Classifications

• • 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
• • 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
  • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/025—Electric or magnetic 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • 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
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J125/00—Adhesives 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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
  • C09J125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to a laminated polyester film having a polyester film and a resin layer, and a coating composition.
• Thermoplastic resin films especially biaxially oriented polyester films, have excellent mechanical properties, electrical properties, dimensional stability, transparency, chemical resistance, etc., and therefore are used in many magnetic recording materials, packaging materials, etc. Widely used in applications.
• the biaxially oriented polyester film has a drawback that it does not have antistatic properties as it is.
• Antistatic property is a property imparted for the purpose of suppressing foreign matter defects caused by the adhesion of dust due to electric charge. For example, by imparting conductivity to the surface or inner layer of an insulating material such as a biaxially oriented polyester film. It can be imparted by neutralizing the bias of the charge.
• the method of providing a conductive coating layer on the surface of the polyester film to impart antistatic properties is easy to maintain various stable characteristics of the film, and various methods have been conventionally studied. It was.
• Patent Document 1 Conventional methods for imparting antistatic properties include a method of applying a styrene sulfonic acid copolymer, which is an ion conductive type antistatic agent, to a polyester resin (see, for example, Patent Document 1), or for the purpose of further enhancing the functionality.
• Patent Document 2 A technique focusing on the dispersibility of a styrene sulfonic acid copolymer and an acrylic resin (Patent Document 2) has been proposed.
• Patent Document 3 a method has been proposed in which an epoxy cross-linking agent is used in combination with a polythiophene-based conductive agent which is an electron conduction type antistatic agent to achieve both transparency and antistatic property of a coating film.
• Patent Document 4 a technique of using a polythiophene-based conductive agent and a hydroxy group-containing compound in combination for the purpose of improving antistatic property
• Patent Document 5 a technique of imparting durability to a boiling resistance test using a polythiophene-based conductive agent
• Patent Document 1 using an ion conductive type antistatic agent and Patent Document 2 which is an improvement thereof has insufficient antistatic property and tends to lose performance due to wear.
• Patent Document 3 the method described in Patent Document 3 and the techniques of Patent Documents 4 and 5 which are improvements thereof lack the antistatic property during the corona discharge treatment described later, and the antistatic component is dark blue. Therefore, there were problems such as being particularly conspicuous and affecting the characteristics in terms of quality control.
• Examples of applications in which an antistatic biaxially oriented polyester film is used include a protective film used for electronic parts and the like.
• the main use of the protective film is for cover tape and the like.
• cover tapes for electronic components in particular.
• the peeling charge of the cover tape causes the electronic component to inadvertently pop out and dissipate, or a discharge occurs between the charged tape and the electronic component, resulting in the electronic component. Occurs the problem of being electrically destroyed.
• the electronic component is packaged with the cover tape and the carrier tape, the electronic component is inspected from the cover tape side.
• the inspection of electronic parts is, for example, an inspection to check whether different types of components are mixed, whether the lead terminal of the IC chip is bent or the filling direction is incorrect.
• the transparency of the cover tape needed to be high.
• As the cover tape a highly transparent transparent polyester film, a transparent polyolefin film, or the like with antistatic treatment applied was used.
• JP-A-61-204240 Japanese Unexamined Patent Publication No. 2003-071995 Japanese Unexamined Patent Publication No. 2004-58648 Japanese Unexamined Patent Publication No. 2016-047881 Japanese Unexamined Patent Publication No. 2016-064625 Japanese Unexamined Patent Publication No. 2010-0113135
• the present invention eliminates the above-mentioned drawbacks and provides a laminated film that can be suitably used for a protective film, particularly a cover tape.
• the present invention has the following configuration in order to solve the above problems.
• the resin component (A) is 15% by weight or more and 75% by weight or less based on the total solid content weight, and polystyrene sulfonic acid and / or a salt thereof (B) is 15% by weight or more and 50% by weight based on the total solid content weight. % Or less coating composition.
• the laminated polyester film of the present invention has excellent antistatic properties, and the antistatic properties are less likely to deteriorate due to wear during transportation in the processing process and surface treatment such as corona discharge treatment.
• the laminated polyester film of the present invention can be used as a protective film used for electronic parts and the like, and can be particularly preferably used as a cover tape.
• the laminated polyester film of the present invention is a laminated polyester film having a polyester film and a resin layer (X), has a resin layer (X) on at least one surface layer, and has a surface specific resistance value (X) of the resin layer (X).
• R X) is 10 6 ⁇ / ⁇ or more, and 10 12 ⁇ / ⁇ or less, the surface ratio of the R X, a resin layer under the following conditions (resin layer after the surface has been worn process X) (X) the value of the ratio R Y / R X of the resistance value (R Y) is 5.0 or less.
• the wear treatment referred to here means that the surface of the resin layer (X) of the laminated polyester film is reciprocated 10 times on the surface of the resin layer (X) using a non-woven fabric (Hizegase NT-4 manufactured by Ozu Corporation) at a load of 20 g / cm 2. Indicates wear.
• Surface specific resistance of the resin layer (X) (R X) is, 10 6 ⁇ / ⁇ or more, if it is 10 12 ⁇ / ⁇ or less, can be a polyester film having a high antistatic performance. Further, if the value of the ratio R Y / R X of the surface resistivity values before and after the wear process of 5.0 or less, it is possible to suppress a reduction in antistatic performance due to wear during transportation. On the other hand, when the value of R Y / R X exceeds 5.0, since the antistatic property is lowered gradually, practically, there is a problem.
• the antistatic property is lowered due to friction in the processing step of forming a plurality of layers such as a primer and a sealant in the process of producing the cover tape.
• a method for reducing the value of R Y / R X for example, adjustment of the amount of the crosslinking component in the coating composition for forming the resin layer (X), the mixing ratio of the conductive material and the crosslinking component and materials It is possible to adjust by combining the material type and preparation conditions such as control of the dispersed state of the conductive component by controlling the seed and drying / stretching, coating thickness and surface shape.
• R X Surface specific resistance of the resin layer (X) (R X) is, 1.5 ⁇ 10 6 ⁇ / ⁇ or more and 5.0 ⁇ 10 9 ⁇ / ⁇ or less. Also, R Y / R X is preferably 4.5 or less, more preferably 3.0 or less, and more preferably 1.0 or more and 2.0 or less.
• the surface resistivity (R X) and a surface resistivity value of the resin layer resin layer after corona discharge treatment on the surface opposite to the surface having the (X) (X) (R Z ) ratio R Z / R X and is preferably not 10.0. If the ratio R Z / R X exceeds 10.0 may achieve both adhesion and antistatic polyester film and various functional layers it becomes difficult.
• the laminated polyester film is placed on the ground plate so that the resin layer (X) faces upward, the corona discharge treatment output is 100 W, the discharge gap with the ceramic electrode is 1 mm, and the electrode moving speed is 1 m / min.
• the corona discharge treatment is performed on the surface opposite to the surface having the resin layer (X) when the number of treatments is one.
• the corona discharge treatment can be performed using, for example, the corona surface modification evaluation device TEC-4AX manufactured by Kasuga Electric Co., Ltd.
• Method of reducing the value of R Z / R X for example, to select an appropriate conductive material species as a conductive material species to be contained in the resin layer (X), crosslinking of the coating composition for forming the resin layer (X) It is possible to adjust by controlling the compounding ratio of the components, controlling the dispersed state of the conductive components by controlling the drying and stretching, and controlling the coating thickness and the uneven distribution state in the thickness direction.
• R X Surface resistivity ratio of the surface specific resistance of the resin layer (X) Resin layer after corona discharge treatment on the surface opposite to the surface having the (X) and (R Z) R Z / R X Is more preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 1.0 or more and 2.0 or less.
• the resin layer (X) of the laminated polyester film of the present invention preferably has an average surface roughness Ra of 3 nm or more and 10 nm or less measured in a range of 1 ⁇ m square.
• Ra is less than 3 nm, the slipperiness of the resin layer (X) is insufficient, so that the surface of the resin layer (X) is worn out due to the lack of slipperiness, and the antistatic property is likely to decrease. In some cases. On the other hand, if it exceeds 10 nm, the transparency may decrease.
• Examples of the method for controlling the surface center line average roughness Ra of the resin layer (X) include a method of adding a particle material to the resin layer (X), a method of adding particles to a polyester base material, and a method of drying and stretching the resin layer. Examples thereof include a method of giving a shape to the surface by control.
• the method of controlling the surface center line average roughness Ra of the resin layer (X) is a method of adding particles to a polyester base material from the viewpoint of maintaining the abrasion resistance of the coating film, and a method of controlling drying and stretching of the resin layer on the surface. A method of imparting a shape is preferable.
• the coefficient of kinetic friction between the surface of the resin layer (X) of the laminated polyester film of the present invention and the opposite surface is 0.5 or less. If the coefficient of kinetic friction exceeds 0.5, the slipperiness may be insufficient and the antistatic property may be easily lowered.
• the lower limit is not particularly limited, but the practical lower limit of measurement is about 0.01. The details of the method for measuring the coefficient of dynamic friction will be described later.
• the coefficient of kinetic friction between the surface of the resin layer (X) of the laminated polyester film of the present invention and the opposite surface is more preferably 0.05 or more and 0.4 or less.
• the resin layer (X) of the laminated polyester film of the present invention preferably has a resin component (A).
• the resin used as the resin component (A) has a glass transition temperature (Tg) of preferably 40 ° C. or higher and 120 ° C. or lower, more preferably 60 ° C. or higher and 120 ° C. or lower, and particularly preferably 70 ° C. or higher and 120 ° C. or lower.
• Tg glass transition temperature
• the ratio R Y / R X value and it becomes easy to adjust the value of the ratio Rz / R X of the surface resistivity values before and after the corona discharge treatment. Further, when manufactured by using the resin layer (X) in-line coating method, deterioration of quality due to cracks and the like can be eliminated. The method for measuring the glass transition temperature (Tg) will be described later.
• Examples of the resin used as the resin component (A) include acrylic resin, polyester resin, polyurethane resin, melamine resin and epoxy resin, and one type or two or more types can be used in combination.
• the value of the ratio R Y / R X of the surface resistivity values before and after abrasion process, and from the viewpoint of adjusting the value of the ratio R z / R X of the surface resistivity values before and after the corona discharge treatment an acrylic resin, a polyester resin, a polyurethane Resin is preferable, and acrylic resin is particularly preferable.
• the acrylic resin for example, an acrylic resin emulsion dispersed in water can be used, and the dispersion diameter thereof is preferably 20 to 200 nm, more preferably 30 to 100 nm.
• the dispersion diameter of the acrylic resin emulsion dispersed in water is 20 to 200 nm, it is desirable for finely dispersing other resins.
• the monomer component constituting the acrylic resin is not particularly limited, but for example, alkyl acrylate, alkyl methacrylate (the alkyl group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl).
• Propyl group-containing monomers acrylic acid, methacrylic acid and monomers containing carboxyl groups such as salts thereof (lithium salt, sodium salt, potassium salt, etc.) or salts thereof can be used, and these may be one or two. It is copolymerized using more than a seed. In addition, they can be used in combination with other types of monomers.
• examples of other types of monomers include epoxy group-containing monomers such as allylglycidyl ether, crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.).
• Monomers containing carboxyl groups such as or salts thereof, monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, Alkyl maleic acid monoesters, alkyl fumalic acid monoesters, acrylonitriles, methacrylonitriles, alkyl itaconic acid monoesters, vinylidene chlorides, vinyl chlorides, vinyl acetates and the like can be used. Further, modified acrylic copolymers, for example, block copolymers modified with polyester, urethane, epoxy, etc., graft copolymers, and the like can also be used.
• Preferred acrylic resins used in the present invention include copolymers selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid.
• emulsion polymerization, suspension polymerization and the like are usually preferably used.
• the polyester resin used as the resin component (A) in the present invention has an ester bond in the main chain or the side chain, and is obtained by polycondensing a dicarboxylic acid and a diol.
• the carboxylic acid component constituting the polyester resin aromatic, aliphatic, alicyclic dicarboxylic acids and trivalent or higher valent carboxylic acids can be used.
• aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2. -Bisphenoxyetane-p, p'-dicarboxylic acid, phenylindandicarboxylic acid and ester-forming derivatives thereof can be used.
• aliphatic and alicyclic dicarboxylic acids examples include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecandioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid.
• 1,4-Cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.
• glycol component of the polyester resin ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3- Diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-trimethyl-1,6-hexanediol,
• the polyester resin used as the resin component (A) in the present invention is preferably used as an aqueous solution dissolved or dispersed in water.
• Examples of the compound containing a sulfonic acid base include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, and 2-sulfo.
• Alkali metal salts such as -1,4-bis (hydroxyethoxy) benzene, alkaline earth metal salts, and ammonium salts can be used.
• Examples of the compound containing a carboxylic acid base include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2, 3,4-Butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7 -Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimericate, 2,2', 3,3'-diphenyltetracarboxylic acid, thiophene-2,3,4,5- Examples thereof include alkali metal salts such as tetracarboxylic acid and ethylene tetracarboxylic acid, alkaline earth metal salt
• polyester resin used as the resin component (A) in the present invention modified polyester copolymers, for example, block copolymers modified with acrylic, urethane, epoxy, etc., graft copolymers, and the like can also be used.
• the polyester resin used as the resin component (A) is produced by a method such as a direct esterification reaction of a dicarboxylic acid component and a glycol component, or a polycondensation reaction of a reaction product obtained by a transesterification reaction. Can be done.
• the reaction catalyst for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound and the like can be used.
• the intrinsic viscosity of the polyester resin used as the resin component (A) is preferably 0.3 dl / g or more, more preferably 0.35 dl / g or more in terms of adhesiveness.
• polyurethane resin used as the resin component (A) in the present invention examples include a water-soluble or water-dispersible polyurethane resin having an anionic group, and the main constituent components are a polyol compound and a polyisocyanate compound.
• the reaction product is the basic structure.
• polyol compound examples include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, and polycaprolactone.
• Polyhexamethylene adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin, acrylic polyol and the like can be used.
• polyisocyanate compound for example, tolylene diisocyanate, hexamethylene diisocyanate, phenylenedi isocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, etc. can be used.
• the main constituents of the polyurethane resin may contain a chain length extender or a cross-linking agent in addition to the polyol compound and the polyisocyanate compound.
• a chain extender or cross-linking agent ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine and the like can be used.
• a carboxylic acid group, a sulfonic acid group, or a sulfuric acid semi-ester group, and ammonium salts, lithium salts, sodium salts, potassium salts and the like thereof can be used. It can. Particularly preferred are sulfonic acids and / or sulfonic acid bases.
• the amount of anionic groups in the polyurethane resin used as the resin component (A) is preferably 0.05% by weight to 15% by weight from the viewpoint of suppressing blocking.
• the polyurethane resin having an anionic group is, for example, a method of using a compound having an anionic group in a polyol, a polyisocyanate, a chain extender or the like, or reacting an unreacted isocyanate group of the produced urethane resin with a compound having an anionic group. It can be produced by a method of reacting a specific compound with a group having an active hydrogen of a urethane resin.
• a polyurethane resin having an anionic group is a resin composed of a polyol having a molecular weight of 300 to 20000, a polyisocyanate, a chain length extender having a reactive hydrogen atom, a group reacting with the isocyanate group, and a compound having at least one anionic group. Is preferable.
• a functional group such as a carboxyl group, a hydroxyl group, a methylol group or an amide group is introduced into the acrylic resin by copolymerization, and a cross-linking reaction with the functional group is carried out. What you get can be mixed. In this case, by using the specific acrylic resin described above, the effect of increasing the reaction efficiency with the cross-linking agent and improving the water resistance and heat resistance of the laminated film is exhibited.
• cross-linking agents examples include melamine-based cross-linking agents, oxazoline-based cross-linking agents, isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, methylolated or alkylolized urea-based, acrylamide-based, and polyamide-based resins. Amidoepoxy compounds, various silane coupling agents, various titanate-based coupling agents and the like can be used. In particular, melamine-based cross-linking agents and oxazoline-based cross-linking agents are preferable.
• the resin layer (X) of the present invention preferably contains polystyrene sulfonic acid and / or a salt thereof.
• polystyrene sulfonic acid and / or a salt thereof By containing polystyrene sulfonic acid and / or a salt thereof, the antistatic property can be improved.
• polystyrene sulfonic acid and / or a salt thereof is uniformly finely dispersed in the matrix of the resin component (A).
• polystyrene sulfonic acid and / or a salt thereof (B) is uniformly finely dispersed in the matrix of the resin component (A).
• a preferable method from the viewpoint of achieving both antistatic properties and abrasion resistance is to add a third component having a solubility parameter between the resin component (A) of 2 and polystyrene sulfonic acid and / or a salt thereof (B).
• the method it is possible to use a solvent component that volatilizes in the manufacturing process or a resin material having a reaction site.
• a polyhydric alcohol compound (C) which will be described later, is particularly preferable in order to achieve both antistatic properties and abrasion resistance.
• polystyrene sulfonic acid and / or a salt thereof is a metal obtained by sulfonated and sulfonated polystyrene and then neutralizing it with a monovalent alkali metal, an alkaline earth metal, for example, a hydroxide such as potassium, sodium, or lithium.
• alkali metal an alkaline earth metal
• hydroxide such as potassium, sodium, or lithium.
• examples thereof include those with counterions, those neutralized with ammonia to make the counterions ammonium, and anionic polymers obtained by polymerizing styrene sulfonic acid or styrene sulfonate (the above metals and ammonium as salts). ..
• the polystyrene sulfonic acid and / or a salt thereof is preferably used as a homopolymer in order to exhibit an antistatic function, but may be copolymerized with various monomers described in the constituent monomers of the resin component (A).
• the resin layer (X) preferably has a polyhydric alcohol compound (C).
• the durability of antistatic property can be improved.
• the polyhydric alcohol compound (C) in the present invention is a compound having three or more hydroxyl groups, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentylglycol, trimethylolpropane, and the like.
• This polyhydric alcohol compound (C) is not a polymer.
• a particularly preferable polyhydric alcohol compound (C) is a sugar alcohol compound, such as sorbitol (melting point 296 ° C.), xylitol (melting point 216 ° C.), erythritol (melting point 329 to 331 ° C.), mannitol (melting point 290 to 295 ° C.), and the like. Can be mentioned.
• the polyhydric alcohol compound (C) may be used alone or in combination of two or more.
• the polyhydric alcohol compound (C) preferably has a boiling point of 200 ° C. or higher, more preferably 220 ° C. or higher, further preferably 240 ° C. or higher, and preferably 500 ° C. or lower as the upper limit.
• the boiling point of the polyhydric alcohol compound (C) is 200 ° C. or higher, the antistatic property of the antistatic layer becomes higher.
• the melting point of the polyhydric alcohol compound (C) is preferably 20 ° C. or higher.
• the boiling point of the hydroxy group-containing compound can be determined by differential scanning calorimetry (DSC).
• the solubility parameter (SP value) of the polyhydric alcohol compound (C) is preferably 35 [MPa 1/2 ] or more and 50 [MPa 1/2 ] or less. If the SP value is less than 35 or more than 50, compatibility with the resin component (A), polystyrene sulfonic acid and / or its salt (B) becomes difficult, and abnormal aggregates are likely to occur. , it may result as a value of the ratio R Y / R X of the surface resistivity values before and after abrasion process, and the value of the ratio R z / R X of the surface resistivity values before and after the corona discharge treatment is likely to exceed the preferred ranges ..
• the solubility parameter is, for example, "Polymer Handbook (fourth Edition)", J. The value is described in BRANDRUP et al. (JOHN WILEY & SONS). On the other hand, when the solubility parameter value is not described in the database, the solubility parameter values are similar to each other and easily dissolve in each other. Therefore, the solubility parameter value is known by the method shown in the examples.
• Hansen Solubility Parameter in Practice HSPiP
• 3.1.03 http://www.hansen-solubility.com/index.php
• the polyhydric alcohol compound (C) has a solubility parameter (SP value) of 35 [MPa 1/2 ] or more and 50 [MPa 1/2 ] or less, which satisfies the following (i) and (ii). .. (Ii)
• SP value solubility parameter
• the boiling point is 200 ° C. or higher. It is particularly preferable to have a sugar alcohol.
• another laminated polyester film of the present invention is a laminated polyester film having a polyester film and a resin layer (X), and has a resin layer (X) on at least one surface layer, and the resin layer (X) is Laminated polyester having a resin component (A), polystyrene sulfonic acid and / or a salt thereof (B), and a polyhydric alcohol (C), and the glass transition temperature of the resin component (A) is 40 ° C. or higher and 120 ° C. or lower. It is a film.
• the other laminated polyester film of the present invention is preferably a laminated polyester film containing at least one resin component (A) selected from acrylic resin, polyester resin, polyurethane resin, melamine resin and epoxy resin.
• A resin component selected from acrylic resin, polyester resin, polyurethane resin, melamine resin and epoxy resin.
• the glass transition temperature of the resin component (A) is 40 ° C. or higher and 120 ° C. or lower.
• the glass transition temperature (Tg) of the resin component (A) is preferably 60 ° C. or higher and 120 ° C. or lower, and particularly preferably 70 ° C. or higher and 120 ° C. or lower.
• Another laminated polyester film of the present invention contains polystyrene sulfonic acid and / or a salt (B) thereof. It is preferable that polystyrene sulfonic acid and / or a salt thereof (B) is uniformly finely dispersed in the matrix of the resin component (A).
• the polyhydric alcohol compound (C) in the present invention is a compound having three or more hydroxyl groups, and a particularly preferable polyhydric alcohol compound (C) is a sugar alcohol compound.
• the polyhydric alcohol compound (C) preferably has a boiling point of 200 ° C. or higher, more preferably 220 ° C. or higher, and even more preferably 240 ° C. or higher.
• the solubility parameter (SP value) of the polyhydric alcohol compound (C) is preferably 35 [MPa 1/2 ] or more and 50 [MPa 1/2 ] or less.
• the resin layer (X) has a compound (D) having an ethylene oxide group.
• the slipperiness of the resin layer (X) can be improved, and the durability of antistatic property can be improved.
• the compound (D) having an ethylene oxide group represents a compound having a structure represented by the formula (1).
• Examples of the compound (D) having an ethylene oxide group include polyoxyethylene-polyoxypropylene block copolymer and polyethylene glycol.
• Commercially available products may be used, specifically, Pluronic (R) PE3100, PE3500, PE4300, PE6100, PE6120, PE6200, PE6400, PE6800, PE7400, PE8100, PE9200, PE9400, PE10100, PE10300, PE10400, PE10500 (manufactured by BAF Japan Co., Ltd.), ADEKA (R) "Pluronic (registered trademark)" L-23, L-31, L-33, L-34, L-35, F-38, L-42 , L-43, L-44, L-61, L-62, L-64, P-65, F-68, L-71, L-72, P-75, P-77, L-81, P -84, P-85, F-88, L-92, P-94, F-98, L-
• the weight average molecular weight of the compound (D) having an ethylene oxide group is preferably 1000 or more and 20000 or less. It is more preferably 2000 or more and 16000 or less, further preferably 6000 or more and 16000 or less, and particularly preferably 11000 or more and 16000 or less.
• the weight average molecular weight of compound (D) having an ethylene oxide group can be determined by measuring using gel permeation chromatography (GPC) in the method described later. Specifically, it is calculated as a weight average molecular weight in terms of standard polymethylmethacrylate under the following measurement conditions.
• Equipment GPC equipment (HLC-8220) manufactured by Tosoh Corporation Columns: TSK GEL SuperH1000, TSK GEL SuperH2000, TSK GEL SuperH3000 (both manufactured by Tosoh Corporation)
• Solvent Water / Ethanol Flow rate: 0.5 mL / min Sample concentration: 1 mg / mL Injection volume: 0.1 mL.
• the thickness of the resin layer (X) in the laminated polyester film of the present invention is preferably 10 to 100 nm. It is more preferably 15 nm or more and 80 nm or less, and further preferably 20 nm or more and 70 nm or less. By setting the thickness of the resin layer to 10 nm or more and 100 nm or less, it is possible to sufficiently develop the initial antistatic property and resistance to deterioration while maintaining excellent transparency.
• the laminated polyester film of the present invention is preferably a layer in which the resin layer (X) is formed of a coating composition containing a resin component (A) and polystyrene sulfonic acid and / or a salt (B) thereof. ..
• the laminated polyester film of the present invention may be provided with an intermediate layer between the resin layer (X) and the polyester film.
• the film may be scratched during winding of the film in which the intermediate layers are laminated and in the subsequent steps until the resin layer (X) of the present invention is provided. Therefore, in the laminated polyester film of the present invention, it is preferable that the resin layer (X) and the polyester film are directly laminated.
• the laminated polyester film of the present invention preferably has a haze of 5.0% or less.
• a haze of 5.0% or less.
• it can be preferably used for a protective film or a cover tape. More preferably, it is 4.0% or less, and even more preferably 3.0% or less.
• the laminated polyester film of the present invention is a laminated polyester film having a polyester film and a resin layer (X).
• the polyester film may be a single-layer film or a laminated film.
• the polyester film represents a component that makes polyester 50% by weight or more based on the entire constituent resin.
• polyester is a general term for polymers having an ester bond in the main chain, and is ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene- ⁇ , ⁇ .
• Those having at least one constituent selected from -bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate and the like can be preferably used.
• the polyester film using polyester is preferably a biaxially oriented polyester film.
• the biaxially oriented polyester film is generally a polyester sheet or film in an unstretched state, which is stretched about 2.5 to 5.0 times in the longitudinal direction and the width direction perpendicular to the longitudinal direction, respectively, and then heat-treated. , The crystal orientation is completed, and the one showing a biaxial orientation pattern by wide-angle X-ray diffraction.
• thermal stability particularly dimensional stability and mechanical strength, is sufficient, and flatness is also good.
• polyester film various additives such as antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, etc.
• a nucleating agent or the like may be added to such an extent that the characteristics of the polyester film are not deteriorated.
• the polyester film preferably contains particles.
• the particle type silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like can be typically used.
• the particle type and particle size may be a single material or a combination of a plurality of materials.
• the particles are particularly preferably contained in at least the surface layer.
• the total amount of particles is preferably 0.1% by weight or less with respect to the entire polyester film.
• the thickness of the polyester film is appropriately selected depending on the application and type, but is usually preferably 5 to 500 ⁇ m, more preferably 6 to 250 ⁇ m, and most preferably 7 to 150 ⁇ m from the viewpoint of mechanical strength, handleability, and the like. Is. Further, the polyester film may be a composite film obtained by coextrusion, or may be a film obtained by laminating the obtained films by various methods.
• the laminated polyester film of the present invention contains a resin component (A), polystyrene sulfonic acid and / or a salt thereof (B), and if necessary, a polyhydric alcohol compound (C) or a compound (D) having an ethylene oxide group.
• a resin component (A) polystyrene sulfonic acid and / or a salt thereof (B)
• C polyhydric alcohol compound
• D a compound having an ethylene oxide group.
• the laminated polyester film of the present invention is preferably used for a cover tape.
• the cover tape of the present invention is a laminated polyester film having a polyester film and a resin layer (X), has a resin layer (X) on at least one surface layer, and has a surface specific resistance value (R) of the resin layer (X).
• X) is 10 6 ⁇ / ⁇ or more, 10 12 ⁇ / ⁇ or less, the surface resistivity of the R X, a resin layer under the following conditions (resin layer after the surface has been worn process X) (X) the value of the ratio R Y / R X between the value (R Y) is 5.0 or less, and a laminated polyester film.
• the cover tape of the present invention is a laminated polyester film having a polyester film and a resin layer (X), and has a resin layer (X) on at least one surface layer, and the resin layer (X) is a resin component (A).
• Polyestersulfonic acid and / or a salt thereof (B), a polyhydric alcohol (C), and a laminated polyester film having a glass transition temperature of the resin component (A) of 40 ° C. or higher and 120 ° C. or lower is used.
• the method for producing a laminated polyester film of the present invention includes a step of applying a coating composition to at least one surface of the polyester film and then applying a stretching treatment and a heat treatment in at least one direction, and the coating composition comprises polystyrene sulfonic acid and / Or has a salt (B) thereof.
• the method for producing a laminated polyester film of the present invention will be described by taking as an example a case where a polyethylene terephthalate (hereinafter referred to as PET) film is used as the polyester film.
• PET polyethylene terephthalate
• the PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melt-extruded into a sheet at about 280 ° C., and cooled and solidified to prepare an unstretched (unoriented) PET film (A film).
• This film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film (B film).
• a coating composition prepared to a predetermined concentration is applied to one side of this B film.
• the method of applying the coating composition to the polyester film is preferably the in-line coating method.
• the in-line coating method is a method of coating in the process of manufacturing a polyester film. Specifically, it refers to a method in which a polyester resin is melt-extruded, biaxially stretched, then heat-treated and applied at any stage, and is usually obtained by melt-extruding and quenching.
• a crystalline unstretched (unaligned) polyester film (A film) then a uniaxially stretched (uniaxially oriented) polyester film (B film) stretched in the longitudinal direction, or a biaxially stretched film in the width direction before heat treatment. It is applied to any film of stretched (biaxially oriented) polyester film (C film).
• the coating composition is applied to any of the above A film and B film before the crystal orientation is completed, and then the polyester film is uniaxially or biaxially applied. It is preferable to adopt a method of stretching in the direction and performing heat treatment at a temperature higher than the boiling point of the solvent to complete the crystal orientation of the polyester film and to provide the resin layer (X). According to this method, the formation of the polyester film and the coating and drying of the coating composition (that is, the formation of the resin layer (X)) can be performed at the same time, which is advantageous in terms of manufacturing cost. By containing the polyhydric alcohol compound (C) in the coating composition, aggregation is suppressed, and a stretched film having good quality can be easily obtained.
• a method of applying a coating composition to a polyester film (B film) uniaxially stretched in the longitudinal direction, then stretching in the width direction and heat-treating is preferable.
• the stretching step is one less, so defects and cracks in the composition layer due to stretching are less likely to occur, and the transparency, smoothness, and antistatic property are excellent. This is because the composition layer can be formed.
• the method for producing a laminated polyester film of the present invention preferably includes a step of applying a coating composition as a resin layer (X) on at least one side of the polyester film, and then performing stretching treatment and heat treatment in at least one direction.
• the resin layer (X) is preferably provided by the in-line coating method.
• the coating method of the coating composition on the polyester film any known coating method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a blade coating method can be used.
• the best method for forming the resin layer (X) in the present invention is a method in which a coating composition using an aqueous solvent is applied onto a polyester film by an in-line coating method, dried, and heat-treated.
• a more preferable method is to in-line coat the coating composition on the B film after uniaxial stretching.
• drying can be preferably carried out in a temperature range of 80 to 130 ° C. to complete the removal of the solvent of the coating composition.
• the heat treatment can be carried out in a temperature range of 160 to 240 ° C. in order to complete the crystal orientation of the polyester film, the thermal curing of the coating composition, and the formation of the resin layer (X).
• the arrangement of polystyrene sulfonic acid and / or its salt (B) is promoted by performing the stretching treatment after applying the coating composition, and excellent antistatic performance.
• the stability of the antistatic performance against wear and surface treatment can be improved by continuously performing the high temperature heat treatment.
• a surface treatment such as a corona discharge treatment may be performed on the coated surface of the PET film before coating.
• surface treatment such as corona discharge treatment
• the wettability of the coating composition to the PET film can be improved, the coating composition can be prevented from repelling, and a resin layer (X) having a uniform coating thickness can be formed. it can.
• a heat treatment zone preheating zone
• it is preferable to grip the end of the PET film with a clip and guide it to a heat treatment zone (preheating zone) at 80 to 130 ° C. to dry the solvent of the coating composition. After drying, it is preferably stretched 1.1 to 5.0 times in the width direction. It is preferable that the crystal orientation is completed by subsequently leading to a heat treatment zone (heat fixing zone) at 160 to 240 ° C. and performing heat treatment for 1 to 30 seconds.
• heat treatment step heat fixing step
• a relaxation treatment of 3 to 15% may be performed in the width direction or the longitudinal direction, if necessary.
• the laminated polyester film thus obtained becomes a film having excellent transparency, antistatic properties, and antistatic properties.
• the coating composition of the present invention will be described.
• the resin component (A) is 15% by weight or more and 75% by weight or less based on the total solid content weight, and polystyrene sulfonic acid and / or a salt thereof (B) is 15% by weight based on the total solid content weight. It has 50% by weight or more and 50% by weight or less. If the resin component (A) is less than 15% by weight, the film-forming property of the coating film is insufficient, and not only the durability of antistatic performance against abrasion cannot be obtained, but also the resin layer (X) is formed from the polyester film. It becomes easy to fall off. On the other hand, if it exceeds 75% by weight, the antistatic property is insufficient.
• polystyrene sulfonic acid and / or a salt (B) thereof is contained in a proportion of 15% by weight or more and 50% by weight or less with respect to the total solid content weight of the coating composition. If it is less than 15% by weight, the antistatic property is insufficient. On the other hand, if it exceeds 50% by weight, the transparency of the coating film is impaired, and the quality is deteriorated due to cracking or scraping of the film.
• the resin component (A) is preferably a resin selected from acrylic resin, polyester resin, polyurethane resin, melamine resin and epoxy resin.
• the glass transition temperature of the resin component (A) is 40 ° C. or higher and 120 ° C. or lower.
• the glass transition temperature (Tg) of the resin component (A) is preferably 60 ° C. or higher and 120 ° C. or lower, and particularly preferably 70 ° C. or higher and 120 ° C. or lower.
• the resin component (A) contained in the coating composition of the present invention is preferably an emulsion dispersed in an aqueous solvent.
• the coating composition of the present invention preferably has a polyhydric alcohol compound (C).
• the polyhydric alcohol compound (C) is preferably contained in a proportion of 5% by weight or more and 20% by weight or less with respect to the total solid content weight of the coating composition. If it is less than 5% by weight, agglomeration of the coating composition is likely to occur, and it may be difficult to obtain durability of the antistatic performance against abrasion. On the other hand, if it exceeds 20% by weight, the film-forming property tends to be insufficient and blocking may easily occur.
• the coating composition of the present invention preferably contains at least one polyhydric alcohol compound (C) selected from sorbitol, xylitol, maltitol, erythritol, mannitol, and lactitol.
• C polyhydric alcohol compound
• the polyhydric alcohol compound (C) satisfies the following (i) and (ii), (i) the solubility parameter (SP value) is 35 [MPa 1/2 ] or more, and 50 [MPa 1 ]. / 2 ] Must be less than or equal to. (Ii) The boiling point is 200 ° C. or higher. It is preferable to have a sugar alcohol.
• the coating composition of the present invention when the coating composition contains a solvent, it is preferable to use an aqueous solvent as the solvent (use a water-based coating agent). This is because the use of an aqueous solvent can suppress rapid evaporation of the solvent in the drying step, can form a uniform composition layer, and is excellent in terms of environmental load.
• the aqueous solvent is soluble in water or water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol.
• alcohols such as methanol, ethanol, isopropyl alcohol and butanol
• ketones such as acetone and methyl ethyl ketone
• glycols such as ethylene glycol, diethylene glycol and propylene glycol.
• the coating composition of the present invention preferably contains a compound (D) having an ethylene oxide group.
• a compound (D) having an ethylene oxide group By having the compound (D) having an ethylene oxide group, it becomes easy to suppress the occurrence of aggregation, and as a result, it becomes easy to suppress the deterioration of the antistatic property due to wear, which is a problem of the resin layer of the present invention.
• Whether or not the coating composition contains the compound (D) having an ethylene oxide group can be measured by using time-of-flight secondary ion gravity analysis (GCIB-TOF-SIMS) under the measurement conditions described later. is there.
• GCIB-TOF-SIMS time-of-flight secondary ion gravity analysis
• the compound (D) having an ethylene oxide group is preferably contained in a proportion of 2% by weight or more and 20% by weight or less based on the total solid content weight of the coating composition. If it is less than 2% by weight, aggregation is likely to occur, and the transparency and the quality of the coating film may be deteriorated. On the other hand, at 20% by weight, the coating appearance may be deteriorated due to foaming.
• the weight average molecular weight of compound (D) is preferably 1000 or more and 20000 or less.
• the coating composition of the present invention is preferably a laminated polyester film having a polyester film and a resin layer (X), having a resin layer (X) on at least one surface layer, and a surface ratio of the resin layer (X).
• resistance (R X) is 10 6 ⁇ / ⁇ or more, and 10 12 ⁇ / ⁇ or less, and R X, a resin layer under the following conditions resin layer after abrasion treatment of the surface of the (X) (X) the value of the ratio R Y / R X of the surface resistivity value (R Y) of 5.0 or less, to form a resin layer of the laminated polyester film (X).
• the coating composition of the present invention is preferably a laminated polyester film having a polyester film and a resin layer (X), and has a resin layer (X) on at least one surface layer, and the resin layer (X) is a resin component.
• a resin layer (X) is formed.
• the surface resistivity value RX is measured at 23 ° C. and 65% relative humidity for 24 hours, and then in that atmosphere, a digital ultra-high resistance / micro ammeter R8340A (manufactured by Advantest Co., Ltd.). After applying an applied voltage of 100 V for 10 seconds, the test was carried out at. The unit is ⁇ / ⁇ . Evaluates the resin laminated surface of the laminate samples was a mean value obtained by measuring a total of 10 times the surface resistivity value R X samples.
• the surface resistivity value RY after wear was measured by the following procedure. First, the resin layer (X) of the laminated polyester film was fixed to Haydon Tribogear TYPE: 38 manufactured by Shinto Kagaku Co., Ltd. so that the surface to be worn faces upward. Next, a non-woven fabric (Hizegase NT-4 manufactured by Ozu Corporation) was attached to the ASTM flat surface indenter. Further, the surface of the resin layer (X) was worn 10 times back and forth under the conditions of a moving distance of 100 mm, a moving speed of 2000 mm / min, and a load of 20 g / cm 2 . Then, measurement was carried out similarly to the surface specific resistance R X above. The unit is ⁇ / ⁇ . The resin laminated surface of the laminated sample was evaluated, and the average value measured 10 times in total was taken as the surface resistivity value RY after wear of the sample.
• the haze haze is measured by leaving the sample for 40 hours in a normal state (23 ° C., relative humidity 50%) and then using a turbidity meter "NDH5000" manufactured by Nippon Denshoku Kogyo Co., Ltd. to JIS K 7136. The method was based on "How to find haze of transparent material” (2000 edition). The measurement was performed by irradiating light from the surface side on which the surface ⁇ of the sample was laminated. As the sample, 10 square samples having a side of 50 mm were prepared, and the average value measured 10 times in total was taken as the haze value of the sample.
• Thickness of Resin Layer The thickness of the resin layer on the polyester film was measured by observing the cross section using a transmission electron microscope (TEM). As for the thickness of the resin layer, the thickness of the resin layer was read from an image taken by TEM at a magnification of 200,000 times. A total of 10 resin layer thicknesses were measured and used as an average value.
• TEM transmission electron microscope
• Presence or absence of resin component (A) and polystyrene sulfonic acid and / or salt (B) and polyvalent alcohol compound (C) The composition analysis of the resin layer is performed by X-ray photoelectron spectroscopy on the surface of the resin layer (X). It was performed by an analyzer (ESCA), a Fourier infrared spectrophotometer (FT-IR) ATR method, and a time-of-flight secondary ion weight analyzer (TOF-SIMS). Further, the resin layer (X) is dissolved and extracted with a solvent, separated by chromatography, and then proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), carbon nuclear magnetic resonance spectroscopy ( 13 C-NMR), and Fourier.
• ESA analyzer
• FT-IR Fourier infrared spectrophotometer
• TOF-SIMS time-of-flight secondary ion weight analyzer
• the structure is analyzed by an infrared spectrophotometer (FT-IR), and thermal decomposition gas chromatography weight analysis (GC-MS) is performed to perform resin component (A), polystyrene sulfonic acid and / or a salt thereof (B), and polyvalence. The presence or absence of the alcohol compound (C) was examined.
• FT-IR infrared spectrophotometer
• GC-MS thermal decomposition gas chromatography weight analysis
• Tables 5 and 6 show Y when the structure of the polyhydric alcohol compound (C) is contained in the resin layer, and N when the resin layer does not contain the structure.
• the glass transition temperature was obtained from the point where the straight line at the same distance in the vertical axis direction from the extended straight line of each baseline intersects with the curve of the stepwise change portion of the glass transition. When two or more stepwise changes in the glass transition were observed, the glass transition temperature was determined for each, and the average value of these temperatures was taken as the glass transition temperature (Tg) (° C.) of the sample.
• Weight Average Molecular Weight of Compound (D) Having an Ethylene Oxide Group The weight average molecular weight of compound (D) having an ethylene oxide group can be determined by measuring using gel permeation chromatography (GPC). .. Specifically, it was calculated as a weight average molecular weight in terms of standard polymethylmethacrylate under the following measurement conditions.
• Blocking property (peeling property after blocking test) Cut the laminated film into 5 cm squares.
• the laminated film was laminated so that the surface of the A layer and the surface of the B layer were in contact with each other, and a 150 kgf load was treated at 50 ° C. for 5 hours using a C-type heatable 60t press (manufactured by Gonno Hydraulic Press Mfg. Co., Ltd.).
• the blocking property was evaluated based on the following criteria for the resistance when the sample after the two laminated films were laminated and peeled off with tweezers. 4: Very low resistance during peeling. 3: There is almost no resistance at the time of peeling, and there is no delamination in the peeled laminated film. 2: There is resistance at the time of peeling, but there is no delamination in the peeled laminated film. 1: Delamination of the A layer and the B layer has occurred in at least one of the peeled laminated films.
• the resin composition A was adjusted as follows.
• A-1 Methyl methacrylate (47 mol%), ethyl acrylate (45 mol%), acrylic acid (2 mol%), N-methylol acrylamide (1 mol%), polyethylene glycol mono with 16 repeating units of ethylene oxide.
• Emulsion solution of acrylic resin emulsion diameter 50 nm at Tg 46 ° C.
• aqueous solution was prepared for each of the other components as follows.
• the compounding ratio of each coating composition is shown in Tables 1 and 2.
• A-3 Acrylic resin (aqueous solution diameter) at Tg 79 ° C. consisting of methyl methacrylate (76 mol%), ethyl acrylate (20 mol%), acrylic acid (3 mol%), and N-methylolacrylamide (1 mol%).
• 50 nm aqueous solution
• A-4 composed of methyl methacrylate (84 mol%), methyl acrylate (11 mol%), acrylic acid (4 mol%), N-methylolacrylamide (1 mol%), Tg 90 ° C.
• Acrylic resin (emulsion diameter 50 nm) emulsion solution B-1 aqueous solution of ammonium polystyrene sulfonic acid salt (weight average molecular weight 70,000)
• B-2 1887 parts by weight aqueous solution containing 20.8 parts by weight of polystyrene sulfonic acid. 49 parts by weight of a 1 wt% iron (III) sulfate aqueous solution, 8.8 parts by weight of 3,4-ethylenedioxythiophene, and 117 parts by weight of a 10.9 wt% peroxodisulfate aqueous solution were added. The mixture was stirred at 18 ° C. for 23 hours.
• C-1 Aqueous solution of sorbitol (boiling point: 296 ° C., SP value: 35.8 MPa 1/2 )
• C-2 Aqueous solution of xylitol (boiling point: 216 ° C., SP value: 36.0 MPa 1/2 )
• C-3 Aqueous solution of erythritol (boiling point: 400 ° C., SP value: 33.8 MPa 1/2 )
• C-4 Aqueous solution of ethylene glycol (boiling point: 197 ° C., SP value: 33.0 MPa 1/2 )
• D-1 Co., Ltd.
• the material was wound around a mirror casting drum having a surface temperature of 25 ° C. and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film (B film).
• the coating composition 1 was applied to the corona discharge-treated surface of the uniaxially stretched film using a bar coat. Grasp both ends of the uniaxially stretched film coated with the coating composition in the width direction with clips to guide it to the preheating zone, set the ambient temperature to 75 ° C, and then use a radiation heater to set the ambient temperature to 110 ° C, and then the ambient temperature. The temperature was 90 ° C., and the coating composition was dried to form a resin layer (X).
• the laminated polyester was continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C., and then heat-treated in a heat treatment zone (heat fixing zone) at 230 ° C. for 20 seconds to complete crystal orientation.
• the thickness of the PET film measured by observing the cross section of the obtained laminated polyester film using a transmission electron microscope (TEM) was 20 ⁇ m, and the thickness of the resin layer (X) was 60 nm.
• the characteristics and the like of the obtained laminated polyester film are shown in Tables 3 and 5.
• a laminated polyester film was obtained in the same manner as in Example 1.
• Example 8 From the conditions described in Example 1, a laminated polyester film was obtained in the same manner as in Example 1 except that pellets containing no colloidal silica were used as PET pellets of the laminated polyester film.
• Example 9 A laminated polyester film was obtained by the following method using the coating composition described in Example 1.
• a PET film “Lumirror T60” base material thickness 38 ⁇ m
• the coating composition was applied onto the substrate using a wire bar, and then heated and cured in a hot air oven at 200 ° C. for 1 min.
• the thickness of the PET film was 38 ⁇ m
• the thickness of the resin layer was 80 nm.
• a laminated polyester film was obtained in the same manner as in Example 1 except that the liquid was prepared.
• Example 18 A laminated polyester film was obtained in the same manner as in Example 9 except that the thickness of the resin layer was 60 nm.
• Example 19 A laminated polyester film was obtained in the same manner as in Example 1 except that the thickness of the resin layer was 150 nm.
• a laminated polyester film was obtained by the following method.
• a PET film "Lumirror T60" base material thickness 38 ⁇ m
• the coating composition was applied onto the substrate using a wire bar, and then heated and cured in a hot air oven at 200 ° C. for 1 min.
• the thickness of the PET film was 38 ⁇ m
• the thickness of the resin layer was 80 nm.
• E is represents the index, for example, 1.0E + 09 represents a 1.0 ⁇ 10 9.
• the laminated polyester film of the present invention is excellent in maintaining antistatic properties and antistatic properties during abrasion and corona discharge treatment.
• the laminated polyester film of the present invention is particularly used for magnetic recording materials, electrically insulating materials, insulating tapes, electrical materials, protective films and the like for optics, graphics, cards, transfer foils, ribbons, and vapor deposition. It can be used as various tapes for, packaging, condenser, cover tape, etc.
• the laminated polyester film of the present invention is preferable for a carrier tape because it can solve dust adhesion due to peeling charging phenomenon, electrical destruction of electronic parts, deterioration of antistatic property in a harsh environment, and deterioration of transparency. Can be used. Further, the laminated polyester film of the present invention can solve the problems of the protective film such as dust adhesion due to peeling charge phenomenon, destruction of electronic elements of the display due to peeling charge, and deterioration of antistatic property in a harsher environment. Therefore, it can be used as a protective film.

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• 2020
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