WO2014051065A1 - Agent antistatique, stratifié antistatique utilisant ledit agent, et procédé de fabrication d'un film antistatique étiré de manière biaxiale - Google Patents

Agent antistatique, stratifié antistatique utilisant ledit agent, et procédé de fabrication d'un film antistatique étiré de manière biaxiale Download PDF

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Publication number
WO2014051065A1
WO2014051065A1 PCT/JP2013/076290 JP2013076290W WO2014051065A1 WO 2014051065 A1 WO2014051065 A1 WO 2014051065A1 JP 2013076290 W JP2013076290 W JP 2013076290W WO 2014051065 A1 WO2014051065 A1 WO 2014051065A1
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Prior art keywords
antistatic
group
resin
aqueous
film
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PCT/JP2013/076290
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English (en)
Japanese (ja)
Inventor
龍啓 菱田
宏 住友
成富　正樹
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丸善薬品産業株式会社
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Publication of WO2014051065A1 publication Critical patent/WO2014051065A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0008—Anti-static agents

Definitions

  • the present invention relates to an antistatic agent, an antistatic laminate using the same, and a method for producing a biaxially stretched antistatic film.
  • plastic films such as polyester films have been used in a wide range of applications such as plate-making films, packaging films, optical component films, films for semiconductor processing tapes, hot stamping films, and plastic molded decorative films.
  • plastics have high electrical resistance, and static electricity generated by friction and peeling is accumulated without leakage. Therefore, the appearance of commercial value is reduced due to dust adhering to the film, or due to electric discharge in electronic devices. There was a problem that a malfunction occurred.
  • an antistatic layer containing a low molecular weight anionic surfactant or an antistatic agent containing a cationic surfactant is applied to the surface of the substrate.
  • Methods of forming are known.
  • high antistatic property is exhibited to some extent under high humidity, the antistatic property is reduced under low humidity (45% RH or less), or charging due to bleedout of surfactant or friction. Since the prevention layer easily falls off, there is a problem that it is difficult to maintain a sufficient effect.
  • a method has been proposed in which a binder resin such as a polyurethane resin is used in combination with the surfactant in order to improve the adhesion between the base material and the antistatic layer. Since the compatibility between the highly polar surfactant and the binder resin is low and the stability of the antistatic agent is not sufficient, the antistatic agent cannot be uniformly applied to the substrate and the desired effect cannot be obtained. There are problems that the antistatic agent aggregates and cannot be used, and the bleed-out of the surfactant cannot be sufficiently suppressed. Furthermore, there has been a problem that the binder resin is altered by heat treatment during processing and use, and the antistatic property is impaired.
  • a binder resin is altered by heat treatment during processing and use, and the antistatic property is impaired.
  • such a binder resin requires absolutely or almost no organic solvent such as dimethylformamide, toluene, or methyl ethyl ketone as a dispersion medium from the viewpoint of preventing deterioration of the working environment and environmental pollution such as air and water quality.
  • organic solvent such as dimethylformamide, toluene, or methyl ethyl ketone
  • an antistatic layer formed of an antistatic agent is used for the purpose of maintaining the appearance and preventing the path of light when the substrate is used as a surface protective film of an optical component such as a polarizing plate. It is required to be thinner and more uniform.
  • the amount of the conventional antistatic agent used is, for example, the thickness of the antistatic layer (in the case of an antistatic layer formed by an inline coating method, the solid content of the antistatic agent at the thickness at the time of application
  • the theoretical antistatic layer thickness an amount that makes the corresponding thickness thin according to the draw ratio, hereinafter referred to as the theoretical antistatic layer thickness is required to be 1 ⁇ m or more.
  • the amount of the antistatic agent used is reduced, there is a problem that sufficient antistatic properties and adhesion to the substrate cannot be obtained.
  • conventional antistatic agents have insufficient wettability, so it is difficult to form a thin and uniform antistatic layer on the surface of a substrate such as a plastic film, or an antistatic layer is formed.
  • the antistatic agent is dried by heating at the time of heating, there is a problem that the antistatic agent aggregates and a uniform layer may not be formed.
  • an antistatic agent is applied on a uniaxially stretched resin film and dried, and then heated in a direction perpendicular to the direction of the uniaxially stretched film.
  • an antistatic agent may be denatured by thermal stretching, or the antistatic property and appearance may be impaired because the antistatic agent cannot follow film stretching while maintaining a conductive mechanism.
  • the in-line coating method since it is heated to a high temperature by thermal stretching or the like, it is desired to use water as a dispersion medium for the antistatic agent from the viewpoint of safety such as explosion prevention.
  • Examples of the antistatic agent that can be used in such an in-line coating method include, for example, a conductive polymer resin such as polythiophene, a polyurethane resin, a cross-linking agent, and a fluororesin in JP-A-2009-83455 (Patent Document 1).
  • a conductive polymer resin such as polythiophene
  • a polyurethane resin such as polythiophene
  • a cross-linking agent such as JP-A-2009-83455
  • the present invention has been made in view of the above-mentioned problems of the prior art, has excellent stability, wettability, film-forming property, stretchability, and can be applied to an in-line coating method. Furthermore, an antistatic layer having excellent adhesion to a base material and heat resistance and capable of exhibiting excellent antistatic properties even at a relatively low humidity than before is formed in a relatively small amount compared to the conventional. It is an object to provide an antistatic agent that can be used, an antistatic laminate using the antistatic agent, and a method for producing a biaxially stretched antistatic film.
  • the present inventors have obtained a specific cationic aqueous resin having a quaternary ammonium group, a specific anionic aqueous resin having an anionic hydrophilic group in an antistatic agent,
  • a specific aqueous resin in combination, excellent stability, wettability, film formability, stretch followability can be exhibited, and it can be sufficiently applied to the in-line coating method.
  • the antistatic layer obtained using such an antistatic agent has excellent adhesion to the substrate and heat resistance even when the amount of the antistatic agent used is relatively small compared to the prior art. It has been found that it is possible to exhibit excellent antistatic properties even under relatively low humidity than before, and the present invention has been completed.
  • the antistatic agent of the present invention is (A) (A1) The following general formula (1):
  • each R 1 independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms
  • R 2 represents an alkylene group having 2 to 5 carbon atoms
  • R 3 represents an alkylene group which has 2 carbon atoms which may be 1-8 an ether group
  • X - represents a monovalent anion independently.
  • a cationic aqueous resin containing as a repeating unit a structure represented by: (A2) The following general formula (2):
  • each R 4 independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, and X ⁇ represents a monovalent anion.
  • a cationic aqueous resin containing a structure represented by (A3) The following general formula (3-1):
  • each R 5 independently represents an alkyl group having 1 to 4 carbon atoms, and X ⁇ represents a monovalent anion.
  • each R 6 independently represents an alkyl group having 1 to 4 carbon atoms, and X ⁇ represents a monovalent anion.
  • X ⁇ represents a monovalent anion.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 8 independently represents an alkyl group having 1 to 4 carbon atoms
  • X ⁇ represents a monovalent anion.
  • the content of nitrogen atoms derived from the quaternary ammonium group in the cationic aqueous resin (A) is preferably 5 to 15% by mass, and the anion (B) In the water-based aqueous resin, the content of the anionic hydrophilic group is preferably 0.1 to 5.0% by mass.
  • the (B) anionic aqueous resin is the (B1) an aqueous polyurethane resin having an anionic hydrophilic group, and (B1-a) a polyester polyol and a polycarbonate polyol. At least one polyol selected from the group consisting of: (B1-b) a compound having an anionic hydrophilic group and two or more active hydrogens; (B1-c) a polyisocyanate; and (B1-d) an amino group. And a polyamine compound having two or more of at least one of the imino groups is preferably obtained.
  • the mass ratio (A: B) of the (A) cationic aqueous resin to the (B) anionic aqueous resin is 90:10 to 20:80. preferable.
  • the antistatic agent of the present invention preferably further contains a release agent.
  • the antistatic laminate of the present invention comprises a base material and an antistatic layer formed from the antistatic agent of the present invention on at least a part of the surface of the base material.
  • the base material is preferably at least one of a resin molded body and a fiber molded body, and the base material is a resin film. It is preferable that the antistatic film has the antistatic layer formed on at least one surface.
  • the method for producing the biaxially stretched antistatic film of the present invention comprises: A step of uniaxially stretching an unstretched resin film to obtain a uniaxially stretched resin film; Forming an antistatic layer from the antistatic agent of the present invention on at least one surface of the uniaxially stretched resin film to obtain a uniaxially stretched antistatic film; and A step of obtaining a biaxially stretched antistatic film by stretching in a direction perpendicular to the direction of uniaxial stretching; It is characterized by including.
  • the aqueous resin refers to a resin having water solubility or self-emulsifying property (performance capable of being emulsified and dispersed by itself without adding an emulsifier).
  • the resin concentration is 5 It refers to a resin in which an aqueous dispersion containing no emulsifier is prepared and no precipitate is formed even if it is left at room temperature (about 25 ° C.) for 1 day.
  • (meth) acryl refers to methacryl and acryl
  • (meth) acrylate refers to methacrylate and acrylate.
  • the present invention has excellent stability, wettability, film formability, stretch followability, can be applied to an in-line coating method, and has excellent adhesion to a substrate and heat resistance.
  • Antistatic agent capable of forming an antistatic layer with a relatively small amount of conventional antistatic layer capable of exhibiting excellent antistatic properties even under relatively low humidity, and antistatic using the same It is possible to provide a method for producing a conductive laminate and a biaxially stretched antistatic film.
  • the antistatic agent of the present invention further contains other various functional agents (water / oil repellent, ultraviolet absorber, mold release agent, antifogging agent, etc.), the functions derived from these agents
  • An antistatic layer capable of sufficiently exhibiting water / oil repellency, ultraviolet absorption, releasability, antifogging, etc.
  • the antistatic agent of the present invention comprises the following (A) cationic aqueous resin, (B) anionic aqueous resin, and (C) an aqueous resin.
  • the cationic aqueous resin (A) is a cationic aqueous resin having a quaternary ammonium group, and the following (A1) cationic aqueous resin, (A2) cationic aqueous resin, and (A3) cationic aqueous resin described below. Is at least one selected from the group consisting of
  • the antistatic agent of the present invention can exhibit excellent stretch followability,
  • the antistatic layer obtained using the antistatic agent of the present invention can exhibit excellent antistatic properties.
  • the antistatic layer obtained by the antistatic agent layer of the present invention having such a combination can exhibit excellent heat resistance and adhesion to a substrate. The present inventors speculate that this is because the resin is ionically complexed (ion complexed) with (B) an anionic aqueous resin described later.
  • the content of nitrogen atoms derived from the quaternary ammonium group is preferably 5 to 15% by mass with respect to the total amount of the (A) cationic aqueous resin, It is more preferably 7 to 12% by mass.
  • the content of nitrogen atoms is less than the lower limit, the antistatic properties of the resulting antistatic layer and the adhesion to the substrate tend to be reduced.
  • the content exceeds the upper limit, it will be described later.
  • the degree of complexation with the anionic aqueous resin tends to decrease, and the film formability, agent stability, and wettability tend to decrease.
  • content of the nitrogen atom derived from the quaternary ammonium group in cationic aqueous resin has the nitrogen atom which becomes the origin of the said nitrogen atom among the monomers used for the synthesis
  • the (A) cationic aqueous resin according to the present invention preferably has a weight average molecular weight of 4,000 to 300,000.
  • the weight average molecular weight is equal to or more than the lower limit, the stretchability and the antistatic property of the resulting antistatic layer and the adhesion to the substrate tend to be further improved.
  • the weight average molecular weight is not more than the above upper limit, the water dispersibility of the cationic aqueous resin is further improved, and when the dispersion medium of the antistatic agent is water, it tends to be easily dispersed.
  • the cationic aqueous resin has a weight average molecular weight of gel permeation chromatography (GPC) (“HLC-8120” manufactured by Tosoh Corporation; solvent: 0.3 M triethanolamine aqueous solution with phosphoric acid at a pH of 2.9. Measured using two columns: “TSK-GEL ⁇ M” and “TSK-GEL ⁇ 3000” (each manufactured by Tosoh Corporation); temperature 40 ° C .; speed: 1.0 ml / min) It can obtain
  • GPC gel permeation chromatography
  • the (A1) cationic aqueous resin according to the present invention is a cationic aqueous resin containing a structure represented by the following general formula (1) as a repeating unit.
  • each R 1 independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. If the carbon number of R 1 exceeds the above upper limit, the content of the quaternary ammonium group becomes insufficient, the antistatic property of the resulting antistatic layer and the adhesion to the substrate are lowered, and the cationic aqueous resin The water dispersibility of the is reduced.
  • R 1 is preferably a methyl group, an ethyl group, or a propyl group from the viewpoint of antistatic properties, adhesion, and water dispersibility.
  • R 2 represents an alkylene group having 2 to 5 carbon atoms. It is difficult to synthesize a cationic aqueous resin having a carbon number of R 2 less than the lower limit. On the other hand, when the carbon number of R 2 exceeds the upper limit, the content of the quaternary ammonium group becomes insufficient. The antistatic properties of the resulting antistatic layer and the adhesion to the substrate are reduced.
  • R 2 is preferably an ethylene group, a trimethylene group, or a tetramethylene group from the viewpoint of antistatic properties, adhesion, and availability.
  • R 3 represents an alkylene group having 2 to 8 carbon atoms which may have an ether group (—O—). It is difficult to synthesize a cationic aqueous resin having a carbon number of R 3 less than the lower limit. On the other hand, if the carbon number of R 3 exceeds the upper limit, the content of the quaternary ammonium group becomes insufficient. The antistatic properties of the resulting antistatic layer and the adhesion to the substrate are reduced.
  • Such R 3 includes a group represented by —C 2 H 4 —O—C 2 H 4 —, —C 3 H 6 —O, from the viewpoint of antistatic properties, adhesion, and availability. A group represented by —C 3 H 6 — and a group represented by —C 4 H 8 —O—C 4 H 8 — are preferred.
  • X ⁇ each independently represents a monovalent anion.
  • the valence of the anion is 2 or more, the cationic aqueous resin is easily gelled and the water dispersibility is lowered.
  • the monovalent anion include halogen ions, nitrate ions, methanesulfonate ions, ethanesulfonate ions, monomethyl sulfate ions, monoethyl sulfate ions, trifluoroacetate ions, and trichloroacetate ions.
  • X ⁇ is a chlorine ion, a methanesulfonate ion, or an ethanesulfonate ion. Preferably there is.
  • the (A1) cationic aqueous resin according to the present invention is preferably a homopolymer containing only the structure represented by the general formula (1) as a repeating unit.
  • Such (A1) cationic aqueous resin includes, for example, N, N, N ′, N′-tetraalkylalkylenediamine represented by the following general formula (A1-a) and the following general formula (A1-b): It can obtain by making it react with the dichloro heteroalkylene compound represented by these.
  • R 1 and R 2 each have the same meanings as R 1 and R 2 in the formula (1).
  • R 3 has the same meaning as R 3 in the formula (1).
  • Examples of the compound represented by the general formula (A1-a) include N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethyl. -1,4-butanediamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N, N ′, N′-2-pentamethyl-1,2-propanediamine, N , N, N ′, N′-tetramethylhexamethylenediamine, one of which may be used alone, or two or more thereof may be used in combination.
  • Examples of the compound represented by the general formula (A1-b) include di (chloromethyl) ether, bis (2-chloroethyl) ether, di (chloromethyl) formal, bis (2-chloroethyl) formal, 1, 2-bis (chloromethoxy) ethane may be mentioned, and one of these may be used alone or two or more may be used in combination.
  • (A1) cationic aqueous resin which concerns on this invention, you may use a commercial item suitably.
  • the (A2) cationic aqueous resin according to the present invention is a cationic aqueous resin containing a structure represented by the following general formula (2) as a repeating unit.
  • each R 4 independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms.
  • R 4 is preferably a methyl group, an ethyl group, or a propyl group from the viewpoint of antistatic properties, adhesion, and water dispersibility.
  • X ⁇ represents a monovalent anion.
  • Such X - is the, X described in the (A1) a cationic aqueous resin - it is similar to that.
  • the (A2) cationic aqueous resin according to the present invention may contain a structure represented by the general formula (2) as a repeating unit, and is a homopolymer containing only the structure as a repeating unit.
  • the copolymer may further contain a structure derived from another monomer within a range that does not impair the effects of the present invention. Examples of the other monomer include ethylenediamine dihydrochloride.
  • the (A2) cationic aqueous resin according to the present invention is a homopolymer containing only the above structure as a repeating unit from the viewpoint that the antistatic property of the resulting antistatic layer and the adhesion to the substrate are more excellent. Preferably there is.
  • Such (A2) cationic aqueous resin can be obtained, for example, by subjecting epichlorohydrin and a dialkylamine having an alkyl group having 1 to 3 carbon atoms to a self-condensation reaction.
  • a commercial item may be used, and UNISONS KHE104L (trade name, manufactured by Senca Co., Ltd.) and the like can be given as such a commercial item.
  • the (A3) cationic aqueous resin according to the present invention has a structure represented by the following general formula (3-1), a structure represented by the following general formula (3-2), and It is a cationic aqueous resin containing at least one of the structures represented by the general formula (4) as a repeating unit.
  • R 5 and R 6 each independently represents an alkyl group having 1 to 4 carbon atoms.
  • R 5 and R 6 are preferably a methyl group, an ethyl group, or a propyl group from the viewpoint of antistatic properties, adhesion, and water dispersibility.
  • X ⁇ each independently represents a monovalent anion. Such X - is the, X described in the (A1) a cationic aqueous resin - it is similar to that.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the carbon number of R 7 exceeds the above upper limit, the content of the quaternary ammonium group becomes insufficient, the antistatic property of the resulting antistatic layer and the adhesion to the substrate are lowered, and the cationic aqueous resin The water dispersibility of the is reduced.
  • R 7 is preferably a methyl group, an ethyl group, or an n-propyl group from the viewpoint of antistatic properties, adhesion, and water dispersibility.
  • each R 8 independently represents an alkyl group having 1 to 4 carbon atoms.
  • R 8 is preferably a methyl group, an ethyl group, or a propyl group from the viewpoint of antistatic properties, adhesion, and water dispersibility.
  • X ⁇ represents a monovalent anion.
  • Such X - is the, X described in the (A1) a cationic aqueous resin - it is similar to that.
  • the structure represented by the general formula (3-1), the structure represented by the following general formula (3-2), and the following general formula (4) It is only necessary to contain at least one of the represented structures as a repeating unit, and even if it is a homopolymer containing only one of the above structures as a repeating unit, two kinds of repeating units may be used.
  • the copolymer containing the above structure may be sufficient, and the copolymer which further contains the structure derived from another monomer in the range which does not inhibit the effect of this invention may be sufficient.
  • Examples of the other monomers include diallylamine hydrochloride, methyldiallylamine hydrochloride, diallylamine acetate, 1-chlorochloroform when polymerized with the structures represented by the general formulas (3-1) and (3-2). Examples include -2-hydroxydiallylamine hydrochloride, (meth) acrylamide, sulfur dioxide, and the like.
  • monoallylamine, monoallylamine hydrochloride, and the like can be given.
  • the (A3) cationic aqueous resin according to the present invention has a structure represented by the general formula (3-1) from the viewpoint that the antistatic property of the resulting antistatic layer and the adhesion to the substrate are more excellent.
  • the total amount of the structure represented by the general formula (3-2) and the structure represented by the general formula (4) is more preferably 60% by mass or more.
  • the content of such a structure having a quaternary ammonium group is quaternary ammonium in the above-mentioned (A) cationic aqueous resin. It can adjust suitably according to content of the nitrogen atom derived from group.
  • Such a cationic aqueous resin (A3) can be prepared by, for example, subjecting dimethyldiallylammonium hydrochloride to a cyclized radical polymerization reaction in a medium mainly composed of water, thereby allowing the general formula (3-1) or (3-2) A cationic aqueous resin having a structure represented by) can be obtained.
  • a cationic aqueous resin having a structure represented by the above general formula (4) can be obtained by radical polymerization reaction of monoallylamine quaternized hydrochloride in a medium mainly containing water. .
  • (A3) cationic aqueous resin a commercially available product may be used.
  • a commercially available product include a cation having a structure represented by the general formula (3-1) as a repeating unit.
  • PAS-H-10L, PAS-H-5L, PAS-24, PAS-J-81, PAS-800 all trade names, manufactured by Nitto Bo Medical Co., Ltd.
  • Unisense FPA100L trade names
  • (A) cationic aqueous resin according to the present invention From the viewpoint that the antistatic property of the resulting antistatic layer tends to be further improved as the (A) cationic aqueous resin according to the present invention, (A1) the cationic aqueous resin and (A2) the cationic aqueous resin. From the viewpoint that the water resistance of the obtained antistatic layer tends to be further improved, (A3) a cationic aqueous resin is preferable.
  • the (B) anionic aqueous resin according to the present invention includes (B1) an aqueous polyurethane resin having an anionic hydrophilic group, (B2) an aqueous poly (meth) acrylic resin having an anionic hydrophilic group, and (B3) an anionic hydrophilic resin. And at least one anionic aqueous resin selected from the group consisting of an ethylene-vinyl acetate copolymer having a group.
  • the antistatic agent of the present invention can exhibit excellent stretch followability. Moreover, the obtained antistatic layer can exhibit excellent heat resistance and adhesion to the substrate.
  • the anionic hydrophilic group possessed by the anionic aqueous resin (B) according to the present invention is a carboxy group, a sulfo group, and a group in which they are neutralized from the viewpoint that water dispersibility tends to be more excellent.
  • it may be one or more of these, but from the viewpoint that the antistatic property of the resulting antistatic layer tends to be further improved, the carboxy group and / or it is More preferably, it is a neutralized group.
  • Examples of the base used for the neutralization include ammonium; amines such as trialkylamines, dialkylmonoalkanolamines, monoalkyldialkanolamines, trialkanolamines in which the alkyl group and alkanol have about 1 to 4 carbon atoms; water Examples thereof include hydroxides such as sodium oxide and potassium hydroxide, and one or more of these may be used. Among these, from the viewpoint that the antistatic agent can be volatilized at a temperature of about 100 to 120 ° C., which is the most common heating temperature, when the antistatic agent is applied to a resin film as one type of substrate and then dried. Ammonium and amines are preferred.
  • the dispersion medium of the antistatic agent of the present invention is preferably water or a mixed solution mainly containing water.
  • a neutralized group is more preferable if it is the same kind of anionic hydrophilic group (for example, a carboxy group and a group in which it is neutralized).
  • the content of the anionic hydrophilic group is preferably 0.1 to 5% by mass based on the total amount of (B) the anionic aqueous resin. More preferably, it is 25 to 2.5% by mass.
  • the content of the anionic hydrophilic group is within the above range, the compounding with the (A) cationic aqueous resin is more optimal, and more excellent wettability, film-forming property and agent stability are exhibited. There is a tendency that the adhesion of the antistatic layer to the base material is further improved and the water dispersibility of the anionic aqueous resin is further improved.
  • the content of the anionic hydrophilic group in the anionic aqueous resin refers to a value obtained using the molecular weight of the structure in a state of being not neutralized (not deprotonated). That is, for example, in the case of a carboxy group, the content is calculated using the molecular weight of the structure (—COOH) as it is, and in the case of a carbochelate group (—COO ⁇ ), for example, the state is not neutralized The content is determined using the structure of the above, that is, the molecular weight of the carboxy group (—COOH).
  • Such a content is determined by the amount of potassium hydroxide required to neutralize an anionic hydrophilic group (for example, carboxy group, sulfo group) in 1 g of an unneutralized anionic aqueous resin according to JIS K 0070 (1992). It can obtain
  • an anionic hydrophilic group for example, carboxy group, sulfo group
  • the weight average molecular weight of the following anionic aqueous resin is determined by gel permeation chromatography (GPC) (“HLC-8020” manufactured by Tosoh Corporation; solvent: tetrahydrofuran; column: “TSK-GEL G5000HHR”, “ Measure using TSK-GEL G4000HHR and TSK-GEL G3000HHR (each manufactured by Tosoh Corporation); temperature 40 ° C .; speed: 1.0 ml / min) and calculate by standard polystyrene. be able to.
  • GPC gel permeation chromatography
  • (B1) An aqueous polyurethane resin having an anionic hydrophilic group (hereinafter referred to as (B1) an aqueous polyurethane resin)
  • the (B1) aqueous polyurethane resin according to the present invention preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 20,000 to 100,000. When the weight average molecular weight is within the above range, the agent stability is further improved, and the adhesion of the resulting antistatic layer to the substrate tends to be further improved.
  • the (B1) aqueous polyurethane resin has a structure derived from polyester polyol and / or polycarbonate polyol from the viewpoint that the adhesion of the resulting antistatic layer to the substrate tends to be further improved. Preferably, it has a structure derived from polycarbonate polyol.
  • examples of such (B1) aqueous polyurethane resin include (B1-a) at least one polyol (more preferably polycarbonate polyol) selected from the group consisting of polyester polyol and polycarbonate polyol, and (B1-b) anionic property.
  • a compound having a hydrophilic group and two or more active hydrogens, (B1-c) polyisocyanate and (B1-d) a polyamine compound having at least one of amino groups and imino groups are reacted. It is more preferable to be obtained.
  • polyester polyol in the (B1-a) polyol examples include a compound obtained by a dehydration condensation reaction between a dihydroxy compound and an acid, and a compound obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone. It is done.
  • dihydroxy compound examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.
  • Examples of the acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and fumaric acid, and cyclohexane such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
  • aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and fumaric acid
  • cyclohexane such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
  • Examples of the polycarbonate polyol in the (B1-a) polyol include compounds obtained by reacting a carbonate and / or phosgene with a polyol.
  • Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and the like.
  • Examples of the polyol include ethylene glycol, diethylene glycol, and triethylene glycol.
  • the weight average molecular weight is preferably from 500 to 5,000, more preferably from 500 to 4,000, from the viewpoint of further improving the adhesion of the resulting antistatic layer to the substrate. preferable.
  • the anionic hydrophilic group in the compound (B1-b) having an anionic hydrophilic group and two or more active hydrogens is the anionic hydrophilic group of the (B1) aqueous polyurethane resin. It is preferably a carboxy group, a sulfo group, and a neutralized group thereof, more preferably a carboxy group and / or a neutralized group thereof.
  • Examples of such (B1-b) compounds include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2′-dimethylolpentanoic acid and salts thereof; 5-sulfoisophthalate Acids, sulfoterephthalic acid, 4-sulfophthalic acid, dicarboxylic acids such as 5- [4-sulfophenoxy] isophthalic acid and their salts, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And sulfo group and / or sulfonate group-containing polyester polyol obtained by reacting with a low molecular weight polyol such as neopentyl glycol, etc., and using one of these alone or in combination of two or more thereof Also good.
  • a low molecular weight polyol such as neopentyl glycol, etc.
  • the polyester polyol which has a pendant type carboxy group obtained by making the diol which has a carboxy group, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, etc. react, or its salt is also mentioned. Further, it may be obtained by further mixing and reacting a diol having no carboxy group during the reaction.
  • the (B1-c) polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in one molecule.
  • aromatic polyisocyanates examples include tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, tetrahydronaphthalene diisocyanate and the like.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, and lysine diisocyanate.
  • Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1, Examples include 3-bis (isocyanatomethyl) cyclohexane.
  • the (B1-c) polyisocyanate is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate from the viewpoint that yellowing of the obtained (B1) aqueous polyurethane resin can be further suppressed. More preferred are diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane.
  • Examples of the polyamine compound having two or more of (B1-d) amino group and imino group include, for example, tetramethylenediamine, hydrazine, norbornanediamine, Diamines such as diaminodiphenylmethane, tolylenediamine, xylylenediamine; low molecular weight polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine; tetraethylene Polyamines such as pentamine, iminobispropylamine, tris (2-aminoethyl) amine; amidoamines derived from diprimary amines and monocarboxylic acids; Amine derivatives of monoamines such as monoketimines; oxalic
  • the (B1-a) polyol, the (B1-b) compound, the (B1-c) polyisocyanate, and the (B1-d) polyamine compound are reacted to obtain the (B1) aqueous polyurethane resin.
  • the method for example, an isocyanate group-terminated urethane prepolymer obtained by reacting the (B1-a) polyol, the (B1-b) compound, and the (B1-c) polyisocyanate is reacted with the (B1-d) )
  • a method in which a chain is extended using a polyamine compound is reacted.
  • the isocyanate group-terminated urethane prepolymer can be obtained by appropriately applying conventionally known methods. For example, it can be obtained by mixing the (B1-a) polyol, the (B1-b) compound and the (B1-c) polyisocyanate, and subjecting the isocyanate group and active hydrogen reacting thereto to a polyaddition reaction.
  • the polyaddition reaction may be a one-stage one-shot method or a multi-stage method.
  • the conditions for such a polyaddition reaction are not particularly limited, but for example, it is preferably 15 minutes to 10 hours at 40 to 150 ° C.
  • the mixing ratio of the respective raw materials in the reaction composition is that the isocyanate group derived from the (B1-c) polyisocyanate is the (B1-a) polyol and the (B1-b)
  • the mixing ratio is preferably excessive with respect to the active hydrogen derived from the compound, and the molar ratio of the isocyanate group to the active hydrogen (number of moles of isocyanate group / number of moles of active hydrogen) is 100/80 to 100 It is more preferable to adjust to 50/50, and it is further preferable to adjust to 100/75 to 100/65.
  • the amount of the (B1-b) compound used is such that the content of the anionic hydrophilic group derived from the (B1-b) compound in the obtained (B1) aqueous polyurethane resin is 0.1.
  • the amount is preferably 5 to 5% by mass, and more preferably 0.25 to 2.5% by mass.
  • dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine, 1,8-diazabicyclo (5,4 , 0) -undecene or the like may be added.
  • other components such as polyether polyol, dimer diol, low molecular weight compound other than the compound (B1-b) having two or more active hydrogens may be contained.
  • the content thereof is from the viewpoint that the adhesion of the resulting antistatic layer to the substrate tends to be further improved, and the (B1-a) polyol and the other The content is preferably 1 to 50% by mass based on the total amount of the components.
  • polyether polyol examples include compounds obtained by addition polymerization of alkylene oxide using a low molecular weight polyhydric alcohol as an initiator.
  • the low molecular weight polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, and propylene. Examples include glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, and trimethylolpropane.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
  • Examples of the dimer diol include those mainly composed of a diol obtained by reducing polymerized fatty acid.
  • Examples of the polymerized fatty acid include unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid; Semi-drying oil fatty acids; and reaction products obtained by bimolecular polymerization of lower monoalcohol esters of these compounds by Diels-Alder reaction.
  • a polymerized fatty acid various types of polymerized fatty acid are commercially available, and typical examples thereof include 0 to 5% by mass of a monocarboxylic acid having 18 carbon atoms and 70 to 98 dimer acid having 36 carbon atoms. Examples thereof include those consisting of 0 to 30% by mass of trimer acid having 54% by mass and 54 carbon atoms.
  • low molecular weight compound examples include low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and sorbitol. It is done.
  • low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and sorbitol. It is done.
  • the isocyanate group-terminated prepolymer thus obtained preferably has a free isocyanate group content of 0.5 to 8% by mass based on the total amount of the isocyanate group-terminated prepolymer at the end of the polyaddition reaction.
  • the isocyanate group-terminated prepolymer, the (B1-d) polyamine compound, and water are mixed and reacted at a temperature of 10 to 60 ° C. for 10 minutes to 2 hours. The method of letting it be mentioned.
  • a free isocyanate group in the isocyanate group-terminated prepolymer and an amino group and an imino group in the polyamine compound (B1-d) Is preferably adjusted so that the molar ratio (the number of moles of isocyanate groups / the total number of moles of amino groups and imino groups) is 1 / 1.2 to 1.2 / 1.
  • the aqueous polyurethane resin (B1) thus obtained is used in the antistatic agent of the present invention, it is preferably used as a dispersion dispersed in water. According to the above-mentioned method, since the aqueous polyurethane resin (B1) is obtained as a dispersion dispersed in water, it can be used as it is for the antistatic agent of the present invention.
  • the concentration of the (B) aqueous polyurethane resin in such a dispersion is preferably 10 to 60% by mass.
  • (B1 A method of neutralizing an anionic hydrophilic group derived from the compound -b) is preferred. Such neutralization facilitates dispersion of the (B1) aqueous polyurethane resin in water.
  • the base used for the neutralization include the same bases as those used for the neutralization of the anionic hydrophilic group of the (B) anionic aqueous resin.
  • (B1) water-based polyurethane resin which concerns on this invention you may use a commercial item suitably.
  • (B2) Aqueous poly (meth) acrylic resin having an anionic hydrophilic group (hereinafter referred to as (B2) aqueous poly (meth) acrylic resin)
  • the (B2) aqueous poly (meth) acrylic resin according to the present invention preferably has a weight average molecular weight of 7,000 to 300,000, more preferably 10,000 to 200,000. When the weight average molecular weight is within the above range, the stretchability is further improved, and the adhesion of the resulting antistatic layer to the substrate tends to be further improved.
  • aqueous poly (meth) acrylic resin (B2-a) an alkyl group has a tendency to further improve stretch followability and adhesion of the resulting antistatic layer to the base material. It is preferable that it is obtained by copolymerizing an alkyl (meth) acrylate having 1 to 8 carbon atoms with an ethylenically unsaturated monomer having (B2-b) an anionic hydrophilic group.
  • Examples of the alkyl (meth) acrylate having 1 to 8 carbon atoms in the (B2-a) alkyl group include, for example, methyl (meth) acrylate, ) Ethyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and one of these is used alone It may be used in combination of two or more.
  • such a (B2-a) alkyl (meth) acrylate is an alkyl having an alkyl group with 4 or less carbon atoms ( It is preferable to use a combination of (meth) acrylate and an alkyl (meth) acrylate having 5 or more carbon atoms in the alkyl group.
  • the anionic hydrophilic group in the (B2-b) ethylenically unsaturated monomer having an anionic hydrophilic group is the (B2) aqueous poly ( It is an anionic hydrophilic group of a (meth) acrylic resin, preferably a carboxy group, a sulfo group, and a group in which they are neutralized, and a carboxy group and / or a group in which it is neutralized. Is more preferable.
  • Examples of the (B2-b) ethylenically unsaturated monomer include (meth) acrylic acid; crotonic acid; (anhydrous) itaconic acid; (anhydrous) maleic acid; monoallyl adipate; monoallyl sebacate; Monoallyl acid; monovinyl succinate; monovinyl adipate; monovinyl sebacate; vinyl sulfonic acid; 2- (acryloyloxy) ethanesulfonic acid, 2- (methacryloyloxy) ethanesulfonic acid, 3- (acryloyloxy) propane-1-sulfone Acid, (acryloyloxy) alkanesulfonic acid or (methacryloyloxy) alkanesulfonic acid having alkanesulfonic acid groups such as 3- (methacryloyloxy) propane-1-sulfonic acid having 1 to 4 carbon cords; and salts thereof Using one of these alone It may be used in combination of two or more.
  • the (B2) aqueous poly (meth) acrylic resin by copolymerizing the (B2-a) alkyl (meth) acrylate and the (B2-b) ethylenically unsaturated monomer multi-stage emulsification is used.
  • the (B2-a) alkyl (meth) acrylate, the (B2-b) ethylenically unsaturated monomer, and water are mixed, and in the presence of an emulsifier and a polymerization initiator,
  • An example is a method in which the emulsion polymerization step is usually repeated a plurality of times under the condition of pH of 4 or less, usually at 60 to 90 ° C.
  • the (B2) aqueous poly (meth) acrylic resin is used in the antistatic agent of the present invention, it is preferably used as a dispersion dispersed in water. According to this method, the (B2) aqueous poly (acrylic) resin is used. Since the (meth) acrylic resin is obtained as a dispersion dispersed in water, it can be used as it is for the antistatic agent of the present invention.
  • the mixing ratio (B2-a: B2-b) of the (B2-a) alkyl (meth) acrylate and the (B2-b) ethylenically unsaturated monomer is 99 by mass. : 1 to 92:10 is preferred.
  • the amount of the (B2-b) ethylenically unsaturated monomer used is an anion derived from the (B2-b) ethylenically unsaturated monomer in the obtained (B2) aqueous poly (meth) acrylic resin.
  • the amount of the hydrophilic hydrophilic group is preferably 0.1 to 5% by mass, and more preferably 0.25 to 2.5% by mass.
  • (B2) aqueous poly (meth) acrylic resin other copolymerizable monomers may be copolymerized within the range in which the effects of the present invention are not inhibited.
  • examples of such monomers include 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, and the following general formula (5) ):
  • A represents a hydrogen atom or a methyl group
  • EO represents an oxyethylene group
  • n represents the average number of added moles of (EO) and represents an integer of 3 to 15.
  • the compound represented by these is mentioned.
  • the compound represented by the above formula (5) is preferable from the viewpoint that the water dispersibility of the obtained (B2) aqueous poly (meth) acrylic resin tends to be further improved. Further, when these monomers are copolymerized, the content thereof is preferably 5% by mass or less based on the total amount of the (B2) aqueous poly (meth) acrylic resin.
  • (B2) aqueous poly (meth) acrylic resin according to the present invention commercially available products may be used.
  • commercially available products may be used.
  • (B3) An ethylene-vinyl acetate copolymer having an anionic hydrophilic group (hereinafter referred to as (B3) an ethylene-vinyl acetate copolymer)
  • the (B3) ethylene-vinyl acetate copolymer according to the present invention preferably has a weight average molecular weight of 50,000 to 1,000,000, more preferably 100,000 to 500,000. . When the weight average molecular weight is within the above range, the stretch followability is further improved, and the adhesion of the resulting antistatic layer to the substrate tends to be further improved.
  • the copolymer is obtained by copolymerizing ethylene, vinyl acetate, and the (B2-b) ethylenically unsaturated monomer.
  • the (B3) ethylene-vinyl acetate copolymer by the copolymerization a known method can be employed without particular limitation, and examples thereof include ethylene, vinyl acetate, and the (B2-b) ethylenic one.
  • An example is a method in which an unsaturated monomer and water are mixed and emulsion polymerization is performed under high pressure conditions (usually 0.2 to 3.92 MPa) in the presence of an emulsifier and a polymerization initiator.
  • the (B3) ethylene-vinyl acetate copolymer is used in the antistatic agent of the present invention, it is preferably used as a dispersion dispersed in water.
  • the (B3) ethylene -Since the vinyl acetate copolymer is obtained as a dispersion dispersed in water, it can be used as it is for the antistatic agent of the present invention.
  • the mixing ratio of ethylene, vinyl acetate and the (B2-b) ethylenically unsaturated monomer (ethylene: vinyl acetate: B2-b) is 5: 94.8: 0.2 to 40 : 52: 8 is preferable.
  • the amount of the (B2-b) ethylenically unsaturated monomer used is derived from the (B2-b) ethylenically unsaturated monomer in the obtained (B3) ethylene-vinyl acetate copolymer.
  • the amount of the anionic hydrophilic group is preferably from 0.1 to 5% by mass, and more preferably from 0.25 to 2.5% by mass.
  • (B3) ethylene-vinyl acetate copolymer other copolymerizable monomers may be copolymerized within a range in which the effect of the present invention is not inhibited.
  • examples of such monomers include (meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, and ethyl (meth) acrylate; vinyl esters such as vinyl versatate. Vinyl chloride; styrene and the like.
  • the content is 8 mass% or less with respect to the total amount of all the monomers.
  • (B3) ethylene-vinyl acetate copolymer according to the present invention commercially available products may be used.
  • EXEVAL trade name, manufactured by Kuraray Co., Ltd.
  • Rikabond BA-53, BA-58 In either case, a trade name, manufactured by Chuo Rika Kogyo Co., Ltd. can be used.
  • (B) anionic aqueous resin according to the present invention from the viewpoint that the stretchable followability is further improved and the adhesion of the resulting antistatic layer to the substrate tends to be further improved, (B1 It is preferably at least one of water-based polyurethane resin and (B2) water-based poly (meth) acrylic resin, and more preferably (B1) water-based polyurethane resin.
  • the (C) aqueous resin according to the present invention includes (C1) polyvinyl alcohol having a saponification degree of 65 to 90 mol%, (C2) an aqueous polyester resin containing 70 to 90% by mass of a polyoxyethylene chain, and (C3) a glucose ring. Selected from the group consisting of aqueous cellulose derivatives in which the hydrogen atom of the hydroxyl group is substituted with at least one of a methyl group and an acyl group having 2 to 4 carbon atoms and the degree of substitution is 1.3 to 2.0 At least one aqueous resin.
  • (C1) polyvinyl alcohol having a saponification degree of 65 to 90 mol% (hereinafter referred to as (C1) partially saponified polyvinyl alcohol)
  • the degree of saponification is 65 to 90 mol%.
  • the saponification degree is more preferably 70 to 85 mol% from the viewpoint that the stability tends to be further improved.
  • the saponification degree can be determined according to JIS K 6726 (1994).
  • the (C1) partially saponified polyvinyl alcohol according to the present invention preferably has a weight average molecular weight of 200,000 to 500,000, and more preferably 30,000 to 300,000. When the weight average molecular weight is within the above range, the agent stability and the stretch followability tend to be further improved.
  • (C1) partially saponified polyvinyl alcohol commercially available products may be used.
  • Gohsenol NK-05R, KP-08R, KL-03, KL-05, KH-17, KH-20, GH- 17, GM-14L, GL-03, GL-05 all trade names, manufactured by Nippon Synthetic Chemical Co., Ltd.
  • Gohsenol NK-05R, KP-08R, KL-03, KL-05, KH-17, KH-20, GH- 17, GM-14L, GL-03, GL-05 all trade names, manufactured by Nippon Synthetic Chemical Co., Ltd.
  • (C2) Water-based polyester resin containing 70 to 90% by mass of polyoxyethylene chain (hereinafter referred to as (C2) water-based polyester resin)
  • the polyoxyethylene chain content is 70 to 90% by mass relative to the total amount of the (C2) aqueous polyester resin.
  • the content of the polyoxyethylene chain is less than the lower limit, the stability of the antistatic agent is lowered, and the water dispersibility of the aqueous polyester resin is lowered.
  • the above upper limit is exceeded, the wettability and film-forming property of the antistatic agent are lowered.
  • the content of such polyoxyethylene chains is preferably 75 to 85% by weight from the viewpoint that the stability, wettability and film formability tend to be further improved.
  • the (C2) aqueous polyester resin according to the present invention preferably has a weight average molecular weight of 5,000 to 100,000 from the viewpoint that the stability of the antistatic agent tends to be further improved. More preferably, it is from 50,000 to 50,000.
  • the (C2) aqueous polyester resin according to the present invention is obtained by polycondensation of a polyol having a polyoxyethylene chain, a polycarboxylic acid, and, if necessary, a polyol other than the polyol having a polyoxyethylene chain. It is preferable. At this time, the polyoxyethylene chain in the obtained (C2) aqueous polyester resin is derived from the polyol having the polyoxyethylene chain.
  • Examples of such a polyol having a polyoxyethylene chain include polyethylene glycol and low molecular weight polyhydric alcohols obtained by block or random addition polymerization of ethylene oxide and, if necessary, propylene oxide or butylene oxide.
  • Examples of the low molecular weight polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neo Diols such as pentyl glycol; and triols such as glycerin, trimethylolethane, and trimethylolpropane.
  • a diol is preferable from the viewpoint that the stability, wettability, and film formability of the antistatic agent tend to be further improved.
  • the polyol having a polyoxyethylene chain preferably has a polyoxyethylene chain content of 60% by mass or more, more preferably 80% by mass or more, and still more preferably polyethylene glycol. Further, from the viewpoint that the stability, wettability and film-forming property of the antistatic agent tend to be further improved, the weight average molecular weight is preferably 600 to 10,000.
  • polycarboxylic acid examples include aromatic polycarboxylic acids, aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and anhydrides thereof; ester-forming derivatives such as halides and salts thereof; methyl terephthalate, diethyl terephthalate, and the like
  • ester-forming derivatives such as halides and salts thereof
  • methyl terephthalate, diethyl terephthalate, and the like The lower alkyl ester may be used, and one of these may be used alone, or two or more may be used in combination.
  • aromatic polycarboxylic acids and their anhydrides examples include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl.
  • Aromatic dicarboxylic acid such as dicarboxylic acid; aromatic dicarboxylic anhydride such as phthalic anhydride; 3 such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate) A functional or higher aromatic polycarboxylic acid; a trifunctional or higher functional aromatic polycarboxylic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride.
  • Examples of the aliphatic polycarboxylic acids and anhydrides thereof include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and hydrogenated dimer acid.
  • Saturated aliphatic dicarboxylic acid anhydrides such as succinic anhydride; unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, citraconic acid and dimer acid; maleic anhydride, itaconic anhydride, cytosanolic acid anhydride, etc.
  • Examples thereof include unsaturated aliphatic dicarboxylic acid anhydrides; tri- or higher functional aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and anhydrides thereof.
  • Examples of the alicyclic polycarboxylic acids and their anhydrides include 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, Examples thereof include alicyclic dicarboxylic acids such as cyclohexene dicarboxylic acid and 2,5-norbornene dicarboxylic acid, and anhydrides thereof.
  • polycarboxylic acids from the viewpoint that the stability, wettability and film-forming property of the antistatic agent tend to be further improved, aromatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, unsaturated aliphatic dicarboxylic acids, It is preferable to use alicyclic dicarboxylic acid and its anhydride.
  • polyols other than the polyol having a polyoxyethylene chain examples include aliphatic polyols, alicyclic polyols, and aromatic polyols.
  • the aliphatic polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, dimethylol heptane, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tripropylene glycol, polypropylene glycol, polytetra
  • aliphatic diols such as methylene glycol
  • aliphatic triols such as trimethylolethane, trimethylolpropane, glycer
  • alicyclic polyol examples include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, hydrogenated bisphenol A, or hydrogenated bisphenol S ethylene oxide adduct or propylene oxide addition.
  • alicyclic diols such as tricyclodecane diol, tricyclodecane dimethanol, and dimer diol.
  • aromatic polyol examples include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, bishydroxyethoxybenzene, hydroquinone, ethylene oxide adduct of 1,4-phenylene glycol; bisphenol A, Aromatic diols such as ethylene oxide adducts or propylene oxide adducts of bisphenol S, bisphenol A or bisphenol S can be mentioned.
  • diols such as aliphatic diols, alicyclic diols, and aromatic diols are used from the viewpoint that the stability, wettability, and film formability of the antistatic agent tend to be further improved. preferable.
  • the method for obtaining the (C2) aqueous polyester resin by polycondensation a known method can be employed without any particular limitation.
  • the amount of the polyol having the polyoxyethylene chain is obtained (C2 )
  • the amount of polyoxyethylene chain in the aqueous polyester resin is preferably 70 to 90% by mass, more preferably 75 to 85% by weight.
  • (C2) water-based polyester resin according to the present invention commercially available products may be used.
  • Plus Coat FR-550 and FR-627 both are trade names, manufactured by Kyoyo Chemical Industry Co., Ltd.
  • the weight average molecular weights of the partially saponified polyvinyl alcohol and the aqueous polyester resin are gel permeation chromatography (GPC) (“HLC-8020” manufactured by Tosoh Corporation; solvent: tetrahydrofuran; column: “TSK-GEL G5000HHR”. ”,“ TSK-GEL G4000HHR ”and“ TSK-GEL G3000HHR ”(each manufactured by Tosoh Corporation) are connected; temperature is 40 ° C .; speed is 1.0 ml / min) and converted to standard polystyrene. Can be obtained.
  • GPC gel permeation chromatography
  • the hydrogen atom of the hydroxyl group of the glucose ring is substituted with at least one of a methyl group and an acyl group having 2 to 4 carbon atoms, and the degree of substitution is 1. 3 to 2.0.
  • the substituent is preferably a methyl group from the viewpoint that the stability, wettability and film-forming property of the antistatic agent tend to be further improved.
  • the hydrogen atom of the remaining hydroxyl group of the glucose ring not substituted with a methyl group and / or an acyl group having 2 to 4 carbon atoms is —CH 2 CH (OH) CH 3 , It may be substituted with a hydroxyalkyl group having 2 to 4 carbon atoms such as —CH 2 CH 2 OH.
  • the degree of substitution means the average number of hydroxyl groups in which the hydrogen atom is substituted with a methyl group and / or an acyl group having 2 to 4 carbon atoms, among the three hydroxyl groups of the glucose ring.
  • the degree of substitution is less than the lower limit and / or exceeds the upper limit, the agent stability, wettability and film formability are lowered, and the water dispersibility of the aqueous cellulose derivative is significantly lowered.
  • the degree of substitution is J.P. G. Gobler, E .; P. Samsel, and G. H.
  • Such a (C3) aqueous cellulose derivative preferably has a viscosity of 20 to 5,000 mPa ⁇ s, more preferably 50 to 2,000 mPa ⁇ s.
  • a viscosity can be calculated
  • (C3) aqueous cellulose derivative according to the present invention commercially available products may be used.
  • Metroles SM series, SH series, SE series all are trade names, manufactured by Kyoyo Chemical Industry Co., Ltd.). Can be used.
  • the (C) aqueous resin according to the present invention is preferably the (C1) partially saponified polyvinyl alcohol from the viewpoint that the agent stability, wettability, and film forming property tend to be further improved.
  • the mass ratio (A: B) of the (A) cationic aqueous resin to the (B) anionic aqueous resin is preferably 90:10 to 20:80, 80:30 to 30:70 is more preferable, and 70:30 to 40:60 is more preferable.
  • the mass ratio is within the above range, more excellent stretch followability and agent stability are exhibited, and the antistatic property of the resulting antistatic film and the adhesion to the substrate tend to be further improved.
  • the content of the (C) aqueous resin is 5 to 60% by mass based on the total amount of the (A) cationic aqueous resin and the (B) anionic aqueous resin. It is preferably 25 to 50% by mass.
  • the content of the (C) aqueous resin is within the above range, better agent stability, wettability and film formability tend to be exhibited.
  • the antistatic agent of the present invention preferably further contains water or a mixed liquid mainly composed of water as a dispersion medium from the viewpoints of work environment, safety, environmental problems, and the like.
  • the total solid content of the (A) cationic aqueous resin, the (B) anionic aqueous resin, and the (C) aqueous resin is, for example, 0.02 to 10% by mass. It is done.
  • the solid content means a residue after the sample is allowed to stand at 105 ° C. for 3 hours.
  • Examples of the mixed solution include a mixed solution of water and an organic solvent compatible with water from the viewpoint of improving the storage stability and wettability of the antistatic agent.
  • Examples of the organic solvent include alcohols such as ethanol, isopropanol, ethylene glycol, and glycerin; ethers such as ethyl cellosolve, t-butyl cellosolve, propylene glycol monomethyl ether, and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; Examples include amines such as dimethylethanolamine and trimethanolamine; amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide. One of these may be used alone, or two or more may be used in combination. May be.
  • the antistatic agent of the present invention preferably contains 40% by mass or more of water.
  • the organic solvent The content is preferably 10% by mass or less.
  • the antistatic agent of the present invention may contain other components as necessary.
  • the other components include functional agents such as water and oil repellents, ultraviolet absorbers, mold release agents, and antifogging agents. Even if the antistatic agent of the present invention further contains the above functional drugs, the functions derived from these drugs (water / oil repellency, ultraviolet absorption, releasability, antifogging, etc.) are sufficiently exhibited. An antistatic layer that can be formed can be formed. Among these, the antistatic agent of the present invention preferably further contains a release agent.
  • As the water / oil repellent a conventionally known one can be used without particular limitation, and it may be fluorine or non-fluorine. Commercially available products may also be used.
  • Asahi Guard E-081, E-082, E-092, 500D all trade names, manufactured by Asahi Glass Co., Ltd.
  • Nuba N2114 trade names, Clariant Co., Ltd.
  • M guard PF-10, PF-11 both trade names, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
  • NK guard S-22, S-11, S-80, Neoseed NR-90, Adesso WR-1 and WR-3 both trade names, manufactured by Nikka Chemical Co., Ltd.
  • ultraviolet absorber conventionally known ones can be used without particular limitation, and examples thereof include benzotriazole-based, benzoate-based, benzophenone-based, cyanoacrylate-based, and phenyl salicylate-based ultraviolet absorbers.
  • Commercial products may also be used.
  • Tinuvin PS, 99-2, 384-2, 900, 928, 1130, 400, 405, 460, 479, 326 (all trade names, BASF Japan K.K.) Can be used.
  • the release agent conventionally known ones can be used without particular limitation, and examples include silicones, waxes, long-chain alkyl compounds, and fluorine-containing compounds.
  • silicones waxes, long-chain alkyl compounds, and fluorine-containing compounds.
  • Charine R-170EM, NE500, and FE-230N all trade names, manufactured by Nissin Chemical Industry Co., Ltd., from the viewpoint that superior release properties are exhibited in the obtained antistatic layer.
  • X-52-6015 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), R2701, DEHESIVE EM431, DEHESIVE 400E, DEHESIVE 920, DEHESIVE 924, DEHESIVE 927, DEHESIVE 929, DEHESIVE 430, DEHESIVE 420, all manufactured by Asahi Kasei Co., Ltd.
  • Silwet L-7210, Silwet L-7657, Silwet L-8500 (all trade names, manufactured by Momentive Performance Materials Japan GK) Silicone resin, Neoseed NR-90, Adesso WR-1, WR-3 (all trade names, manufactured by Nikka Chemical Co., Ltd.), PE wax MYE-35G, paraffin wax MYW-20 (all trade names, Aqueous long-chain alkyl compounds such as Maruyoshi Chemical Co., Ltd.), NKguard S-22, S-07, S-11, S-80 (all trade names, manufactured by Nikka Chemical Co., Ltd.), Unidyne Aqueous fluorine compounds such as TG-5541 (trade name, manufactured by Daikin Industries, Ltd.) and Fluorosurf FS-6130 (trade name, manufactured by Fluoro Technology Co., Ltd.) are preferred.
  • an aqueous silicone resin, an aqueous long-chain alkyl compound, and an aqueous fluorine compound aqueous means water-soluble or self-emulsifying (performance capable of being emulsified and dispersed without adding an emulsifier), Specifically, the concentration of the resin or the compound is 5% by mass, and each of the aqueous dispersions containing no emulsifier is prepared. Even if this is left at room temperature (about 25 ° C.) for 1 day, a precipitate is formed. It does not occur.
  • the release agent excludes the (A) cationic aqueous resin, the (B) anionic aqueous resin, and the (C) aqueous resin.
  • the antistatic agent of the present invention further contains these release agents, the content thereof is excellent in adhesion between the obtained antistatic layer and the base material, and the base material of the antistatic layer
  • the total mass of the (A) cationic aqueous resin, the (B) anionic aqueous resin and the (C) aqueous resin is 100 parts by mass.
  • the amount is preferably 50 to 500 parts by mass, and more preferably 100 to 200 parts by mass.
  • antifogging agent conventionally known antifogging agents can be used without particular limitation, and inorganic aqueous colloidal particles such as alumina, silica, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate are used as water.
  • distributed in the hydrophilic solvent is mentioned, Among these, a silica sol and an alumina sol can be used conveniently.
  • ferulic acid In addition to these components, ferulic acid, ferulic acid derivatives, antioxidants such as hindered phenol compounds, light stabilizers such as hindered amine compounds, surfactants, antifoaming agents and the like are further contained. Also good. Commercially available products may be used as appropriate.
  • the hindered phenolic compound (antioxidant) IRGANOX 1010 (trade name, manufactured by BASF Japan Ltd.) is used as the hindered amine compound (light stabilizer).
  • IRGANOX 1010 trade name, manufactured by BASF Japan Ltd.
  • CHIMASSORB944FDL both trade names, manufactured by BASF Japan Ltd.
  • the base material to which the antistatic agent of the present invention is used is not particularly limited, and can be applied to any base material that requires antistatic properties, and examples thereof include a resin molded body and a fiber molded body.
  • Examples of the form of the resin molding include thin articles such as films and sheets, and three-dimensional containers such as boxes and bottles.
  • the form of the resin molded body does not include the form listed in the following fiber molded body. Moreover, it does not restrict
  • the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene; polystyrene resins; styrene-acrylonitrile copolymer resins; ABS resins; polyester resins; polycarbonate resins; polyamide resins; A polyurethane resin is mentioned.
  • thermosetting resin an epoxy resin, a urethane resin, a thermosetting acrylic resin etc. are mentioned, for example.
  • the resin molded body may be molded from one of these resins, or may be molded from a combination of two or more, and other components such as the following fibers may further include It may be contained.
  • Examples of the form of the fiber molded body include yarn, woven fabric, knitted fabric, and non-woven fabric. Moreover, the artificial leather made from a nonwoven fabric, a urethane resin, etc. is also mentioned.
  • the fiber used as the material of the fiber molded body is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyester, nylon, acrylic, and polyolefin; semisynthetic fibers such as acetate; Examples thereof include regenerated fibers such as rayon and composite fibers thereof.
  • the antistatic agent of the present invention has excellent stability, wettability, film-forming property, stretch followability, can be applied to in-line coating methods, and is relatively less than before. Even in a small amount, it is possible to form an antistatic layer that has excellent adhesion to a substrate and heat resistance and can exhibit excellent antistatic properties even under low humidity. Therefore, it can be suitably used for the resin film that is the resin molded body.
  • the antistatic laminate of the present invention comprises a base material and an antistatic layer formed from the antistatic agent of the present invention on at least a part of the surface of the base material.
  • Such a laminate is not particularly limited, and can be an antistatic laminate using any substrate that requires antistatic properties.
  • an antistatic using the above resin molded body as the substrate.
  • the method for forming the antistatic layer on the surface of the substrate is not particularly limited, and a conventionally known method can be appropriately employed.
  • the method of the present invention can be applied to at least a part of the surface of the substrate.
  • the method of drying after providing an antistatic agent is mentioned.
  • the method for applying the antistatic agent to the surface of the resin molding is not particularly limited, and examples thereof include a bar coating method, a spray coating method, a roll coating method, a gravure coating method, an air knife coating method, a kiss coating method, and a brush treatment. , Coating by a pulverization process or the like.
  • the drying conditions at this time are not particularly limited, and are usually dried at a temperature of 50 to 250 ° C. for about 1 second to 5 minutes.
  • an in-line coating method can be applied.
  • the amount of the antistatic agent applied to the resin molded body is not particularly limited, and depends on the form and size of the base material.
  • the theoretical antistatic layer thickness is 0.001 to 5 ⁇ m.
  • the amount is preferably 0.002 to 3 ⁇ m, more preferably 0.005 to 0.05 ⁇ m.
  • the theoretical antistatic layer thickness means the thickness of the antistatic layer obtained after drying, that is, the thickness corresponding to the solid content of the applied antistatic agent.
  • an antistatic layer formed by a coating method it means a thickness obtained by reducing the thickness corresponding to the solid content of the antistatic agent in accordance with the draw ratio.
  • the antistatic agent of the present invention has excellent stability, wettability, and film formability, and also has excellent antistatic properties, adhesion to a substrate, and heat resistance even in a relatively small amount as compared with conventional ones. It is possible to form an antistatic layer having For this reason, the application amount required in the conventional antistatic agent is an amount that gives a theoretical antistatic layer thickness of 1 ⁇ m or more, whereas the application amount of the antistatic agent of the present invention is smaller than that. And an antistatic layer thinner than the conventional one can be formed, and the appearance and the like of the substrate can be maintained well.
  • the method for applying the antistatic agent to the surface of the fiber molded body is not particularly limited.
  • the antistatic agent is dissolved in water or a mixed solution of water and alcohol such as methanol, ethanol, isopropyl alcohol.
  • the method of providing the diluted process liquid to a fiber molded object by a conventionally well-known padding process method, a crushing process method, a spray process method etc. is mentioned.
  • the concentration of the treatment liquid is, for example, a concentration at which the total solid content of the (A) cationic aqueous resin, the (B) anionic aqueous resin, and the (C) aqueous resin is 0.1 to 10% by mass, More preferably, the concentration is 0.6 to 2% by mass.
  • the drying conditions at this time are not particularly limited, and are usually dried at a temperature of 80 to 150 ° C. for about 1 to 10 minutes. Further, if necessary, after drying, a heat treatment (curing) may be performed at a temperature of 100 ° C. or higher, preferably at a temperature of about 140 to 180 ° C. for 10 seconds to 10 minutes, preferably about 30 seconds to 3 minutes. it can.
  • the amount of the antistatic agent applied to the fiber molded body is not particularly limited and can be appropriately adjusted according to the purpose of use, but the (A) cationic aqueous resin and the (B) anionic property.
  • the total amount of the solid content of the aqueous resin and the (C) aqueous resin is 0.01 to 3% by mass, preferably 0.05 to 0.7% by mass, based on the mass of the fiber.
  • the antistatic layer of the present invention is formed using the antistatic agent further containing the functional agent (water / oil repellent, ultraviolet absorber, release agent, antifogging agent, etc.). Can sufficiently exhibit functions derived from these agents (water / oil repellency, ultraviolet absorption, releasability, antifogging, etc.).
  • the antistatic agent contains a release agent, and the antistatic layer has releasability. In this case, from the viewpoint that excellent adhesion is exhibited between the base material and the antistatic layer, and on the other hand, excellent releasability is exhibited on the surface opposite to the base material.
  • the prevention layer is preferably obtained by drying after applying the antistatic agent of the present invention to at least a part of the surface of the substrate.
  • the base material is a resin film
  • the antistatic layer is provided on at least one surface of the resin film. It can be set as the formed antistatic film.
  • a so-called plastic film can be preferably used from the viewpoint that electrical resistance is high and antistatic properties are particularly required.
  • a conventional plastic film can be used without any particular limitation, and examples thereof include various plastic films such as polyester, polyethylene, polypropylene, polystyrene, and polyvinyl chloride.
  • the resin film is preferably a polyester film from the viewpoint of better adhesion with the antistatic agent of the present invention.
  • the resin film may be unstretched, uniaxially stretched, or biaxially stretched.
  • the method for forming the antistatic layer is not particularly limited, and examples thereof include the same method as the method for forming the antistatic layer on the surface of the resin molded body.
  • the drying conditions are preferably about 30 seconds to 5 minutes at a temperature of 50 to 250 ° C.
  • the in-line coating method is a method of performing the coating (coating) in the film manufacturing process. Specifically, after the resin as a film material is melt-extruded, it is biaxially stretched, heat-fixed and wound up. In this method, the film is coated at an arbitrary stage.
  • the antistatic agent of the present invention a substantially amorphous unstretched sheet obtained by rapid cooling after melting, and then a uniaxially stretched film stretched in the machine direction (MD direction) or the transverse direction (TD direction)
  • MD direction machine direction
  • TD direction transverse direction
  • the film may be coated on any of the biaxially stretched films before heat setting, from the viewpoint that the film formation and the application of the antistatic agent can be performed simultaneously, and the manufacturing cost can be reduced. It is preferable to coat a uniaxially stretched film.
  • Such a biaxially stretched antistatic film can be produced by the method for producing a biaxially stretched antistatic film of the present invention.
  • the method for producing the biaxially stretched antistatic film of the present invention comprises: A step of uniaxially stretching an unstretched resin film to obtain a uniaxially stretched resin film; Forming an antistatic layer from the antistatic agent of the present invention on at least one surface of the uniaxially stretched resin film to obtain a uniaxially stretched antistatic film; and A step of obtaining a biaxially stretched antistatic film by stretching in a direction perpendicular to the direction of uniaxial stretching; It is characterized by including.
  • the unstretched resin film examples include a substantially amorphous unstretched sheet obtained by melting and quenching the resin used as a film material such as polyester resin.
  • the uniaxial stretching method examples include an inflation method, a die method, a calendar method, and the like, and a die method can be particularly preferably used.
  • the die method can be classified into a straight die method, a crosshead die method, a flat die method, and a special die method according to the shape of the die, and among them, the flat die method can be particularly preferably used.
  • the method for forming the antistatic layer is as described above.
  • the stretching may be performed in a direction orthogonal to the direction of the uniaxial stretching.
  • the direction orthogonal to the direction intersects the direction of the uniaxial stretching in a range of 90-5 ° to 90 + 5 °.
  • the direction of the axis examples include a tenter method.
  • the stretching temperature is usually about 90 to 250 ° C.
  • excellent stretchability is exhibited even when stretched at such a high temperature. It is possible to form an antistatic layer having
  • a fixing treatment is further performed by heating at 90 to 250 ° C for 1 second to 3 minutes.
  • the thickness of the antistatic layer in the antistatic film of the present invention obtained in this way is not particularly limited and cannot be generally specified because it is appropriately adjusted according to the purpose.
  • the thickness of the prevention layer is preferably 0.001 to 5 ⁇ m, more preferably 0.002 to 3 ⁇ m, and further preferably 0.005 to 0.05 ⁇ m. When the in-line coating method is adopted, it is more preferably 0.001 to 5 ⁇ m. Since the antistatic agent of the present invention has excellent stability, wettability, film-forming property and stretchability, the antistatic agent and the base having excellent antistatic property even if the amount of the antistatic agent used is small. An antistatic layer having adhesion to the material and heat resistance can be formed.
  • the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
  • evaluation of the antistatic agent obtained by each Example and the comparative example was performed by the method shown below, respectively.
  • the antistatic film used for each evaluation was manufactured by the method of manufacturing method 1 or manufacturing method 2 using the following uniaxially stretched PET film or biaxially stretched PET film, respectively.
  • ⁇ Uniaxially stretched PET film> a polyester chip (bottle grade, manufactured by Ryori Enterprise Co., Ltd.) was sufficiently dried, then melted by heating at 280 to 300 ° C., and extruded from a T-shaped base into a sheet shape. This sheet was wound around a mirror-cooled drum having a surface temperature of 20 ° C. while using an electrostatic adhesion method, and cooled and solidified to produce an unstretched polyester film. Next, the obtained unstretched polyester film was stretched 3.3 times in the MD direction (longitudinal (film length) direction) while passing through a 85 ° C. heated roll group, and a uniaxially stretched polyester film (hereinafter referred to as uniaxial). A stretched PET film) was obtained.
  • Lumirror T60 manufactured by Toray Industries, Inc., film thickness 25 ⁇ m, hereinafter referred to as biaxially stretched PET film
  • ⁇ Production Method 1 Antistatic Film 1> After applying the antistatic agent obtained in each Example and Comparative Example on one surface of the biaxially stretched PET film so that the thickness of the coating layer is about 12 ⁇ m using a # 5 bar coater The film was dried at 120 ° C. for 2 minutes to form an antistatic layer, whereby an antistatic film 1 was obtained.
  • ⁇ Production Method 2 Antistatic Film 2> First, the uniaxially stretched PET film was cut so as to be 30 mm in the MD direction and 90 mm in the TD direction (lateral (film width) direction), and on each side, a # 5 bar coater was used. And after apply
  • Agent stability The antistatic agent obtained in each Example and Comparative Example was allowed to stand at 45 ° C., and the state was observed. A: No sedimentation for 1-2 weeks B: No sedimentation for 3-6 days C: Evaluation was performed according to sedimentation for 1-2 days.
  • the antistatic film 1 was produced using the antistatic agent obtained in each Example and Comparative Example, and the surface resistivity was measured according to JIS C 2151 (2006). Each measurement was carried out by leaving the obtained antistatic film 1 at 20 ° C. and 40% RH for 24 hours to adjust the humidity, and under the same conditions, a resistance meter (manufactured by Toa Denpa Kogyo Co., Ltd., SM-8210 ultra-super insulation meter) and a sample chamber (manufactured by Advantest Corporation, TR42). It shows that antistatic property is excellent, so that the value of surface resistivity is small.
  • Adhesiveness to base material The above-mentioned antistatic film 1 was prepared using the antistatic agent obtained in each Example and Comparative Example, and each antistatic layer was erased (MONO eraser manufactured by Dragonfly Pencil Co., Ltd.). Then, the surface resistivity of the portion was measured by the same method as in the above (4) Antistatic test. Measure the number of frictions when the surface resistivity is 10 12 ⁇ or more and use the following criteria: A: Friction number for surface resistivity is equal to or greater than 10 12 Omega is needed more than 10 times B: Friction number for surface resistivity is equal to or greater than 10 12 Omega are required more than five times C: surface resistivity The number of frictions is required to be 3 times or more for the rate to be 10 12 ⁇ or more. D: Evaluation was performed as the number of frictions was less than 3 and the surface resistivity was 10 12 ⁇ or more. In addition, the number of times of friction means rubbing once in one direction with the eraser.
  • the antistatic film 1 was prepared using the antistatic agent obtained in each of the examples and comparative examples, and after standing at 120 ° C. for 100 hours, the antistatic property was 4) Measured in the same manner as the antistatic test, and the following criteria: A: 10 9 to 10 10 ⁇ B: More than 10 10 ⁇ and less than 10 12 ⁇ C: Evaluated according to 10 12 ⁇ or more.
  • the antistatic film 2 is produced using the antistatic agent obtained in each of the examples and comparative examples, and (i) an antistatic layer (before biaxial stretching) and (ii) antistatic.
  • the antistatic property of the layer (after biaxial stretching) was measured by the same method as in the above (4) antistatic property test.
  • a water repellent and oil repellency test apparatus used in the JIS L 1092 (2009) spray method is applied to the antistatic film 1 produced using the antistatic agent obtained in Example 27. And tested in accordance with the spray method, using the following criteria: A: The antistatic layer does not whiten when wet and water droplets do not adhere B: The antistatic layer does not whiten when wet, but small water droplets remain B ⁇ : The antistatic layer partially whitens when wet C: Antistatic The layer is whitened by more than half when wet, and the antistatic layer falls off in less than 20% of the total. D: The antistatic layer is almost whitened by wetness, and the antistatic layer falls off over 20% of the total. Evaluated according to.
  • one drop (about 0.05 g) of the minimum series of oil agent in the following series test oil agent was dropped on the surface of the antistatic layer of the antistatic film 1,
  • the contact angle of the oil droplet immediately after dropping is 90 degrees or more visually, and the oil droplet does not spread even after 1 minute, and the contact angle of 90 degrees or more is maintained visually, it is one larger series.
  • the oil agent was dropped in the same manner, and the state of the oil droplets was observed.
  • the contact angle of the oil droplet immediately after dropping is 90 degrees or less visually or 90 degrees or more, but the oil droplet gradually spreads within 1 minute, the series of the oil agent is determined as the antistatic property of the test object.
  • the antistatic film 1 produced using the antistatic agent obtained in Example 28 and the polyester knit cloth dyed black are used, and the antistatic layer of the antistatic film 1 is a polyester.
  • the layers were overlapped so as to be on the knit cloth side, and irradiated with light at 63 ° C. for 6 hours from the antistatic film side using a carbon arc lamp light resistance tester (manufactured by Suga Test Instruments Co., Ltd.).
  • the degree of discoloration of the polyester knit cloth was evaluated by making a visual series (grade 5 to 1 grade) judgment with a gray scale for discoloration (JIS L 0804 (2004)). The larger the series, the better the light fastness.
  • the ease with which the cured adhesive peels from the antistatic film is determined by the following criteria: A: B cured adhesive is spontaneously peeled off from the film: B of the cured adhesive is peeled off and picking up with tweezers -: C be easily peeled and Kosogu spatula from the edge of the cured adhesive: When peeled off with a spatula from the edge of the cured adhesive, a part of the unpeeled part remains. D: Evaluation was performed as the cured adhesive could not be peeled off.
  • the antistatic agent of each Example and the comparative example was prepared using the compound obtained by the following synthesis example, and the compound of a commercial item.
  • solid content of each sample means the residue after leaving a sample to stand at 105 degreeC for 3 hours.
  • An aqueous dispersion of a cationic aqueous resin 1 comprising a repeating unit which is a group represented by 4- O—C 2 H 4 — and X ⁇ is a chlorine ion (Cl ⁇ ) was obtained.
  • the solid content concentration of the obtained aqueous dispersion is 60% by mass
  • the content of nitrogen atoms derived from the quaternary ammonium group in the cationic aqueous resin 1 is 10.3% by mass
  • the weight average molecular weight of the cationic aqueous resin 1 is 15,000.
  • the resulting aqueous dispersion has a solid content concentration of 41% by mass, the content of nitrogen atoms derived from the quaternary ammonium group in the cationic aqueous resin 2 is 8.5% by mass, and the weight average molecular weight of the cationic aqueous resin 2 is 280,000.
  • R 5 is a methyl group in the formula (3-1)
  • X - is a chlorine ion (Cl -)
  • R 6 is a methyl group in the repeating unit and the formula (3-2) is, X -
  • An aqueous dispersion of cationic aqueous resin 3 having a repeating unit in which is a chloride ion (Cl ⁇ ) was obtained.
  • the resulting aqueous dispersion had a solid content concentration of 45.8% by mass, the nitrogen atom content derived from the quaternary ammonium group in the cationic aqueous resin 3 was 7.9% by mass, and the weight average of the cationic aqueous resin 3 The molecular weight was 150,000.
  • R 5 is a methyl group in the formula (3-1)
  • X - is a chlorine ion (Cl -)
  • R 6 is a methyl group in the repeating unit and the formula (3-2) is, X -
  • An aqueous dispersion of a cationic aqueous resin 4 having a repeating unit in which is a chloride ion (Cl ⁇ ) was obtained.
  • the solid content concentration of the obtained aqueous dispersion was 45.8% by mass
  • the nitrogen atom content derived from the quaternary ammonium group in the cationic aqueous resin 4 was 6.4% by mass
  • the weight average of the cationic aqueous resin 4 The molecular weight was 180,000.
  • the solid concentration of the obtained aqueous dispersion is 60% by mass
  • the content of nitrogen atom derived from the quaternary ammonium group in the cationic aqueous resin 5 is 10.3% by mass
  • the weight average molecular weight of the cationic aqueous resin 5 is 200,000.
  • aqueous polyurethane resin 1 poly(polyester-based aqueous polyurethane resin having a carboxyl group and / or a group in which it was neutralized).
  • a dispersion aqueous polyurethane resin solid content concentration: 36.5% by mass was obtained.
  • the anionic hydrophilic group content in the obtained aqueous polyurethane resin 1 was 1.2% by mass.
  • aqueous polyurethane resin 2 a polycarbonate-based aqueous polyurethane resin having a carboxyl group and / or a group in which it was neutralized.
  • An aqueous dispersion (aqueous polyurethane resin solid content concentration: 40% by mass) was obtained.
  • the anionic hydrophilic group content in the obtained aqueous polyurethane resin 2 was 1.45% by mass.
  • aqueous polyacrylic resin 1 aqueous polyacrylic resin having a carboxy group and / or a group in which it is neutralized
  • Acrylic resin solid content concentration: 51.2 mass%) was obtained.
  • the anionic hydrophilic group content in the obtained aqueous polyacrylic resin 1 was 2.1% by mass, and the weight average molecular weight of the aqueous polyacrylic resin 1 was 180,000.
  • the solution was added dropwise at 80 to 90 ° C. over 3 hours, and then reacted at 80 ° C. for 4 hours.
  • 203 g of ion-exchanged water was added and cooled to 40 ° C. or lower to obtain an aqueous dispersion of an aqueous resin.
  • the obtained aqueous dispersion had a solid content concentration of 60%, and the weight average molecular weight of the aqueous resin was 200,000.
  • the nitrogen atom derived from the quaternary ammonium group was not contained in the obtained aqueous resin.
  • the obtained compound was cooled to room temperature and dispersed in 2000 g of ion exchange water to obtain an aqueous dispersion of an aqueous polyester resin having a sulfo group and / or a group in which it was neutralized.
  • the content of the anionic hydrophilic group in the obtained aqueous polyester resin was 1.0% by mass, and the weight average molecular weight of the aqueous polyester resin was 15,000.
  • Example 1 Cationic aqueous resin 1 obtained in Synthesis Example 1, aqueous polyurethane resin 1 obtained in Synthesis Example 6, and partially saponified polyvinyl alcohol (partially saponified PVA1, Gohsenol KP-08R (trade name), Nippon Synthetic Chemical Industry Co., Ltd. ), Saponification degree: 71 to 73.5 mol%) is dispersed or dissolved in ion-exchanged water so that the solid concentration is 5% by mass, and these are added to the ion-exchanged water and mixed with stirring. An antistatic agent was prepared.
  • the cationic aqueous resin 1 was 0.8 parts by mass
  • the aqueous polyurethane resin 1 was 0.1 parts by mass
  • the PVA-1 was 0.2 parts by mass.
  • Table 1 shows the theoretical antistatic layer thickness of the antistatic layer in each film produced in Production Example 1 and Production Example 2 using the obtained antistatic agent (the thickness of the obtained antistatic layer). Itself).
  • Examples 2 to 32 Comparative Examples 1 to 10.
  • An antistatic agent was obtained in the same manner as in Example 1 except that the composition of the antistatic agent was changed to the compositions shown in Tables 1 to 6.
  • the evaluation results of the obtained antistatic agents are shown in Tables 1 to 6 together with the compositions of the antistatic agents.
  • Table 5 also shows the evaluation results for films (raw films) obtained in the same manner as the films in each evaluation except that no antistatic agent was applied.
  • Tables 1 to 6 show the theoretical antistatic layer thickness of the antistatic layer in each film produced in Production Example 1 and Production Example 2 using each obtained antistatic agent (the obtained antistatic layer). Are shown together.
  • Cationic aqueous resin 6 PAS-H-5L (trade name); manufactured by Nitto Bo Medical Co., Ltd .
  • R 5 in formula (3-1) is a methyl group
  • a cationic aqueous resin comprising a repeating unit in which X ⁇ is chlorine ion (Cl ⁇ ); content of nitrogen atom derived from quaternary ammonium group: 8.7% by mass; weight average molecular weight: 30,000
  • EAV copolymer 1 ethylene-vinyl acetate copolymer, Rikabond BA-53 (trade name), manufactured by Chuo Rika Kogyo Co., Ltd., an anionic hydrophilic group (carboxy group and / or it was neutralized) Group) content: 0.8-2.0 mass%
  • Partially saponified PVA2 Gohsenol KL-05R (trade name), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of saponification: 78.5 to 82.0 mol%
  • NK Guard S-22 (trade name), manufactured by Nikka Chemical Co., Ltd.
  • UV absorber Tinuvin 326 (trade name), manufactured by BASF Japan Ltd.
  • Release agent DEHESIVE 400E (product) Name), manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
  • Antifogging agent Snowtex 20 (trade name), manufactured by Nissan Chemical Industries, Ltd. Lauryldimethylethylamine etosulphate: Nitrogen atom content derived from quaternary ammonium group: 4.
  • Carboxymethylcellulose Na salt Sunrose PN20L (trade name), xanthan gum manufactured by Nippon Paper Chemicals Co., Ltd .: Roadpol 23 (trade name), Rhodia Nikka Co., Ltd. ) Made by company.
  • the antistatic agent of the present invention (Examples 1 to 32) has excellent stability, wettability, film formability, stretch followability, and in-line coating. It can be applied to other methods, and it has excellent adhesion to a base material and heat resistance even in a relatively small amount as compared with the conventional method, and under a relatively low humidity (40% RH) as compared with the conventional method. However, it was confirmed that an antistatic layer capable of exhibiting excellent antistatic properties can be formed. In addition, the antistatic layers obtained by the antistatic agents of the present invention (Examples 1 to 32) were not colored even after biaxial stretching.
  • an antistatic agent capable of forming an antistatic layer with a relatively small amount of conventional antistatic layer, which can exhibit excellent antistatic properties even under relatively low humidity compared to the prior art, It becomes possible to provide an antistatic laminate using the same and a method for producing a biaxially stretched antistatic film.
  • the antistatic agent of the present invention can form a thin and uniform antistatic layer, and can be suitably used particularly as an antistatic agent for a film, and loss of appearance of a resin film as a substrate. Can be suppressed. Furthermore, when used for a transparent polyester film or the like for a surface protective film of an optical component such as a polarizing plate, it is possible to suppress light path obstruction. In addition, for example, the rainbow color that appears on the oil film is caused by light interference that occurs when the film thickness is not less than visible light (approximately 350 nm or more) and is non-uniform, but the antistatic agent of the present invention Accordingly, it is possible to form an antistatic layer in which the generation of such rainbow colors is sufficiently suppressed.
  • the antistatic agent of the present invention coloring is sufficiently suppressed even after being heated at a relatively high temperature, and excellent antistatic properties, heat resistance, etc. Since it is possible to obtain an antistatic plastic product whose appearance is sufficiently maintained, it is possible to reduce the cost of cleaning when the used plastic product is cleaned and recycled. Moreover, since the antistatic agent of this invention can be applied also to an in-line coating method, the manufacturing cost at the time of using a biaxially stretched film as a base material can also be fully suppressed. Furthermore, since the antistatic agent of the present invention can use water as a dispersion medium, it can prevent deterioration of the working environment and environmental pollution such as air and water quality.
  • the antistatic agent of the present invention further contains other various functional agents (water / oil repellent, ultraviolet absorber, mold release agent, antifogging agent, etc.), the functions derived from these agents
  • An antistatic layer capable of sufficiently exhibiting water / oil repellency, ultraviolet absorption, releasability, antifogging, etc.

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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)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

La présente invention concerne un agent antistatique comprenant : une résine cationique comprenant un groupe ammonium quaternaire, par exemple une résine aqueuse cationique qui comprend comme motif répété la structure représentée par la formule générale (1) (dans la formule (1), R1 représente un groupe alkyle ou un groupe hydroxyalkyle, R2 représente un groupe alkylène, R3 représente un groupe alkylène pouvant comprendre un groupe éther, et X− représente un anion monovalent); une résine aqueuse anionique comprenant un groupe anionique hydrophile, par exemple une résine aqueuse polyuréthane contenant un groupe anionique hydrophile; et une résine aqueuse telle qu'un alcool polyvinylique à l'aide d'une saponification à 65-90 % en moles.
PCT/JP2013/076290 2012-09-27 2013-09-27 Agent antistatique, stratifié antistatique utilisant ledit agent, et procédé de fabrication d'un film antistatique étiré de manière biaxiale WO2014051065A1 (fr)

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JP2012214070A JP2014065869A (ja) 2012-09-27 2012-09-27 帯電防止剤、それを用いた帯電防止性積層体、及び２軸延伸帯電防止性フィルムの製造方法
JP2012-214070 2012-09-27

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Cited By (1)

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CN111893769A (zh) * 2020-08-20 2020-11-06 江苏阳光股份有限公司 一种抗静电毛涤精纺面料的生产工艺

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JP2015131922A (ja) * 2014-01-15 2015-07-23 東ソー株式会社 水系樹脂組成物、該組成物を用いた繊維性基材用接着剤、該接着剤を用いた積層体、及び積層体の製造方法
JP2016113499A (ja) * 2014-12-12 2016-06-23 日本エクスラン工業株式会社 樹脂成型体
CN116438078A (zh) * 2020-10-26 2023-07-14 东洋纺株式会社 易粘接性聚酯薄膜
JPWO2022219970A1 (fr) * 2021-04-12 2022-10-20

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JPH01156337A (ja) * 1987-12-14 1989-06-19 Diafoil Co Ltd 塗布層を有するポリエステルフイルム
JPH08157626A (ja) * 1994-12-07 1996-06-18 Teijin Ltd 制電性フイルム
JPH08157625A (ja) * 1994-12-06 1996-06-18 Teijin Ltd 制電性フイルム
JPH08224847A (ja) * 1994-12-06 1996-09-03 Teijin Ltd 易接着性白色ポリエステルフィルム
JP2002088180A (ja) * 2000-07-10 2002-03-27 Teijin Ltd 帯電防止性積層ポリエステルフィルム
WO2011135993A1 (fr) * 2010-04-28 2011-11-03 三菱樹脂株式会社 Film de polyester stratifié

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01156337A (ja) * 1987-12-14 1989-06-19 Diafoil Co Ltd 塗布層を有するポリエステルフイルム
JPH08157625A (ja) * 1994-12-06 1996-06-18 Teijin Ltd 制電性フイルム
JPH08224847A (ja) * 1994-12-06 1996-09-03 Teijin Ltd 易接着性白色ポリエステルフィルム
JPH08157626A (ja) * 1994-12-07 1996-06-18 Teijin Ltd 制電性フイルム
JP2002088180A (ja) * 2000-07-10 2002-03-27 Teijin Ltd 帯電防止性積層ポリエステルフィルム
WO2011135993A1 (fr) * 2010-04-28 2011-11-03 三菱樹脂株式会社 Film de polyester stratifié

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111893769A (zh) * 2020-08-20 2020-11-06 江苏阳光股份有限公司 一种抗静电毛涤精纺面料的生产工艺
CN111893769B (zh) * 2020-08-20 2024-03-08 江苏阳光股份有限公司 一种抗静电毛涤精纺面料的生产工艺

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