WO2019151229A1 - Anti-static agent - Google Patents

Anti-static agent Download PDF

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Publication number
WO2019151229A1
WO2019151229A1 PCT/JP2019/002930 JP2019002930W WO2019151229A1 WO 2019151229 A1 WO2019151229 A1 WO 2019151229A1 JP 2019002930 W JP2019002930 W JP 2019002930W WO 2019151229 A1 WO2019151229 A1 WO 2019151229A1
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Prior art keywords
antistatic agent
ethyl
propyl
triethoxysilyl
general formula
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PCT/JP2019/002930
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French (fr)
Japanese (ja)
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角光 横田
晋一 門野
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マナック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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 containing a silicon-containing quaternary ammonium compound represented by the following general formula (1).
  • Synthetic resins can be produced at low cost and in large quantities from chemical raw materials such as petroleum, and because they are easy to mold, they are now used as raw materials for various daily necessities, industrial products, and medical products. Widely used.
  • a general characteristic of synthetic resins is that they have excellent insulating properties (dielectric properties).
  • dielectric properties dielectric properties
  • various problems such as discharge and dust collection occur. For example, a high voltage due to static electricity causes electric discharge, which may cause malfunction of electronic equipment and destruction of electronic components. Furthermore, since the charged object attracts dust and dust, it may cause a product defect in the manufacturing site of electronic devices and electronic components, and may impair the beauty and reduce the commercial value of daily necessities.
  • a surface resistivity of approximately 10 9 ⁇ or less for preventing charging of a resin.
  • a surfactant is prevented from being charged. Methods used as agents are known.
  • Surfactants are generally classified into cationic, anionic, nonionic and amphoteric, but the antistatic effect is said to have the highest cationicity (for example, see Non-Patent Document 1).
  • Antistatic agents are broadly classified into kneading molds that are melt-mixed in the resin and application molds that are diluted with water or an organic solvent and applied directly to the surface of the resin molding, depending on the application method to the resin.
  • the coating type does not need to consider the surface migration of the surfactant and is used regardless of the type of resin.
  • the coating mold can be used in a wide range of fields because an antistatic film can be directly formed on the surface of the resin molded body, and an antistatic effect can be obtained relatively quickly.
  • coating-type antistatic agents examples include anionic antistatic agents such as alkyl sulfonates having 10 to 20 carbon atoms and alkylaryl sulfonates, and lower ether glycols such as ethylene glycol ethyl ether.
  • An antistatic agent for example, see Patent Document 1
  • an antistatic agent containing an alkylene oxide adduct of an alkylamine having an alkyl group having 12 to 18 carbon atoms and an organic acid such as citric acid or lactic acid for example, Patent Document 1
  • an antistatic agent containing an imidazolium salt and a quaternary ammonium compound for example, see Patent Document 3).
  • an antibacterial agent composition and an antiviral agent composition containing a silicon-containing quaternary ammonium compound that is a silane coupling agent have been developed (see, for example, Patent Document 4).
  • Silane coupling agents that is, alkoxysilane compounds
  • surface modifiers when these compositions are applied to the surface of a resin molded body, the silane coupling agents in the composition become the target. It has been reported that it is immobilized and can exert antibacterial and antiviral effects for a long period of time.
  • an alkoxysilane compound having an alkoxysilane group and a betaine group in the molecule is excellent in hydrophilizing the surface of an inorganic material or an organic material, and is therefore useful as an antifogging agent or an antistatic agent.
  • an antistatic effect see, for example, Patent Document 5).
  • the antistatic agent has a problem that, when the surface of an object such as a resin molded body is washed with water or wiped off, the applied or surface-transferred antistatic agent is removed and the antistatic effect is impaired. was there. Therefore, when the subject of this invention is applied to objects, such as glass and a resin molding, a desired antistatic effect is acquired and it is stably fixed to the surface of objects, such as glass and a resin molding. It is to provide an antistatic agent.
  • the present inventors have found that a specific silicon-containing quaternary ammonium compound has an excellent antistatic effect, and when this is applied to a resin or a molded body thereof, the compound is stably immobilized and a desired The inventors have found that the antistatic effect can be exhibited, and completed the present invention. That is, the present invention is as follows.
  • R 1 represents a methyl group or an ethyl group
  • R 2 represents the following formula (2):
  • R 3 is an alkyl group having 1 to 4 carbon atoms,
  • X is a halogen atom,
  • m and n are each independently an integer of 1 to 4 and
  • R 1 is an ethyl group.
  • p is 1.
  • the antistatic agent of the present invention When the antistatic agent of the present invention is applied to an object such as a resin or a molded body thereof, an excellent antistatic effect can be obtained.
  • the antistatic agent of the present invention is applied to the surface of an object such as a resin molded body, or when molded after being kneaded into a resin, the silicon-containing quaternary that has been applied or migrated after kneading. Since the ammonium compound is stably immobilized on the surface of the object, the durability against cleaning and wiping is excellent. That is, according to the present invention, it is possible to provide an antistatic agent that has an excellent antistatic effect and is stably immobilized on the surface of an object such as a resin molded body.
  • Example 1 is a 1 H-NMR spectrum of the compound obtained in Example 1.
  • ⁇ Antistatic agent ⁇ Silicon-containing quaternary ammonium compound
  • the antistatic agent of the present invention has the following general formula (1):
  • R 1 represents a methyl group or an ethyl group
  • R 2 represents the following formula (2):
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • X is a halogen atom
  • m and n are each independently an integer of 1 to 4
  • R 1 is a methyl group or an ethyl group, preferably an ethyl group.
  • R 2 is preferably a monovalent group represented by the above formula (2) wherein n is an integer of 1 to 3, that is, a 3-hydroxypropyl group, a 2-hydroxyethyl group or a hydroxymethyl group, and more Preferably, n is 2 or 3, a monovalent group represented by the above formula (2), that is, a 3-hydroxypropyl group or a 2-hydroxyethyl group, and particularly preferably, n is 3. A monovalent group represented by (2), that is, a 3-hydroxypropyl group.
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes methyl, ethyl, propyl, i-propyl, butyl, s-butyl. Group, i-butyl group or t-butyl group.
  • R 3 is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • X is a halogen atom, that is, X ⁇ is a halide ion.
  • the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • the halide ion means a fluoride ion, a chloride ion, a bromide ion or an iodide ion.
  • X is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.
  • m is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3, and more preferably 3.
  • p is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
  • Preferable examples of the compound represented by the general formula (1) include the following compounds: N- (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride, N- (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride, N- (2-hydroxyethyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride, N, N-diethyl-N- (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride, N, N-diethyl-N- (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride, N, N-diethyl-N- (2-hydroxye
  • More preferable examples of the compound represented by the general formula (1) include the following compounds: N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride, N- [3- (triethoxysilyl) propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride, N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (3-hydroxypropyl) ammonium chloride, N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (2-hydroxyethyl) ammonium chloride, N- [3- (triethoxysilyl) propyl] -N, N-di (3-hydroxypropyl) -N-methylammonium chloride, N- [3- (triethoxysilyl)
  • More preferable examples of the compound represented by the general formula (1) include the following compounds: N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride, or N- [3- (triethoxysilyl) propyl] -N- (2-hydroxy Ethyl) -N, N-dimethylammonium chloride.
  • the silicon-containing quaternary ammonium compound represented by the general formula (1) contained in the antistatic agent of the present invention can be produced according to a known method.
  • a tertiary amine compound represented by the following formula (4) and a trialkoxysilane compound represented by the following formula (5) are optionally mixed with a solvent.
  • R 1 , R 2 , R 3 , X, m, and p are as defined above.
  • the compound represented by the above formula (4) is a known compound, which can be prepared from a commercially available reagent by a known production method, or 3- (dimethylamino) -1-propanol, 2- (dimethylamino) ethanol, It can be obtained as 2- (diethylamino) ethanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, triethanolamine, etc. from reagent suppliers such as Merck and Tokyo Chemical Industry Co., Ltd.
  • the compound represented by the above formula (5) is a known compound and can be prepared from a commercially available reagent by a known production method, or (3-bromopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane , (3-bromopropyl) triethoxysilane, (3-chloropropyl) triethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, etc., obtained from reagent suppliers such as Merck and Tokyo Chemical Industry Co., Ltd. it can.
  • the compound represented by the above formula (5) is used in an amount of 0.8 to 2.0 mol, preferably 0.9 to 1.2 mol, per 1 mol of the compound represented by the above formula (4).
  • the reaction solvent is not particularly limited as long as it can dissolve the compound represented by the above formula (4) and the compound represented by the above formula (5) and is inert to the reaction of both compounds.
  • methanol, ethanol, isopropyl Alcohol solvents such as alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, cyclopentanone, cyclohexanone; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran Ether solvents such as 1,4-dioxane and cyclopentyl methyl ether; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, ⁇ -butyrolactone and ⁇ -valerolactone; nitrile solvents such
  • the antistatic agent of the present invention includes a solvent, an antioxidant, a heat stabilizer, It may contain a light stabilizer, an ultraviolet absorber, a flame retardant, a plasticizer, a pigment, a dye, and the like.
  • the solvent is not particularly limited as long as it is a solvent that can uniformly dissolve or disperse the compound represented by the above general formula (1), and the material of the surface to which the antistatic agent of the present invention is applied or kneaded. Although it is appropriately selected depending on the properties of the resin, water, an organic solvent, or a mixture thereof is preferable because each step such as coating or kneading or drying can be easily performed.
  • the organic solvent include the solvents exemplified as the reaction solvent.
  • the organic solvent is preferably one or more solvents selected from water-soluble organic solvents, and the water-soluble organic solvent may be any one that is miscible with water at 20 ° C. at an arbitrary ratio.
  • water-soluble organic solvent examples include methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol, nitromethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methyl.
  • the concentration of the compound represented by the general formula (1) ranges from 0.1% by weight to 90% by weight. Preferably, it is in the range of 1% to 80% by weight.
  • the solvent the reaction solvent used in the reaction of the compound represented by the above formula (4) and the compound represented by the above formula (5) may be used as it is or after adjusting the concentration appropriately.
  • the compound represented by the general formula (1) includes a quaternary ammonium salt structure and a trimethoxysilane or triethoxysilane structure.
  • the quaternary ammonium salt structure is the same structure as the cationic surfactant and is considered to exhibit an antistatic effect.
  • the trimethoxysilane or triethoxysilane structural portion is chemically bonded and fixed to a material (for example, glass, synthetic resin, etc.), for example, an object coated with the antistatic agent of the present invention.
  • the surface is covered with the structure portion exhibiting the above-mentioned antistatic effect, and the antistatic effect for a certain period can be maintained.
  • antistatic effect means that the surface resistance value of the target is suppressed to 1/10 or less, preferably 1/50 or less, more preferably 1/100 or less, before applying the antistatic agent. It means to do.
  • the target to which the antistatic agent of the present invention is applied is not particularly limited as long as it is charged, and examples thereof include glass, metal, metal-containing compound or metalloid-containing compound, and resin.
  • the metal for example, aluminum, nickel titanium, stainless steel, etc.
  • the metal-containing compound or the semi-metal-containing compound is, for example, ceramic, silicon, which is a sintered body that is a metal oxide as a basic component and baked and hardened by heat treatment at high temperature.
  • Semiconductors such as, metal oxides or metalloid oxides (silicon oxide, alumina, etc.), metal carbides or metalloid carbides, metal nitrides or metalloid nitrides (silicon nitride, etc.), metal borides or metalloids
  • An inorganic solid material such as a molded body of an inorganic compound such as boride can be used.
  • the resin may be a natural resin or a derivative thereof, or a synthetic resin.
  • the natural resin or derivative thereof include cellulose, cellulose triacetate, nitrocellulose, and cellulose with dextran sulfate immobilized thereon.
  • the material to be applied may be one type or a combination of two or more types.
  • the antistatic agent of the present invention is applied.
  • examples of the form include various forms such as a film (sheet), a hollow product, an injection product, a woven fabric, and a nonwoven fabric. Can do.
  • the method for applying the antistatic agent to the surface of the resin molded body is not particularly limited, and examples thereof include a roll coating method, a roll brush method, a spray coating method, an air knife method, an impregnation method, and a curtain method. May be combined.
  • the present invention relates to an antistatic film having an antistatic agent containing a silicon-containing quaternary ammonium compound represented by the general formula (1).
  • the antistatic film of the present invention can be obtained, for example, by applying the antistatic agent of the present invention to at least a part of the surface of a film formed from the above-mentioned resin and drying the solvent as necessary. That is, the antistatic film of the present invention is preferably at least 50% of the surface area of the film, more preferably at least 70% of the surface area of the film, more preferably at least 80% of the surface area of the film, particularly preferably at least of the surface area of the film. 90% is provided with a coating layer of the antistatic agent of the present invention.
  • the antistatic film of the present invention may be obtained, for example, by kneading an antistatic agent into the above-mentioned resin, forming a film, and drying the solvent as necessary.
  • 3- (dimethylamino) The same operation was carried out except that 2- (dimethylamino) ethanol was used instead of -1-propanol to obtain 88.0 g of the target ethanol solution.
  • the content of the target product contained in this solution was 61.7% by weight.
  • Example 1 The ethanol solution (62.1% by weight) of the target product obtained in Example 1 was further diluted with ethanol to make the content of the target product 20% by weight. Next, a 70 mm ⁇ 50 mm, 4 mm thick glass plate was wiped off with methanol, and then the ethanol solution of Example 1 (20 wt%) and the methanol solution of Comparative Example 1 (20 wt%) were wet films using a coating bar. The coating was applied with a thickness of 2 ⁇ m. After drying at room temperature for 30 minutes, drying was further performed at 120 ° C. for 1 hour. The surface resistance value of the obtained coated glass and uncoated glass was measured under the following measurement conditions to examine the antistatic function. The results are shown in Table 1 below.
  • Example 3 The ethanol solution (62.1 wt%) of the target product obtained in Example 1 was further diluted with ethanol to make the content of the target product 6 wt%. Next, the ethanol solution (6% by weight) of Example 1 was spray-coated on a polyester film having a thickness of 100 ⁇ m (manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A4300). Thereafter, drying was performed at 80 ° C. for 2 minutes to obtain an antistatic film.
  • Example 4 In place of the ethanol solution of the target product obtained in Example 1 used in Example 3, the ethanol solution (61.7% by weight) of the target product obtained in Example 2 was used and diluted in the same manner. After setting the content of the target product to 6% by weight, spray coating was conducted to obtain an antistatic film in the same manner as in Example 3.
  • the antistatic agent of the present invention exhibits an excellent antistatic effect when applied to a resin or a molded body thereof.
  • the antistatic agent of the present invention is applied to the surface of an object such as a resin molded body, or a silicon-containing quaternary ammonium compound that has been applied or kneaded into a resin and then migrated to the surface after kneading. Is stably immobilized on the surface of the object, and is excellent in durability against cleaning and wiping. Therefore, it is particularly useful as an antistatic agent for resin products that are widely used as raw materials for various daily necessities, industrial products, and medical products.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention provides an anti-static agent which exhibits an excellent anti-static effect when used in a resin and is stably fixed to a surface of an object such as a resin molded product. This anti-static agent contains a silicon-containing quaternary ammonium compound represented by general formula (1) {in the formula, R1, R2, R3, X, m and p are as set forth in the description and claims}.

Description

帯電防止剤Antistatic agent
　本発明は、後述の一般式（１）で示されるケイ素含有第４級アンモニウム化合物を含む帯電防止剤に関する。 The present invention relates to an antistatic agent containing a silicon-containing quaternary ammonium compound represented by the following general formula (1).
　合成樹脂（プラスチック）は、石油などの化学原料から、安価にかつ大量に生産可能であり、また成形加工が容易であるため、現在では、各種日用品や工業分野、医療分野の製品などの原材料として幅広く用いられている。合成樹脂の一般的な特徴として、絶縁性（誘電性）に優れる点が挙げられるが、一方で、絶縁性による帯電の結果、放電や集塵などによる種々の問題が生じる。例えば、静電気による高電圧は放電を招き、電子機器の誤作動や電子部品の破壊を招く恐れがある。さらに帯電した物体は埃や塵を吸い寄せるため、電子機器や電子部品の製造現場において製品不良の原因となり得ると共に、日用品などにおいても、美観を損ね、商品価値を低下させ得る。 Synthetic resins (plastics) can be produced at low cost and in large quantities from chemical raw materials such as petroleum, and because they are easy to mold, they are now used as raw materials for various daily necessities, industrial products, and medical products. Widely used. A general characteristic of synthetic resins is that they have excellent insulating properties (dielectric properties). On the other hand, as a result of charging due to insulating properties, various problems such as discharge and dust collection occur. For example, a high voltage due to static electricity causes electric discharge, which may cause malfunction of electronic equipment and destruction of electronic components. Furthermore, since the charged object attracts dust and dust, it may cause a product defect in the manufacturing site of electronic devices and electronic components, and may impair the beauty and reduce the commercial value of daily necessities.
　通常、樹脂の帯電防止には、表面固有抵抗値をおおよそ１０９Ω以下とすることが望ましいとされており、合成樹脂における、このような帯電による問題を防ぐ手段として、界面活性剤を帯電防止剤として用いる方法が知られている。界面活性剤は、一般に、カチオン性、アニオン性、ノニオン性および両性に分類されるが、帯電防止効果はカチオン性が最も高いと言われている（例えば、非特許文献１参照）。 In general, it is desirable to have a surface resistivity of approximately 10 9 Ω or less for preventing charging of a resin. As a means for preventing problems caused by such charging in a synthetic resin, a surfactant is prevented from being charged. Methods used as agents are known. Surfactants are generally classified into cationic, anionic, nonionic and amphoteric, but the antistatic effect is said to have the highest cationicity (for example, see Non-Patent Document 1).
　帯電防止剤は、その樹脂への適用方法から、樹脂に溶融混合する練込型と、水や有機溶剤で希釈し樹脂成形体の表面に直接塗布する塗布型とに大別される。塗布型は、界面活性剤の表面移行を考慮する必要がなく、樹脂の種類を問わず用いられる。また塗布型は、樹脂成形体の表面に直接、帯電防止膜を形成でき、帯電防止効果が比較的即座に得られるので、幅広い分野で用いられる。そのような塗布型の帯電防止剤として、例えば、炭素数１０～２０のアルキルスルホン酸塩、アルキルアリールスルホン酸塩などのアニオン系帯電防止剤と、エチレングリコールエチルエーテルなどの低級エーテルグリコールとを含む帯電防止剤（例えば、特許文献１参照）、アルキル基の炭素数が１２～１８のアルキルアミンのアルキレンオキシド付加体と、クエン酸、乳酸などの有機酸とを含む帯電防止剤（例えば、特許文献２参照）、およびイミダゾリウム塩と、第４級アンモニウム化合物とを含む帯電防止剤（例えば、特許文献３参照）などが知られている。 Antistatic agents are broadly classified into kneading molds that are melt-mixed in the resin and application molds that are diluted with water or an organic solvent and applied directly to the surface of the resin molding, depending on the application method to the resin. The coating type does not need to consider the surface migration of the surfactant and is used regardless of the type of resin. The coating mold can be used in a wide range of fields because an antistatic film can be directly formed on the surface of the resin molded body, and an antistatic effect can be obtained relatively quickly. Examples of such coating-type antistatic agents include anionic antistatic agents such as alkyl sulfonates having 10 to 20 carbon atoms and alkylaryl sulfonates, and lower ether glycols such as ethylene glycol ethyl ether. An antistatic agent (for example, see Patent Document 1), an antistatic agent containing an alkylene oxide adduct of an alkylamine having an alkyl group having 12 to 18 carbon atoms and an organic acid such as citric acid or lactic acid (for example, Patent Document 1) 2), and an antistatic agent containing an imidazolium salt and a quaternary ammonium compound (for example, see Patent Document 3).
　一方で、シランカップリング剤であるケイ素含有第４級アンモニウム化合物を含む抗菌剤組成物および抗ウイルス剤組成物が開発されている（例えば、特許文献４参照）。シランカップリング剤（すなわち、アルコキシシラン化合物）は、表面改質剤としても知られており、これらの組成物を樹脂成形体の表面に塗布すると、組成物中のシランカップリング剤が対象物に固定化され、抗菌および抗ウイルス効果を長期間発揮できることが報告されている。また、分子内にアルコキシシラン基とベタイン基とを有するアルコキシシラン化合物が、無機材料または有機材料の表面を親水化することに優れることが開示され、したがって防曇剤、帯電防止剤としても有用である旨が言及されているが、帯電防止効果について具体的な開示は無い（例えば、特許文献５参照）。 On the other hand, an antibacterial agent composition and an antiviral agent composition containing a silicon-containing quaternary ammonium compound that is a silane coupling agent have been developed (see, for example, Patent Document 4). Silane coupling agents (that is, alkoxysilane compounds) are also known as surface modifiers, and when these compositions are applied to the surface of a resin molded body, the silane coupling agents in the composition become the target. It has been reported that it is immobilized and can exert antibacterial and antiviral effects for a long period of time. Further, it has been disclosed that an alkoxysilane compound having an alkoxysilane group and a betaine group in the molecule is excellent in hydrophilizing the surface of an inorganic material or an organic material, and is therefore useful as an antifogging agent or an antistatic agent. Although there is a mention of this, there is no specific disclosure regarding the antistatic effect (see, for example, Patent Document 5).
特開平４－２８７２８号公報Japanese Patent Laid-Open No. 4-28728 特開２００１－１１５１４９号公報JP 2001-115149 A 特開２０１０－１２１０９３号公報JP 2010-121093 A 特開２００７－３１２９０号公報JP 2007-31290 A 特開平０７－１０１９６５号公報Japanese Patent Application Laid-Open No. 07-101965
　界面活性剤を帯電防止剤として用いる従来の方法では、所望の帯電防止効果が得られない場合があった。また、帯電防止剤は、樹脂成形体などの対象の表面が水で洗浄されたり、拭き取られたりすると、塗布されたまたは表面移行した帯電防止剤が除去され、帯電防止効果が損なわれるという問題があった。したがって、本発明の課題は、ガラスや樹脂成形体などの対象に適用した場合に、所望の帯電防止効果が得られ、かつガラスや樹脂成形体などの対象の表面に安定的に固定化される帯電防止剤を提供することである。 In the conventional method using a surfactant as an antistatic agent, a desired antistatic effect may not be obtained. In addition, the antistatic agent has a problem that, when the surface of an object such as a resin molded body is washed with water or wiped off, the applied or surface-transferred antistatic agent is removed and the antistatic effect is impaired. was there. Therefore, when the subject of this invention is applied to objects, such as glass and a resin molding, a desired antistatic effect is acquired and it is stably fixed to the surface of objects, such as glass and a resin molding. It is to provide an antistatic agent.
　本発明者らは、特定のケイ素含有第４級アンモニウム化合物が、優れた帯電防止効果を有し、これを樹脂またはその成形体に適用すると、化合物が安定的に固定化されると共に、所望の帯電防止効果を発揮できることを見出し、本発明を完成させた。
　すなわち、本発明は以下のとおりである。
［１］　下記一般式（１）：
Figure JPOXMLDOC01-appb-C000004
｛式中、Ｒ１はメチル基またはエチル基であり、Ｒ２は下記式（２）：
Figure JPOXMLDOC01-appb-C000005
で表わされる一価の基であり、Ｒ３は炭素数１～４のアルキル基であり、Ｘはハロゲン原子であり、ｍおよびｎは、互いに独立して、１～４の整数であり、ｐは１～３の整数である｝
で示されるケイ素含有第４級アンモニウム化合物を含む、帯電防止剤。
［２］　前記一般式（１）において、Ｒ１がエチル基である、上記［１］記載の帯電防止剤。
［３］　前記一般式（１）において、ｐが１である、上記［１］または［２］記載の帯電防止剤。
［４］　前記一般式（１）において、ｍが３である、上記［１］～［３］のいずれか記載の帯電防止剤。
［５］　前記一般式（１）において、Ｘが塩素原子である、上記［１］～［４］のいずれか記載の帯電防止剤。
［６］　前記一般式（１）の化合物が、Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリドまたはＮ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリドである、上記［１］～［５］のいずれか記載の帯電防止剤。
［７］　上記［１］～［６］のいずれか記載の帯電防止剤を有する帯電防止フィルム。
［８］　下記式（３）：
Figure JPOXMLDOC01-appb-C000006
で示される化合物。 The present inventors have found that a specific silicon-containing quaternary ammonium compound has an excellent antistatic effect, and when this is applied to a resin or a molded body thereof, the compound is stably immobilized and a desired The inventors have found that the antistatic effect can be exhibited, and completed the present invention.
That is, the present invention is as follows.
[1] The following general formula (1):
Figure JPOXMLDOC01-appb-C000004
{In the formula, R 1 represents a methyl group or an ethyl group, and R 2 represents the following formula (2):
Figure JPOXMLDOC01-appb-C000005
R 3 is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom, m and n are each independently an integer of 1 to 4 and p Is an integer from 1 to 3}
The antistatic agent containing the silicon containing quaternary ammonium compound shown by these.
[2] The antistatic agent according to the above [1], wherein in the general formula (1), R 1 is an ethyl group.
[3] The antistatic agent according to the above [1] or [2], wherein in the general formula (1), p is 1.
[4] The antistatic agent according to any one of [1] to [3], wherein m is 3 in the general formula (1).
[5] The antistatic agent according to any one of the above [1] to [4], wherein in the general formula (1), X is a chlorine atom.
[6] The compound of the general formula (1) is N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride or N- [3- (tri The antistatic agent according to any one of the above [1] to [5], which is ethoxysilyl) propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride.
[7] An antistatic film comprising the antistatic agent according to any one of [1] to [6].
[8] The following formula (3):
Figure JPOXMLDOC01-appb-C000006
A compound represented by
　本発明の帯電防止剤は、樹脂またはその成形体などの対象に適用すると、優れた帯電防止効果が得られる。また、本発明の帯電防止剤は、例えば、樹脂成形体などの対象の表面に塗布するか、または樹脂に練り込んだ後に成形すると、塗布されたまたは練り込み後に表面移行したケイ素含有第４級アンモニウム化合物が対象の表面に安定的に固定化されるため、洗浄や拭き取りに対する耐久性に優れる。すなわち、本発明により、優れた帯電防止効果を有し、かつ樹脂成形体などの対象の表面に安定的に固定化される帯電防止剤を提供できる。 When the antistatic agent of the present invention is applied to an object such as a resin or a molded body thereof, an excellent antistatic effect can be obtained. In addition, the antistatic agent of the present invention is applied to the surface of an object such as a resin molded body, or when molded after being kneaded into a resin, the silicon-containing quaternary that has been applied or migrated after kneading. Since the ammonium compound is stably immobilized on the surface of the object, the durability against cleaning and wiping is excellent. That is, according to the present invention, it is possible to provide an antistatic agent that has an excellent antistatic effect and is stably immobilized on the surface of an object such as a resin molded body.
実施例１で得られた化合物の１Ｈ－ＮＭＲスペクトルである。1 is a 1 H-NMR spectrum of the compound obtained in Example 1.
　以下に本発明の実施の態様を詳細に説明する。
≪帯電防止剤≫
（ケイ素含有第４級アンモニウム化合物）
　本発明の帯電防止剤は、下記一般式（１）： Hereinafter, embodiments of the present invention will be described in detail.
≪Antistatic agent≫
(Silicon-containing quaternary ammonium compound)
The antistatic agent of the present invention has the following general formula (1):
Figure JPOXMLDOC01-appb-C000007
｛式中、Ｒ１はメチル基またはエチル基であり、Ｒ２は下記式（２）：
Figure JPOXMLDOC01-appb-C000007
{In the formula, R 1 represents a methyl group or an ethyl group, and R 2 represents the following formula (2):
Figure JPOXMLDOC01-appb-C000008
で表わされる一価の基であり、Ｒ３は炭素数１～４のアルキル基であり、Ｘはハロゲン原子であり、ｍおよびｎは、互いに独立して、１～４の整数であり、ｐは１～３の整数である｝で示されるケイ素含有第４級アンモニウム化合物を含む。
Figure JPOXMLDOC01-appb-C000008
R 3 is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom, m and n are each independently an integer of 1 to 4 and p Is an integer of 1 to 3, including a silicon-containing quaternary ammonium compound.
　上記一般式（１）で示される化合物において、Ｒ１はメチル基またはエチル基であり、好ましくはエチル基である。 In the compound represented by the general formula (1), R 1 is a methyl group or an ethyl group, preferably an ethyl group.
　上記一般式（１）で示される化合物において、Ｒ２は上記式（２）で表される一価の基であり、ｎは、１～４の整数である。すなわち、Ｒ２は、４－ヒドロキシブチル基（ｎ＝４）、３－ヒドロキシプロピル基（ｎ＝３）、２－ヒドロキシエチル基（ｎ＝２）またはヒドロキシメチル基（ｎ＝１）である。Ｒ２は、好ましくはｎが１～３の整数である、上記式（２）で表される一価の基、すなわち３－ヒドロキシプロピル基、２－ヒドロキシエチル基またはヒドロキシメチル基であり、より好ましくはｎが２または３である、上記式（２）で表される一価の基、すなわち３－ヒドロキシプロピル基または２－ヒドロキシエチル基であり、特に好ましくはｎが３である、上記式（２）で表される一価の基、すなわち３－ヒドロキシプロピル基である。 In the compound represented by the general formula (1), R 2 is a monovalent group represented by the above formula (2), and n is an integer of 1 to 4. That is, R 2 is a 4-hydroxybutyl group (n = 4), a 3-hydroxypropyl group (n = 3), a 2-hydroxyethyl group (n = 2), or a hydroxymethyl group (n = 1). R 2 is preferably a monovalent group represented by the above formula (2) wherein n is an integer of 1 to 3, that is, a 3-hydroxypropyl group, a 2-hydroxyethyl group or a hydroxymethyl group, and more Preferably, n is 2 or 3, a monovalent group represented by the above formula (2), that is, a 3-hydroxypropyl group or a 2-hydroxyethyl group, and particularly preferably, n is 3. A monovalent group represented by (2), that is, a 3-hydroxypropyl group.
　上記一般式（１）で示される化合物において、Ｒ３は炭素数１～４のアルキル基である。ここで、炭素数１～４のアルキル基は、直鎖状または分岐鎖状であってよく、具体的には、メチル基、エチル基、プロピル基、ｉ－プロピル基、ブチル基、ｓ－ブチル基、ｉ－ブチル基またはｔ－ブチル基が挙げられる。Ｒ３は、好ましくはメチル基、エチル基またはプロピル基であり、より好ましくはメチル基またはエチル基であり、特に好ましくはメチル基である。 In the compound represented by the general formula (1), R 3 is an alkyl group having 1 to 4 carbon atoms. Here, the alkyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes methyl, ethyl, propyl, i-propyl, butyl, s-butyl. Group, i-butyl group or t-butyl group. R 3 is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
　上記一般式（１）で示される化合物において、Ｘはハロゲン原子であり、すなわちＸ－は、ハロゲン化物イオンである。ここで、ハロゲン原子は、フッ素原子、塩素原子、臭素原子またはヨウ素原子を意味し、ハロゲン化物イオンは、フッ化物イオン、塩化物イオン、臭化物イオンまたはヨウ化物イオンを意味する。Ｘは、好ましくは塩素原子または臭素原子であり、より好ましくは塩素原子である。 In the compound represented by the above general formula (1), X is a halogen atom, that is, X − is a halide ion. Here, the halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the halide ion means a fluoride ion, a chloride ion, a bromide ion or an iodide ion. X is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.
　上記一般式（１）で示される化合物において、ｍは１～４の整数であり、好ましくは１～３の整数であり、より好ましくは２または３であり、より好ましくは３である。 In the compound represented by the general formula (1), m is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3, and more preferably 3.
　上記一般式（１）で示される化合物において、ｐは１～３の整数であり、好ましくは１または２であり、より好ましくは１である。 In the compound represented by the general formula (1), p is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
　上記一般式（１）で示される化合物の好ましい例としては、以下の化合物が挙げられる：
　Ｎ－（４－ヒドロキシブチル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－（３－ヒドロキシプロピル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－（２－ヒドロキシエチル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（４－ヒドロキシブチル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（３－ヒドロキシプロピル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（２－ヒドロキシエチル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ－（４－ヒドロキシブチル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－（３－ヒドロキシプロピル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－（２－ヒドロキシエチル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（４－ヒドロキシブチル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（３－ヒドロキシプロピル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ，Ｎ－ジエチル－Ｎ－（２－ヒドロキシエチル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－［３－（トリメトキシシリル）プロピル］アンモニウムクロリド、
　Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－［２－（トリメトキシシリル）エチル］－Ｎ－メチルアンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ－エチル－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－［２－（トリメトキシシリル）エチル］アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（４－ヒドロキシブチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジエチル－Ｎ－（４－ヒドロキシブチル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジエチル－Ｎ－（３－ヒドロキシプロピル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジエチル－Ｎ－（２－ヒドロキシエチル）アンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－（４－ヒドロキシブチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジエチル－Ｎ－（４－ヒドロキシブチル）アンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジエチル－Ｎ－（３－ヒドロキシプロピル）アンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジエチル－Ｎ－（２－ヒドロキシエチル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－エチル－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－エチル－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－エチル－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）アンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－エチル－Ｎ，Ｎ－ジ（４－ヒドロキシブチル）アンモニウムクロリド、
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－エチル－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）アンモニウムクロリド、または
　Ｎ－［２－（トリエトキシシリル）エチル］－Ｎ－エチル－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）アンモニウムクロリド。 Preferable examples of the compound represented by the general formula (1) include the following compounds:
N- (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride,
N- (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride,
N- (2-hydroxyethyl) -N- [3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride,
N, N-diethyl-N- (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N, N-diethyl-N- (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N, N-diethyl-N- (2-hydroxyethyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N- (4-hydroxybutyl) -N- [2- (trimethoxysilyl) ethyl] -N, N-dimethylammonium chloride,
N- (3-hydroxypropyl) -N- [2- (trimethoxysilyl) ethyl] -N, N-dimethylammonium chloride,
N- (2-hydroxyethyl) -N- [2- (trimethoxysilyl) ethyl] -N, N-dimethylammonium chloride,
N, N-diethyl-N- (4-hydroxybutyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N, N-diethyl-N- (3-hydroxypropyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N, N-diethyl-N- (2-hydroxyethyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N, N-di (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] -N-methylammonium chloride,
N, N-di (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] -N-methylammonium chloride,
N, N-di (2-hydroxyethyl) -N- [3- (trimethoxysilyl) propyl] -N-methylammonium chloride,
N-ethyl-N, N-di (4-hydroxybutyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N-ethyl-N, N-di (3-hydroxypropyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N-ethyl-N, N-di (2-hydroxyethyl) -N- [3- (trimethoxysilyl) propyl] ammonium chloride,
N, N-di (4-hydroxybutyl) -N- [2- (trimethoxysilyl) ethyl] -N-methylammonium chloride,
N, N-di (3-hydroxypropyl) -N- [2- (trimethoxysilyl) ethyl] -N-methylammonium chloride,
N, N-di (2-hydroxyethyl) -N- [2- (trimethoxysilyl) ethyl] -N-methylammonium chloride,
N-ethyl-N, N-di (4-hydroxybutyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N-ethyl-N, N-di (3-hydroxypropyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N-ethyl-N, N-di (2-hydroxyethyl) -N- [2- (trimethoxysilyl) ethyl] ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N- (4-hydroxybutyl) -N, N-dimethylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (4-hydroxybutyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (3-hydroxypropyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (2-hydroxyethyl) ammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N- (4-hydroxybutyl) -N, N-dimethylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-diethyl-N- (4-hydroxybutyl) ammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-diethyl-N- (3-hydroxypropyl) ammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-diethyl-N- (2-hydroxyethyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-di (4-hydroxybutyl) -N-methylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-di (3-hydroxypropyl) -N-methylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-di (2-hydroxyethyl) -N-methylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N-ethyl-N, N-di (4-hydroxybutyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N-ethyl-N, N-di (3-hydroxypropyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N-ethyl-N, N-di (2-hydroxyethyl) ammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-di (4-hydroxybutyl) -N-methylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-di (3-hydroxypropyl) -N-methylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N, N-di (2-hydroxyethyl) -N-methylammonium chloride,
N- [2- (triethoxysilyl) ethyl] -N-ethyl-N, N-di (4-hydroxybutyl) ammonium chloride;
N- [2- (triethoxysilyl) ethyl] -N-ethyl-N, N-di (3-hydroxypropyl) ammonium chloride, or N- [2- (triethoxysilyl) ethyl] -N-ethyl-N , N-Di (2-hydroxyethyl) ammonium chloride.
　上記一般式（１）で示される化合物のより好ましい例としては、以下の化合物が挙げられる：
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジエチル－Ｎ－（３－ヒドロキシプロピル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジエチル－Ｎ－（２－ヒドロキシエチル）アンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－Ｎ－メチルアンモニウムクロリド、
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－エチル－Ｎ，Ｎ－ジ（３－ヒドロキシプロピル）アンモニウムクロリド、または
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－エチル－Ｎ，Ｎ－ジ（２－ヒドロキシエチル）アンモニウムクロリド。 More preferable examples of the compound represented by the general formula (1) include the following compounds:
N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (3-hydroxypropyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-diethyl-N- (2-hydroxyethyl) ammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-di (3-hydroxypropyl) -N-methylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N, N-di (2-hydroxyethyl) -N-methylammonium chloride,
N- [3- (triethoxysilyl) propyl] -N-ethyl-N, N-di (3-hydroxypropyl) ammonium chloride or N- [3- (triethoxysilyl) propyl] -N-ethyl-N , N-Di (2-hydroxyethyl) ammonium chloride.
　上記一般式（１）で示される化合物のさらに好ましい例としては、以下の化合物が挙げられる：
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド、または
　Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド。 More preferable examples of the compound represented by the general formula (1) include the following compounds:
N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride, or N- [3- (triethoxysilyl) propyl] -N- (2-hydroxy Ethyl) -N, N-dimethylammonium chloride.
　上記一般式（１）で示される化合物の中でも、下記式（３）：
Figure JPOXMLDOC01-appb-C000009
で示される化合物（すなわち、Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド）は、帯電防止効果に優れる新規化合物であるため、特に好ましい。 Among the compounds represented by the general formula (1), the following formula (3):
Figure JPOXMLDOC01-appb-C000009
(Ie, N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride) is a novel compound having an excellent antistatic effect, Particularly preferred.
（ケイ素含有第４級アンモニウム化合物の製造方法）
　本発明の帯電防止剤に含まれる、上記一般式（１）で示されるケイ素含有第４級アンモニウム化合物は、公知の方法に従い製造できる。典型的には、後述の実施例に記載されているように、下記式（４）で示される第３級アミン化合物と、下記式（５）で示されるトリアルコキシシラン化合物とを、場合により溶媒の存在下、０℃～２００℃の温度で、１～４８時間反応させることにより製造できる。 (Method for producing silicon-containing quaternary ammonium compound)
The silicon-containing quaternary ammonium compound represented by the general formula (1) contained in the antistatic agent of the present invention can be produced according to a known method. Typically, as described in Examples below, a tertiary amine compound represented by the following formula (4) and a trialkoxysilane compound represented by the following formula (5) are optionally mixed with a solvent. Can be produced by reacting at a temperature of 0 ° C. to 200 ° C. for 1 to 48 hours.
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘ、ｍおよびｐは、上記と同義である。）
Figure JPOXMLDOC01-appb-C000010
(In the formula, R 1 , R 2 , R 3 , X, m, and p are as defined above.)
　上記式（４）で示される化合物は、公知の化合物であり、市販の試薬から公知の製造方法により調製できるか、あるいは３－（ジメチルアミノ）－１－プロパノール、２－（ジメチルアミノ）エタノール、２－（ジエチルアミノ）エタノール、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－ブチルジエタノールアミン、トリエタノールアミンなどとして、Ｍｅｒｃｋや東京化成工業（株）などの試薬供給業者から入手できる。 The compound represented by the above formula (4) is a known compound, which can be prepared from a commercially available reagent by a known production method, or 3- (dimethylamino) -1-propanol, 2- (dimethylamino) ethanol, It can be obtained as 2- (diethylamino) ethanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, triethanolamine, etc. from reagent suppliers such as Merck and Tokyo Chemical Industry Co., Ltd.
　上記式（５）で示される化合物は、公知の化合物であり、市販の試薬から公知の製造方法により調製できるか、あるいは（３－ブロモプロピル）トリメトキシシラン、（３－クロロプロピル）トリメトキシシラン、（３－ブロモプロピル）トリエトキシシラン、（３－クロロプロピル）トリエトキシシラン、クロロメチルトリメトキシシラン、クロロメチルトリエトキシシランなどとして、Ｍｅｒｃｋや東京化成工業（株）などの試薬供給業者から入手できる。上記式（５）で示される化合物は、上記式（４）で示される化合物１モルに対して、０．８～２．０モル、好ましくは０．９～１．２モル用いられる。 The compound represented by the above formula (5) is a known compound and can be prepared from a commercially available reagent by a known production method, or (3-bromopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane , (3-bromopropyl) triethoxysilane, (3-chloropropyl) triethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, etc., obtained from reagent suppliers such as Merck and Tokyo Chemical Industry Co., Ltd. it can. The compound represented by the above formula (5) is used in an amount of 0.8 to 2.0 mol, preferably 0.9 to 1.2 mol, per 1 mol of the compound represented by the above formula (4).
　反応溶媒は、上記式（４）で示される化合物および上記式（５）で示される化合物を溶解でき、かつ両化合物の反応に不活性であれば特に制限はなく、例えば、メタノール、エタノール、イソプロピルアルコール、ｔ－ブチルアルコール、ｎ－ブチルアルコール、ｔ－アミルアルコールなどのアルコール溶剤；アセトン、メチルエチルケトン、エチルイソブチルケトン、シクロペンタノン、シクロヘキサノンなどのケトン溶剤；ジエチルエーテル、１，２－ジメトキシエタン、テトラヒドロフラン、１，４－ジオキサン、シクロペンチルメチルエーテルなどのエテール溶剤；酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸エチル、γ―ブチロラクトン、γ―バレロラクトンなどのエステル溶剤；アセトニトリルなどのニトリル溶剤、ジメチルアセトアミド、Ｎ－メチルピロリドンなどのアミド溶剤；ニトロメタンなどのニトロアルカン溶剤；ジメチルスルホキシドなどの含硫黄溶剤；酢酸などのアルカン酸溶剤；およびピコリン、ピリジンなどの含窒素溶剤からなる群より選ばれる１種以上の溶剤を挙げることができる。 The reaction solvent is not particularly limited as long as it can dissolve the compound represented by the above formula (4) and the compound represented by the above formula (5) and is inert to the reaction of both compounds. For example, methanol, ethanol, isopropyl Alcohol solvents such as alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, cyclopentanone, cyclohexanone; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran Ether solvents such as 1,4-dioxane and cyclopentyl methyl ether; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, γ-butyrolactone and γ-valerolactone; nitrile solvents such as acetonitrile 1 selected from the group consisting of amide solvents such as methylacetamide and N-methylpyrrolidone; nitroalkane solvents such as nitromethane; sulfur-containing solvents such as dimethyl sulfoxide; alkanoic acid solvents such as acetic acid; and nitrogen-containing solvents such as picoline and pyridine. Mention may be made of more than one type of solvent.
（帯電防止剤の任意成分）
　本発明の帯電防止剤は、上述の一般式（１）で示されるケイ素含有第４級アンモニウム化合物に加えて、本発明の効果を損なわない範囲で、溶剤、酸化防止剤、熱安定化剤、光安定化剤、紫外線吸収剤、難燃剤、可塑剤、顔料、染料などを含んでもよい。 (Optional component of antistatic agent)
In addition to the silicon-containing quaternary ammonium compound represented by the above general formula (1), the antistatic agent of the present invention includes a solvent, an antioxidant, a heat stabilizer, It may contain a light stabilizer, an ultraviolet absorber, a flame retardant, a plasticizer, a pigment, a dye, and the like.
　溶剤としては、上述の一般式（１）で示される化合物を均一に溶解または分散できる溶剤であれば特に制限はなく、本発明の帯電防止剤が塗布される対象の表面の材質または練り込まれる樹脂の性質に応じて、適宜選択されるが、塗布または練り込み、乾燥などの各工程を容易に行えることから、水、有機溶剤またはその混合物が好ましい。有機溶剤としては、反応溶媒として例示した溶剤を挙げることができる。さらに有機溶剤は、好ましくは水溶性有機溶剤から選ばれる１種以上の溶剤であり、ここで水溶性有機溶剤とは、２０℃において水と任意の比率で混和するものであればよい。 The solvent is not particularly limited as long as it is a solvent that can uniformly dissolve or disperse the compound represented by the above general formula (1), and the material of the surface to which the antistatic agent of the present invention is applied or kneaded. Although it is appropriately selected depending on the properties of the resin, water, an organic solvent, or a mixture thereof is preferable because each step such as coating or kneading or drying can be easily performed. Examples of the organic solvent include the solvents exemplified as the reaction solvent. Furthermore, the organic solvent is preferably one or more solvents selected from water-soluble organic solvents, and the water-soluble organic solvent may be any one that is miscible with water at 20 ° C. at an arbitrary ratio.
　水溶性有機溶剤は、例えば、メタノール、エタノール、１，２－プロパンジオール、イソプロピルアルコール、ｔ－ブチルアルコール、ｎ－ブチルアルコール、ｔ－アミルアルコール、ニトロメタン、アセトニトリル、ジメチルスルホキシド、ジメチルホルムアミド、Ｎ－メチルピロリドン、アセトン、酢酸、ピリジン、１，２－ジメトキシエタン、テトラヒドロフラン及び１，４－ジオキサンからなる群より選ばれる１種以上の溶剤である。したがって、帯電防止剤の溶剤としては、水、水溶性有機溶剤またはその混合物がより好ましい。 Examples of the water-soluble organic solvent include methanol, ethanol, 1,2-propanediol, isopropyl alcohol, t-butyl alcohol, n-butyl alcohol, t-amyl alcohol, nitromethane, acetonitrile, dimethyl sulfoxide, dimethylformamide, and N-methyl. One or more solvents selected from the group consisting of pyrrolidone, acetone, acetic acid, pyridine, 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane. Therefore, as the solvent for the antistatic agent, water, a water-soluble organic solvent or a mixture thereof is more preferable.
　本発明の帯電防止剤が、一般式（１）で示される化合物に加えて、溶剤を含む場合、一般式（１）で示される化合物の濃度は、０．１重量％～９０重量％の範囲であってよく、好ましくは１重量％～８０重量％の範囲である。また溶剤は、上記式（４）で示される化合物と、上記式（５）で示される化合物との反応で用いた反応溶媒を、そのまま、または適宜濃度を調整して、使用してもよい。 When the antistatic agent of the present invention contains a solvent in addition to the compound represented by the general formula (1), the concentration of the compound represented by the general formula (1) ranges from 0.1% by weight to 90% by weight. Preferably, it is in the range of 1% to 80% by weight. As the solvent, the reaction solvent used in the reaction of the compound represented by the above formula (4) and the compound represented by the above formula (5) may be used as it is or after adjusting the concentration appropriately.
（帯電防止剤の用途）
　上記一般式（１）で示される化合物は、第４級アンモニウム塩構造と、トリメトキシシランまたはトリエトキシシラン構造とを含んでいる。第４級アンモニウム塩構造は、カチオン性界面活性剤と同様の構造であり、帯電防止効果を発揮すると考えられる。一方、トリメトキシシランまたはトリエトキシシラン構造部分は、素材（例えば、ガラス、合成樹脂など）に化学的に結合して固定化されるため、例えば、本発明の帯電防止剤を塗布された対象物は、上記帯電防止効果を奏する構造部分により表面を覆われ、一定期間の帯電防止効果を保持できる。ここで、「帯電防止効果」とは、対象の表面抵抗値を、帯電防止剤を塗布する前の１０分の１以下、好ましくは５０分の１以下、より好ましくは１００分の１以下に抑制することを意味する。 (Use of antistatic agent)
The compound represented by the general formula (1) includes a quaternary ammonium salt structure and a trimethoxysilane or triethoxysilane structure. The quaternary ammonium salt structure is the same structure as the cationic surfactant and is considered to exhibit an antistatic effect. On the other hand, since the trimethoxysilane or triethoxysilane structural portion is chemically bonded and fixed to a material (for example, glass, synthetic resin, etc.), for example, an object coated with the antistatic agent of the present invention. The surface is covered with the structure portion exhibiting the above-mentioned antistatic effect, and the antistatic effect for a certain period can be maintained. Here, “antistatic effect” means that the surface resistance value of the target is suppressed to 1/10 or less, preferably 1/50 or less, more preferably 1/100 or less, before applying the antistatic agent. It means to do.
　本発明の帯電防止剤を適用する対象としては、帯電するものであれば特に制限はなく、例えば、ガラス、金属、金属含有化合物もしくは半金属含有化合物、または樹脂を挙げることができる。金属としては、例えば、アルミニウム、ニッケルチタン、ステンレスなど、金属含有化合物もしくは半金属含有化合物は、例えば、基本成分が金属酸化物で、高温での熱処理によって焼き固めた焼結体であるセラミックス、シリコンのような半導体、金属酸化物もしくは半金属酸化物（シリコン酸化物、アルミナなど）、金属炭化物もしくは半金属炭化物、金属窒化物もしくは半金属窒化物（シリコン窒化物など）、金属ホウ化物もしくは半金属ホウ化物などの無機化合物の成形体などの無機固体材料が挙げられる。 The target to which the antistatic agent of the present invention is applied is not particularly limited as long as it is charged, and examples thereof include glass, metal, metal-containing compound or metalloid-containing compound, and resin. As the metal, for example, aluminum, nickel titanium, stainless steel, etc., the metal-containing compound or the semi-metal-containing compound is, for example, ceramic, silicon, which is a sintered body that is a metal oxide as a basic component and baked and hardened by heat treatment at high temperature. Semiconductors such as, metal oxides or metalloid oxides (silicon oxide, alumina, etc.), metal carbides or metalloid carbides, metal nitrides or metalloid nitrides (silicon nitride, etc.), metal borides or metalloids An inorganic solid material such as a molded body of an inorganic compound such as boride can be used.
　樹脂としては、天然樹脂若しくはその誘導体、又は合成樹脂いずれでもよく、天然樹脂若しくはその誘導体としては、セルロース、三酢酸セルロース、ニトロセルロース、デキストラン硫酸を固定化したセルロースなど、合成樹脂としてはポリアミド、ポリアクリロニトリル、ポリスチレン、ポリスルホン、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリビニルアルコール、ポリウレタン、エチレン・ビニルアルコール共重合体、ポリエチレン、ポリエステル、ポリプロピレン、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリカーボネート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリテトラフルオロエチレン、超高分子量ポリエチレン、ポリジメチルシロキサン、アクリロニトリル－ブタジエン－スチレン樹脂又はテフロン（登録商標）などが挙げられる。適用対象の材質は、１種類であっても２種類以上の組み合わせであってもよい。 The resin may be a natural resin or a derivative thereof, or a synthetic resin. Examples of the natural resin or derivative thereof include cellulose, cellulose triacetate, nitrocellulose, and cellulose with dextran sulfate immobilized thereon. Acrylonitrile, polystyrene, polysulfone, polyethylene terephthalate, polymethyl methacrylate, polyvinyl alcohol, polyurethane, ethylene / vinyl alcohol copolymer, polyethylene, polyester, polypropylene, polyvinylidene fluoride, polyethersulfone, polycarbonate, polyvinyl chloride, polyvinylidene chloride, Polytetrafluoroethylene, ultrahigh molecular weight polyethylene, polydimethylsiloxane, acrylonitrile-butadiene-styrene resin or And the like Teflon (registered trademark). The material to be applied may be one type or a combination of two or more types.
　本発明の帯電防止剤を適用する対象の形態に特に制限はない。例えば、本発明の帯電防止剤を塗布型として用い、適用対象が樹脂成形体である場合、その形態として、フィルム（シート）、中空品、射出品、織布、不織布などの各種形態を挙げることができる。樹脂成形体の表面に帯電防止剤を塗布する方法についても特に限定はなく、例えばロールコート法、ロールブラッシュ法、スプレーコート法、エアナイフ法、含浸法、カーテン法を挙げることができ、これらの方法を組み合わせてもよい。 There is no particular limitation on the form to which the antistatic agent of the present invention is applied. For example, when the antistatic agent of the present invention is used as a coating mold and the application target is a resin molded body, examples of the form include various forms such as a film (sheet), a hollow product, an injection product, a woven fabric, and a nonwoven fabric. Can do. The method for applying the antistatic agent to the surface of the resin molded body is not particularly limited, and examples thereof include a roll coating method, a roll brush method, a spray coating method, an air knife method, an impregnation method, and a curtain method. May be combined.
　特に、本発明は、上記一般式（１）で示されるケイ素含有第４級アンモニウム化合物を含む帯電防止剤を有する帯電防止フィルムに関する。本発明の帯電防止フィルムは、例えば、上述の樹脂より成形したフィルムの表面の少なくも一部に、本発明の帯電防止剤を塗布し、必要に応じて、溶剤を乾燥することにより得られる。すなわち、本発明の帯電防止フィルムは、好ましくはフィルムの表面積の少なくとも５０％、より好ましくはフィルムの表面積の少なくとも７０％、さらに好ましくはフィルムの表面積の少なくとも８０％、特に好ましくはフィルムの表面積の少なくとも９０％に、本発明の帯電防止剤のコーティング層を備える。あるいは本発明の帯電防止フィルムは、例えば、上述の樹脂に帯電防止剤を練り込んだ後にフィルム成形し、必要に応じて、溶剤を乾燥することにより得てもよい。 In particular, the present invention relates to an antistatic film having an antistatic agent containing a silicon-containing quaternary ammonium compound represented by the general formula (1). The antistatic film of the present invention can be obtained, for example, by applying the antistatic agent of the present invention to at least a part of the surface of a film formed from the above-mentioned resin and drying the solvent as necessary. That is, the antistatic film of the present invention is preferably at least 50% of the surface area of the film, more preferably at least 70% of the surface area of the film, more preferably at least 80% of the surface area of the film, particularly preferably at least of the surface area of the film. 90% is provided with a coating layer of the antistatic agent of the present invention. Alternatively, the antistatic film of the present invention may be obtained, for example, by kneading an antistatic agent into the above-mentioned resin, forming a film, and drying the solvent as necessary.
＜分析条件＞
○ＮＭＲスペクトル
装置：ＪＮＭ－ＡＬ４００（日本電子（株）製）
試料と重ＤＭＳＯ（和光純薬工業（株）製０．０５％ＴＭＳ含有）とを混合した溶液を調整し、１Ｈ－ＮＭＲ測定を行った。 <Analysis conditions>
○ NMR spectrometer: JNM-AL400 (manufactured by JEOL Ltd.)
A solution in which a sample and heavy DMSO (containing 0.05% TMS manufactured by Wako Pure Chemical Industries, Ltd.) were mixed was prepared, and 1 H-NMR measurement was performed.
○含量
０．１ｍｏｌ／Ｌの硝酸銀液で滴定（電位差滴定法）し、目的物の含量を算出した。 ○ Titration (potentiometric titration method) with a silver nitrate solution having a content of 0.1 mol / L, and the content of the target product was calculated.
＜実施例１＞
Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド（ｎ＝３の化合物）の合成
　窒素置換した反応器に３－（ジメチルアミノ）－１－プロパノール（東京化成工業（株）製）５１．６ｇ（０．５０ｍｏｌ）、（３－クロロプロピル）トリエトキシシラン（東京化成工業（株）製）１２６．４ｇ（０．５２ｍｏｌ）およびエタノール（和光純薬工業（株）製）１３０ｍｌを仕込み、１２０℃で２４時間反応した。反応終了後、冷却し、目的物のエタノール溶液を２７３．２ｇ得た。なお、この溶液中に含まれる目的物の含量は６２．１重量％であった。 <Example 1>
Synthesis of N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride (n = 3 compound) 3- (dimethylamino) was added to a nitrogen-substituted reactor. 1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 51.6 g (0.50 mol), (3-chloropropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 126.4 g (0.52 mol) and ethanol 130 ml (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled to obtain 273.2 g of the target ethanol solution. The content of the target product contained in this solution was 62.1% by weight.
　得られた目的物のエタノール溶液から減圧下で溶媒を留去し、１Ｈ－ＮＭＲを測定した。結果を図１に示す。 The solvent was distilled off from the obtained ethanol solution of the target product under reduced pressure, and 1 H-NMR was measured. The results are shown in FIG.
＜実施例２＞
Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリド（ｎ＝２の化合物）の合成
　上記実施例１において、３－（ジメチルアミノ）－１－プロパノールに代えて２－（ジメチルアミノ）エタノールを用いた以外は同様の操作を行い、目的物のエタノール溶液を８８．０ｇ得た。なお、この溶液中に含まれる目的物の含量は６１．７重量％であった。 <Example 2>
Synthesis of N- [3- (triethoxysilyl) propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride (compound with n = 2) In Example 1 above, 3- (dimethylamino) The same operation was carried out except that 2- (dimethylamino) ethanol was used instead of -1-propanol to obtain 88.0 g of the target ethanol solution. The content of the target product contained in this solution was 61.7% by weight.
＜比較例１＞
　特開平７－１０１９６５の実施例１に従い、Ｎ－［３－（トリメトキシシリル）プロピル］－Ｎ，Ｎ－ジメチル－（３－スルホプロピル）アンモニウムヒドロキシド分子内塩を得た。得られた化合物を２０重量％メタノール溶液とし、試験例１に用いた。 <Comparative Example 1>
According to Example 1 of JP-A-7-101965, N- [3- (trimethoxysilyl) propyl] -N, N-dimethyl- (3-sulfopropyl) ammonium hydroxide inner salt was obtained. The obtained compound was made into a 20 wt% methanol solution and used in Test Example 1.
＜試験例１＞
　実施例１で得られた目的物のエタノール溶液（６２．１重量％）を、更にエタノールで希釈し、目的物の含量を２０重量％とした。次いで７０ｍｍ×５０ｍｍ、厚さ４ｍｍのガラス板をメタノールでふき取った後、塗工バーを用いて実施例１のエタノール溶液（２０重量％）および比較例１のメタノール溶液（２０重量％）をｗｅｔ膜厚２μｍで塗布した。室温で３０分間乾燥を行った後、さらに１２０℃で１時間乾燥を行った。
　得られた塗工ガラスおよび未塗工ガラスの表面抵抗値を以下の測定条件で測定し、帯電防止機能を調べた。結果を以下の表１に示す。 <Test Example 1>
The ethanol solution (62.1% by weight) of the target product obtained in Example 1 was further diluted with ethanol to make the content of the target product 20% by weight. Next, a 70 mm × 50 mm, 4 mm thick glass plate was wiped off with methanol, and then the ethanol solution of Example 1 (20 wt%) and the methanol solution of Comparative Example 1 (20 wt%) were wet films using a coating bar. The coating was applied with a thickness of 2 μm. After drying at room temperature for 30 minutes, drying was further performed at 120 ° C. for 1 hour.
The surface resistance value of the obtained coated glass and uncoated glass was measured under the following measurement conditions to examine the antistatic function. The results are shown in Table 1 below.
（測定条件）
負荷電圧：１０００Ｖ、測定時間：１０秒、気温１９℃、湿度：４５％ＲＨ
使用機器：三菱化学（株）　高抵抗率計　ハイレスターＵＰ、ＵＲＳプローブ (Measurement condition)
Load voltage: 1000V, measurement time: 10 seconds, temperature 19 ° C, humidity: 45% RH
Equipment used: Mitsubishi Chemical Corporation High resistivity meter Hi-Lester UP, URS probe
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
＜実施例３＞
　実施例１で得られた目的物のエタノール溶液（６２．１重量％）を、更にエタノールで希釈し、目的物の含量を６重量％とした。次いで１００μｍ厚のポリエステルフィルム（東洋紡（株）製、コスモシャイン（登録商標）Ａ４３００）に、実施例１のエタノール溶液（６重量％）をスプレー塗布した。その後、８０℃で２分間乾燥を行い、帯電防止フィルムを得た。 <Example 3>
The ethanol solution (62.1 wt%) of the target product obtained in Example 1 was further diluted with ethanol to make the content of the target product 6 wt%. Next, the ethanol solution (6% by weight) of Example 1 was spray-coated on a polyester film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A4300). Thereafter, drying was performed at 80 ° C. for 2 minutes to obtain an antistatic film.
＜実施例４＞
　実施例３で用いた、実施例１で得られた目的物のエタノール溶液に代えて、実施例２で得られた目的物のエタノール溶液（６１．７重量％）を用い、同様に希釈して目的物の含量を６重量％とした後、スプレー塗布し、実施例３と同様にして帯電防止フィルムを得た。 <Example 4>
In place of the ethanol solution of the target product obtained in Example 1 used in Example 3, the ethanol solution (61.7% by weight) of the target product obtained in Example 2 was used and diluted in the same manner. After setting the content of the target product to 6% by weight, spray coating was conducted to obtain an antistatic film in the same manner as in Example 3.
＜試験例２＞
　実施例３および４で得られた帯電防止フィルム、ならびに未加工のポリエステルフィルムの表面抵抗値を以下の測定条件で測定し、帯電防止機能を調べた。結果を以下の表２に示す。 <Test Example 2>
The surface resistance values of the antistatic films obtained in Examples 3 and 4 and the unprocessed polyester film were measured under the following measurement conditions to examine the antistatic function. The results are shown in Table 2 below.
（測定条件）
負荷電圧：１０００Ｖ、測定時間：１０秒、気温２１℃、湿度：４０％ＲＨ
使用機器：三菱化学（株）　高抵抗率計　ハイレスターＵＰ、ＵＲＳプローブ (Measurement condition)
Load voltage: 1000V, measurement time: 10 seconds, temperature 21 ° C, humidity: 40% RH
Equipment used: Mitsubishi Chemical Corporation High resistivity meter Hi-Lester UP, URS probe
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　本発明の帯電防止剤は、樹脂またはその成形体などに適用すると、優れた帯電防止効果を示す。また、本発明の帯電防止剤は、樹脂成形体などの対象の表面に塗布するか、または樹脂に練り込んだ後に成形すると、塗布されたまたは練り込み後に表面移行したケイ素含有第４級アンモニウム化合物が対象の表面に安定的に固定化されるため、洗浄や拭き取りに対する耐久性に優れる。したがって、特に各種日用品や工業分野、医療分野の製品などの原材料として幅広く用いられている樹脂製品の帯電防止剤として有用である。 The antistatic agent of the present invention exhibits an excellent antistatic effect when applied to a resin or a molded body thereof. In addition, the antistatic agent of the present invention is applied to the surface of an object such as a resin molded body, or a silicon-containing quaternary ammonium compound that has been applied or kneaded into a resin and then migrated to the surface after kneading. Is stably immobilized on the surface of the object, and is excellent in durability against cleaning and wiping. Therefore, it is particularly useful as an antistatic agent for resin products that are widely used as raw materials for various daily necessities, industrial products, and medical products.

Claims (8)

  1. 　下記一般式（１）
    Figure JPOXMLDOC01-appb-C000001
    ｛式中、Ｒ１はメチル基またはエチル基であり、Ｒ２は下記式（２）：
    Figure JPOXMLDOC01-appb-C000002
    で表わされる一価の基であり、Ｒ３は炭素数１～４のアルキル基であり、Ｘはハロゲン原子であり、ｍおよびｎは、互いに独立して、１～４の整数であり、ｐは１～３の整数である｝
    で示されるケイ素含有第４級アンモニウム化合物を含む、帯電防止剤。     The following general formula (1)
    Figure JPOXMLDOC01-appb-C000001
    {In the formula, R 1 represents a methyl group or an ethyl group, and R 2 represents the following formula (2):
    Figure JPOXMLDOC01-appb-C000002
    R 3 is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom, m and n are each independently an integer of 1 to 4 and p Is an integer from 1 to 3}
    The antistatic agent containing the silicon containing quaternary ammonium compound shown by these.
  2. 　前記一般式（１）において、Ｒ１がエチル基である、請求項１記載の帯電防止剤。 The antistatic agent according to claim 1 , wherein R 1 in the general formula (1) is an ethyl group.
  3. 　前記一般式（１）において、ｐが１である、請求項１または２記載の帯電防止剤。 The antistatic agent according to claim 1 or 2, wherein p is 1 in the general formula (1).
  4. 　前記一般式（１）において、ｍが３である、請求項１～３のいずれか記載の帯電防止剤。 The antistatic agent according to any one of claims 1 to 3, wherein m is 3 in the general formula (1).
  5. 　前記一般式（１）において、Ｘが塩素原子である、請求項１～４のいずれか記載の帯電防止剤。 The antistatic agent according to any one of claims 1 to 4, wherein, in the general formula (1), X is a chlorine atom.
  6. 　前記一般式（１）の化合物が、Ｎ－［３－（トリエトキシシリル）プロピル］－Ｎ－（３－ヒドロキシプロピル）－Ｎ，Ｎ－ジメチルアンモニウムクロリドまたはＮ－［３－（トリエトキシシリル）プロピル］－Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ－ジメチルアンモニウムクロリドである、請求項１～５のいずれか記載の帯電防止剤。 The compound of the general formula (1) is N- [3- (triethoxysilyl) propyl] -N- (3-hydroxypropyl) -N, N-dimethylammonium chloride or N- [3- (triethoxysilyl) The antistatic agent according to any one of claims 1 to 5, which is propyl] -N- (2-hydroxyethyl) -N, N-dimethylammonium chloride.
  7. 　請求項１～６のいずれか記載の帯電防止剤を有する帯電防止フィルム。 An antistatic film comprising the antistatic agent according to any one of claims 1 to 6.
  8. 　下記式（３）：
    Figure JPOXMLDOC01-appb-C000003
    で示される化合物。     Following formula (3):
    Figure JPOXMLDOC01-appb-C000003
    A compound represented by
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5888146A (en) * 1981-11-16 1983-05-26 Nippon Valqua Ind Ltd Making glass and glass fiber hydrophilic
JPS60206900A (en) * 1984-03-02 1985-10-18 ダウ　コーニング　コーポレーシヨン Detergent composition containing cationic surface-treated insoluble granular substance
JPH06322319A (en) * 1993-03-22 1994-11-22 Dow Corning Corp Water-repellent organosilicon composition
JPH0834160A (en) * 1994-07-22 1996-02-06 Fuji Photo Film Co Ltd Recording sheet
JP2010524683A (en) * 2007-04-24 2010-07-22 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Method for applying anti-corrosive and / or adhesion promoting coating agent to metal and resulting coated metal
WO2015163022A1 (en) * 2014-04-21 2015-10-29 広栄化学工業株式会社 Polysiloxane copolymer and antistatic agent comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5888146A (en) * 1981-11-16 1983-05-26 Nippon Valqua Ind Ltd Making glass and glass fiber hydrophilic
JPS60206900A (en) * 1984-03-02 1985-10-18 ダウ　コーニング　コーポレーシヨン Detergent composition containing cationic surface-treated insoluble granular substance
JPH06322319A (en) * 1993-03-22 1994-11-22 Dow Corning Corp Water-repellent organosilicon composition
JPH0834160A (en) * 1994-07-22 1996-02-06 Fuji Photo Film Co Ltd Recording sheet
JP2010524683A (en) * 2007-04-24 2010-07-22 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Method for applying anti-corrosive and / or adhesion promoting coating agent to metal and resulting coated metal
WO2015163022A1 (en) * 2014-04-21 2015-10-29 広栄化学工業株式会社 Polysiloxane copolymer and antistatic agent comprising same

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