halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants and phosphorus-containing flame retardants.
  • Halogen-containing flame retardants include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, hexabromocyclo Dodecane, etc .;
  • nitrogen-containing flame retardants urea compounds, guanidine compounds or triazine compounds (melamine, guanamine, etc.) and salts of cyanuric acid or isocyanuric acid, etc .
  • sulfur-containing flame retardants sulfates, organic sul
  • flame retardants may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.
  • a flame retardant aid for example, polytetrafluoroethylene, metal oxide (for example, zinc oxide), etc.
  • nitrogen-containing flame retardants are preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.
  • plasticizers include aromatic carboxylic acid esters [phthalic acid esters (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid esters [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], aliphatic dicarboxylic acid esters.
  • thermoplastic resin According to the other form of this invention, the thermoplastic resin composition containing a thermoplastic resin and the antistatic agent for thermoplastic resins which concerns on the form mentioned above is also provided.
  • thermoplastic resin used in the present invention is not particularly limited.
  • the form of the copolymer when the thermoplastic resin is a copolymer may be any of a block copolymer, a random copolymer, a graft copolymer, and an alternating copolymer.
  • a thermoplastic resin a synthetic product may be used and a commercial item may be used.
  • the polymerization method for synthesizing these thermoplastic resins is not particularly limited, and a known method can be used. Examples thereof include a high pressure radical polymerization method, a medium to low pressure polymerization method, a solution polymerization method, a slurry polymerization method, a bulk polymerization method, an emulsion polymerization method, and a gas phase polymerization method.
  • the catalyst used for the polymerization is not particularly limited, and examples thereof include peroxide catalysts, Ziegler-Natta catalysts, metallocene catalysts, and the like.
  • thermoplastic resin is preferably at least one selected from the group consisting of (meth) acrylic resins, styrene resins, olefin resins, polyester resins, and acrylonitrile-butadiene-styrene copolymers (ABS resins). And ABS resin is particularly preferable.
  • ABS resin refers to a resin in which “polybutadiene” (PBD) is uniformly dispersed in “AS resin” which is a copolymer of acrylonitrile (AN) and styrene (ST).
  • PBD polybutadiene
  • AS resin a copolymer of acrylonitrile
  • ST styrene
  • the resin composition is appropriately changed depending on the required performance.
  • ST / AN 90/10 to 50/50.
  • a monomer such as methyl methacrylate (MMA), ⁇ -methylstyrene (AMS) or N-phenylmaleimide (PMI) may be added as a copolymerization component of the AS resin phase during the production.
  • the constituent amount as the polybutadiene component is 10 to 80% with respect to 100 parts by weight of the ABS resin, but generally 10 to 30% is preferably used.
  • copolymer rubber (SBR) of styrene and butadiene, acrylic rubber (AR), copolymer of ethylene and propylene (EPR), chlorinated polyethylene (CPE) Etc. may be added during production as required.
  • the content of the antistatic agent for thermoplastic resins in the thermoplastic resin composition is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, with respect to 100% by weight of the thermoplastic resin composition. %.
  • the weight ratio of thermoplastic resin: polymer type antistatic agent is preferably 99: 1 to 70:30, more preferably 98: 2 to 80:20. More preferably 97: 3 to 85:15.
  • the content of the ion-binding salt is preferably 0.1 to 10% by weight, more preferably 0.8% with respect to 100% by weight of the total weight of the above-described polymer type antistatic agent and the thermoplastic resin. It is 5 to 5% by weight, more preferably 1 to 3% by weight.
  • thermoplastic resin composition According to the present invention, an antistatic agent capable of stably exhibiting sufficient antistatic performance over a long period of time and a thermoplastic resin composition containing the antistatic agent are provided. Therefore, the thermoplastic resin composition according to the present embodiment is useful for OA equipment, electronic members, automobile housings, medical members, various containers, covers, films, sheets and the like.
  • test piece whose surface resistivity was measured was rubbed 10 times with a sponge with three drops of neutral detergent, the foam was washed away with running water, and the water drops were wiped off and dried at 110 ° C. for 5 minutes.
  • the surface resistivity after washing with water was measured in the same manner as described above except that the surface resistivity of the test piece after performing these steps 5 times was measured. The measurement results are shown in Tables 1 to 3 below.
  • an antistatic agent is used in combination with an ion-binding salt having a predetermined structure in the polymer antistatic agent.
  • ABS resin composition evaluation example 2 After mixing “Pelestat NC6321” which is the above-mentioned “other antistatic agent” (polymer type antistatic agent) with 100 parts by weight of ABS resin (Stylac (registered trademark) -ABS190F; manufactured by Asahi Kasei Chemicals Corporation). Was added so as to have a content of 10% by weight to obtain a mixture of an ABS resin and a polymer antistatic agent. Subsequently, in the examples (experimental examples of the present invention), the above-described ion-binding salt ([MEM] [Cum-SO 3 ]) was added to the obtained mixture in an amount of 2% by weight based on the weight of the mixture. It added so that it might become. On the other hand, in the comparative example (experimental example that departs from the present invention), the ion-binding salt was not added (see Table 4 below for the type and amount of the added antistatic agent).
  • the polymer type antistatic agent has ions having a predetermined structure.
  • a binding salt as an antistatic agent, it is possible to impart excellent antistatic properties even when added in a small amount to a thermoplastic resin, and water resistance against operations such as washing with water is also possible. It can be seen that a high and inexpensive antistatic agent is provided.
  • the polymer type is similar to the results in Tables 1 to 4.
  • an antistatic agent in combination with an ion-binding salt having a predetermined structure as an antistatic agent, it is possible to impart excellent antistatic properties even when added in a small amount to a thermoplastic resin. It can be seen that an inexpensive antistatic agent is provided.
  • the ion-binding salt used in this example does not have a halogen in the structure.
  • the ion-binding salt according to the present invention can be produced without using any halogen in the raw material if a synthesis method is selected. In such a case (that is, when an ion-binding salt that does not contain halogen is used), it is also suitably used in applications where the use of halogen is avoided, such as adhesive sheets and tapes for electronic members, etc. Therefore, it is preferable. That is, in a preferred embodiment of the present invention, the predetermined ion-binding salt does not contain a halogen.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème à la base de l'invention concerne un agent antistatique peu coûteux qui présente une résistance élevée à l'eau par rapport à des opérations telles que le rinçage et peut conférer une excellente propriété antistatique, même lorsqu'il est ajouté à une résine thermoplastique en une petite quantité. La solution porte sur un mélange d'un agent antistatique polymère et d'un sel de liaison d'ions représenté par la formule chimique (1) ou la formule chimique (2), utilisé comme agent antistatique pour des résines thermoplastiques. Dans la formule chimique (1), A représente un groupe alkylène en C2-4, linéaire ou ramifié, n représente un nombre entier de 0 à 50, Q1+ représente un ion d'ammonium secondaire ou un ion d'ammonium tertiaire et R1 représente : un groupe alkyle en C1–30, éventuellement substitué, qui est linéaire, ramifié ou cyclique ; un groupe aryle en C6–30 éventuellement substitué ; ou un groupe arylalkyle en C7-31 éventuellement substitué. Dans la formule chimique (2), A représente un groupe alkylène en C2-4, linéaire ou ramifié, Q2+ représente un ion d'ammonium secondaire ou un ion d'ammonium tertiaire et R2 représente : un groupe alkyle en C1–30, éventuellement substitué, qui est linéaire, ramifié ou cyclique ; un groupe aryle en C6–30 éventuellement substitué ; ou un groupe arylalkyle en C7-31 éventuellement substitué.
PCT/JP2015/083470 2014-11-28 2015-11-27 Agent antistatique pour une résine thermoplastique et composition de résine thermoplastique Ceased WO2016084954A1 (fr)

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WO2018212352A1 (fr) * 2017-05-19 2018-11-22 日本乳化剤株式会社 Agent antistatique de type revêtement et matériau polymère revêtu de celui-ci
WO2020045552A1 (fr) 2018-08-30 2020-03-05 デンカ株式会社 Composition de résine électroconductrice et article moulé constitué de celle-ci
CN111100417A (zh) * 2018-10-29 2020-05-05 合肥杰事杰新材料股份有限公司 一种抗冲增强防霉丙烯腈-丁二烯-苯乙烯共聚物材料及其制备方法
US11649314B2 (en) 2021-06-18 2023-05-16 Sanyo Chemical Industries, Ltd. Antistatic agent for thermoplastic resin
EP4137625A4 (fr) * 2021-07-05 2023-07-19 Sanyo Chemical Industries, Ltd. Agent antistatique
WO2023189132A1 (fr) 2022-03-30 2023-10-05 デンカ株式会社 Stratifié métallique de composition de résine conductrice

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Publication number Priority date Publication date Assignee Title
WO2018212352A1 (fr) * 2017-05-19 2018-11-22 日本乳化剤株式会社 Agent antistatique de type revêtement et matériau polymère revêtu de celui-ci
JPWO2018212352A1 (ja) * 2017-05-19 2020-03-26 日本乳化剤株式会社 塗布型帯電防止剤およびこれを塗布した高分子材料
JP7064486B2 (ja) 2017-05-19 2022-05-10 日本乳化剤株式会社 塗布型帯電防止剤およびこれを塗布した高分子材料
WO2020045552A1 (fr) 2018-08-30 2020-03-05 デンカ株式会社 Composition de résine électroconductrice et article moulé constitué de celle-ci
US12466956B2 (en) 2018-08-30 2025-11-11 Denka Company Limited Electroconductive resin composition and molded article of same
CN111100417A (zh) * 2018-10-29 2020-05-05 合肥杰事杰新材料股份有限公司 一种抗冲增强防霉丙烯腈-丁二烯-苯乙烯共聚物材料及其制备方法
US11649314B2 (en) 2021-06-18 2023-05-16 Sanyo Chemical Industries, Ltd. Antistatic agent for thermoplastic resin
EP4137625A4 (fr) * 2021-07-05 2023-07-19 Sanyo Chemical Industries, Ltd. Agent antistatique
WO2023189132A1 (fr) 2022-03-30 2023-10-05 デンカ株式会社 Stratifié métallique de composition de résine conductrice

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