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WO2018066618A1 - Film de polyester stratifié - Google Patents

Film de polyester stratifié Download PDF

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Publication number
WO2018066618A1
WO2018066618A1 PCT/JP2017/036194 JP2017036194W WO2018066618A1 WO 2018066618 A1 WO2018066618 A1 WO 2018066618A1 JP 2017036194 W JP2017036194 W JP 2017036194W WO 2018066618 A1 WO2018066618 A1 WO 2018066618A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester film
layer
film
weight
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/036194
Other languages
English (en)
Japanese (ja)
Inventor
恵美 源
秀和 森井
公裕 井崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to KR1020227003577A priority Critical patent/KR102494640B1/ko
Priority to CN201780060353.2A priority patent/CN109789691B/zh
Priority to CN202210037345.9A priority patent/CN114407470B/zh
Priority to KR1020197008934A priority patent/KR102359332B1/ko
Publication of WO2018066618A1 publication Critical patent/WO2018066618A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the present invention relates to a laminated polyester film, and more specifically, various types of deposition such as a synthetic resin plate, a glass plate, a metal plate, an optical member, an automobile member, an electric or electronic member, a building material member, a stationery, or an office supplies member.
  • the present invention relates to a laminated polyester film suitable for body surface protection.
  • synthetic resin plate, glass plate, metal plate, glass substrate for optical member, light diffusion film, liquid crystal display member (polarizing plate, retardation plate, light guide plate, prism plate, etc.), touch panel, automobile member, electric or electronic member A surface with an adhesive layer on one side of a polyethylene substrate for the purpose of protecting the surface of various adherends to prevent dirt, scratches, dust, etc. on the surface of building materials, stationery or office supplies A protective film is used.
  • the surface protective film for example, a surface protective film using a low density polyethylene resin as a substrate and an ethylene-vinyl acetate copolymer (EVA) as an adhesive has been proposed (Patent Documents 1 and 2). ).
  • EVA ethylene-vinyl acetate copolymer
  • the base film may be contaminated with an adhesive or a pressure-sensitive adhesive when forming the pressure-sensitive adhesive layer.
  • an adhesive layer is formed, and another base film is subsequently bonded, the pressure-sensitive adhesive protrudes from the peripheral portion and may contaminate the base film.
  • the adhesive sheet is bonded together, when the adhesive sheet is transported, the adhesive layer is pressed and the adhesive layer protrudes from the adhesive layer in order to grip the side end face side of the sheet. The material film could get dirty.
  • Patent Document 3 As a countermeasure against the above-mentioned concerns, for example, as described in Patent Document 3, there is a proposal of laser processing so that the area of the adhesive is smaller than the film on the protective film side.
  • This method is a laminated structure in which a plastic film is bonded to both sides via an adhesive layer, and is effective if there is no particular problem in use in terms of adhesion of foreign matters derived from a surface protective film or occurrence of burr in a member. It is a technique.
  • Patent Document 3 when using a laser to perform laser processing with minimal adhesion of foreign matters derived from the surface protection film or generation of burrs on members, it may be difficult to handle with a general-purpose polyester film. It was.
  • the present invention has been made in view of the above circumstances, and the problem is that, even when a high-performance inspection apparatus is used, inspection with optical evaluation is easy in a state of being bonded to a member to be inspected.
  • Laser processing cutting, marking, trimming
  • the antistatic property is good and, for example, the surface protective film is adhered to the member, and foreign matter adhesion from the surface protective film or generation of burrs on the member is minimized. It is possible to provide a laminated polyester film suitable as a substrate for a surface protective film.
  • the gist of the present invention is a laminated polyester film having an antistatic layer on at least one side of the polyester film, the antistatic layer containing polythiophene or a polythiophene derivative, and the outermost layer of the polyester film in contact with the antistatic layer Exists in a laminated polyester film characterized by not containing particles.
  • the laminated polyester film of the present invention is used for optical member applications that require particularly high visibility (for example, glass substrates, light diffusion films, liquid crystal displays (polarizing plates, retardation, light guide plates, prism plates, etc.)) and the like.
  • optical member applications for example, glass substrates, light diffusion films, liquid crystal displays (polarizing plates, retardation, light guide plates, prism plates, etc.)
  • Laser processing cutting, marking, trimming, drilling, etc.
  • the polyester film constituting the laminated polyester film of the present invention may have a single layer structure or a laminated structure.
  • the laminated configuration may be, for example, two layers, three layers, four layers or more, and is not particularly limited.
  • the polyester film preferably has a laminated structure of at least three layers, and a three-layer structure in which an outermost layer (surface layer A), an intermediate layer, and an outermost layer (surface layer B) are laminated in this order. It is more preferable that
  • the polyester used for the polyester film may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Representative polyester includes polyethylene terephthalate (PET) and the like.
  • examples of the dicarboxylic acid component of the copolyester include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and the like.
  • examples thereof include one or more of glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like.
  • the polyester as used in the present invention is preferably a polyester that is polyethylene terephthalate in which 60 mol% or more, preferably 80 mol% or more is an ethylene terephthalate unit.
  • the polyester constituting the outermost layer contains 80% by weight or more of polyester having an oligomer (ester cyclic trimer) content of 0.5% by weight or less. It is preferable. This makes it possible to obtain the desired oligomer precipitation preventing effect.
  • the polyester having an oligomer content of 0.5% by weight or less it is possible to suppress a significant increase in haze after the heat treatment step, and after processing, in terms of optical characteristics, for example, visibility It becomes a preferable polyester film for optical members.
  • the polyester film contains at least one compound selected from the group consisting of a titanium compound and a phosphorus compound in order to reduce the amount of oligomer in the film.
  • the titanium element content (Ti amount) in the polyester film is preferably 20 ppm or less, more preferably 2 to 10 ppm.
  • the amount of Ti exceeds 20 ppm, oligomers are by-produced in the step of melt-extruding polyester, and a film having low oligomers and high transparency may not be obtained. In optical applications, it may be difficult to cope with applications in which color tone is important.
  • the phosphorus element content (P amount) in the polyester film is preferably 20 ppm or less, more preferably 5 to 15 ppm.
  • the amount of P exceeds 20 ppm, gelation may occur during the production of polyester, which may be a foreign matter, reducing the quality of the film and, for example, making it difficult to handle inspection processes involving optical evaluation.
  • the Ti amount and the P amount are satisfied at the same time. This makes it possible to exert a remarkable effect on the reduction of the oligomer content in the polyester film.
  • titanium-based polymerization catalysts such as tetraisopropyl titanate and tetrabutyl titanate are more preferable.
  • type of phosphorus compound is not particularly limited, but phosphates such as ethyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, and alkyl acid phosphate are more preferable.
  • the outermost layer (surface layer A) of the polyester film on the side in contact with the antistatic layer does not contain particles from the viewpoint of facilitating inspection involving optical evaluation.
  • the surface of the polyester film can be sufficiently smoothed, so that the thickness of an antistatic layer to be described later laminated thereon becomes uniform.
  • the antistatic layer contains a colored polythiophene or polythiophene derivative, the difference in the appearance of the laminated polyester film caused by uneven thickness of the antistatic layer can be suppressed. Therefore, foreign object misidentification due to the difference in density is reduced.
  • the surface layer A contains particles, voids and defects are generated at the interface between the polyester film and the particles, and these cause the oligomer to easily move to the surface of the polyester film. Oligomer may be generated. Therefore, by not containing particles in the surface layer A, generation of oligomers can be suppressed. From the above points, by not containing particles in the surface layer A, a laminated polyester film having good testability can be obtained.
  • “does not contain particles” means, for example, in the case of inorganic particles in the surface layer A, when inorganic elements are quantified by XRF (fluorescence X-ray) analysis, 50 ppm or less, preferably 10 ppm or less, most preferably The particle content is defined as being below the detection limit.
  • the infrared absorption spectrum of the surface layer A measured by infrared spectroscopy is defined as no peak different from the polyester raw material. This is because even if particles are not intentionally included in the surface layer A, the possibility of contamination by external foreign matters or the like is taken into consideration during the manufacturing process.
  • particles in the other outermost layer that is, the outermost layer of the polyester film on the side opposite to the antistatic layer; surface layer B
  • the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
  • Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and magnesium phosphate.
  • the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
  • thermosetting urea resins examples include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
  • precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
  • the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction
  • the average particle diameter (d50) of the particles contained in the surface layer B is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, in that it can cope with an inspection process involving optical evaluation. And preferably it is 3.0 micrometers or less, More preferably, it is 1.0 micrometers or less. When the average particle size is less than 0.1 ⁇ m, the film surface may be too flat and the film winding property may be lowered. On the other hand, when the average particle diameter exceeds 3.0 ⁇ m, the presence of the particles contained in the film may cause trouble in the inspection process involving optical evaluation.
  • the particle content in the surface layer B is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and preferably 3% by weight or less, more preferably 2% by weight or less. It is.
  • the particle content is less than 0.001% by weight, the slipperiness of the film may be insufficient.
  • the content exceeds 3% by weight, the transparency of the film becomes insufficient. It may interfere with the inspection process that involves optical evaluation.
  • the method for adding particles to the surface layer B is not particularly limited, and a conventionally known method can be adopted.
  • it can be added at any stage of producing the polyester constituting each layer, but preferably a polycondensation reaction may be carried out after the esterification stage or after the transesterification reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester material or a method of blending dried particles and a polyester material using a kneading extruder Etc.
  • antioxidants In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added to the polyester film as necessary.
  • the polyester film preferably contains an ultraviolet absorber.
  • the intermediate layer preferably contains an ultraviolet absorber.
  • the polyester film contains an ultraviolet absorber, the surface protective film is adhered to the member, and when laser processing (cutting, marking, trimming, drilling, etc.) is performed, the foreign matter adhered to the surface protective film or the member Laser processing with minimal burr generation can be made possible.
  • laser processing cutting, marking, trimming, drilling, etc.
  • the wavelength of the laser beam is in the ultraviolet region (350 nm or less)
  • laser processing that efficiently uses the thermal energy generated along with ultraviolet absorption is possible.
  • the surface protection film itself can prevent excessive thermal energy from being applied to the bonded member itself during laser irradiation, for example, electronic components such as heat-sensitive electronic circuits are protected from damage due to laser irradiation. It becomes possible.
  • UV absorber to be used examples include organic UV absorbers and inorganic UV absorbers, but it is preferable to use organic UV absorbers from the viewpoint of transparency and easy inclusion in polyester.
  • organic ultraviolet absorbers examples include salicylic acid compounds such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
  • benzoxazine compounds include 2, 2- (1,4-phenylene) bis [4H-3,1-benzoxazin-4-one]
  • benzotriazole compounds include 2,2′-methylenebis [6- (benzotriazole-2 -Yl) -4-tert-octylphenol]
  • benzophenone compounds include, for example, 2-hydroxy-4-benzyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octane Xybenzophenone, 2-hydroxy-4-dodecyloxy Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
  • the benzoxazine compound and the benzotriazole compound have good compatibility with the polyester film, the maximum absorption is 350 nm or less, and the amount of the compound incorporated in the film is a relatively small amount in the ultraviolet region of 350 nm or less. It is preferable in terms of increasing the ultraviolet absorption efficiency.
  • Examples of the method of blending the UV absorber into the polyester film include a method of directly adding the UV absorber to the extruder, a method of adding a polyester resin kneaded in advance to the extruder, and the like. One method may be adopted and two methods may be used in combination.
  • the content of the ultraviolet absorber is preferably 0.5% by weight or more, more preferably 0.7% by weight or more, and preferably 3.0% by weight or less, based on the total weight with respect to the entire polyester film. More preferably, it is 2.5% by weight or less.
  • the content of the ultraviolet absorber exceeds the upper limit in the film, the laser light absorption performance may already be saturated.
  • the content of the ultraviolet absorber is lower than the lower limit, for example, the laser irradiation time becomes longer as the laser light absorption efficiency is lowered, and problems such as adhesion of foreign matters derived from the surface protective film are likely to occur.
  • the ultraviolet absorber it is preferable to use at least two types of ultraviolet absorbers in combination.
  • the content ratio of the UV absorber having a high content and other UV absorbers is preferably 2: 1 to 10: 1, more preferably by weight. 2: 1 to 8: 1.
  • the ratio of the ultraviolet absorber having the largest content is larger than the above upper limit, the concentration of one ultraviolet absorber becomes too high, and the wavelength selectivity of the ultraviolet absorber may become poor.
  • the light transmittance at a wavelength of 350 nm or less of the polyester film in the present invention is preferably 10% or less, more preferably 7% or less, from the viewpoint of imparting a laser light absorption function.
  • the light transmittance at a wavelength of 350 nm or less is larger than 10%, when used as a substrate for a surface protective film, the laser light absorption efficiency is poor, for example, the laser irradiation time becomes long, and foreign matters derived from the surface protective film are generated. It may be easier.
  • a conventionally known laser such as a solid laser, a semiconductor laser, a liquid laser, or a gas laser is used.
  • a CO 2 laser and a YAG laser are preferable, and a YAG laser is more preferable from the viewpoint of preventing generation of foreign matters derived from the surface protective film by laser irradiation or preventing generation of burrs in a product after laser irradiation.
  • the thickness of the polyester film is not particularly limited as long as it can be formed into a film, but for use, is preferably 12 ⁇ m or more, more preferably 25 ⁇ m or more, and preferably 250 ⁇ m or less, more preferably Is 125 ⁇ m or less.
  • the thickness of the surface layer A is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, More preferably, it is 3 ⁇ m or more, and preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 20 ⁇ m or less.
  • the thickness of the surface layer A is within the above range, the surface of the polyester film can be sufficiently smoothed.
  • the thickness of the surface layer B is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 3 ⁇ m or more, and preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less. It is. When the thickness of the surface layer B is within the above range, sufficient slipperiness can be obtained.
  • polyester film constituting the laminated polyester film of the present invention will be specifically described, but is not limited to the following production examples.
  • manufacture examples are manufacture examples of a biaxially stretched film
  • the polyester film in this invention is not limited to a biaxially stretched film, A uniaxially stretched film and a non-stretched film may be sufficient.
  • the polyester raw material described above is used and the molten sheet extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched sheet is preferable.
  • a method in which the polyester raw material described above is used and the molten sheet extruded from the die is cooled and solidified with a cooling roll to obtain an unstretched sheet is preferable.
  • an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed.
  • the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
  • the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7.0 times, preferably 3.0 to 6.0 times.
  • the stretching temperature orthogonal to the first-stage stretching direction is usually 70 to 170 ° C., and the draw ratio is usually 3.0 to 7.0 times, preferably 3.5 to 6.0 times.
  • heat treatment is performed at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film.
  • a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
  • the simultaneous biaxial stretching method can be adopted for the production of the polyester film.
  • conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be adopted.
  • a so-called coating stretching method for treating the film surface during the above-described polyester film stretching step can be performed.
  • a coating layer for example, an antistatic layer
  • coating can be performed simultaneously with stretching, and the thickness of the coating layer can be reduced according to the stretching ratio.
  • a suitable film can be produced.
  • the laminated polyester film of the present invention has an antistatic layer (coating layer 1) on at least one side of the polyester film.
  • the polyester film has a three-layer structure in which the outermost layer (surface layer A), the intermediate layer, and the outermost layer (surface layer B) are laminated in this order, the polyester film has an antistatic layer on the surface layer A in the polyester film.
  • the antistatic layer constituting the laminated polyester film contains polythiophene or a polythiophene derivative as an antistatic agent, and preferably further contains a binder polymer, as an antistatic agent, as a constituent member of the surface protective film. By using polythiophene or a polythiophene derivative as the antistatic layer, higher conductivity can be obtained.
  • the polyester film may cause rainbow-like color unevenness (rainbow unevenness) due to phase difference.
  • rainbow unevenness is suppressed by using colored polythiophene or a polythiophene derivative, and misperception due to rainbow unevenness can be suppressed in the foreign substance inspection.
  • the antistatic layer may contain other components as long as the gist of the present invention is not impaired.
  • polythiophene derivatives include compounds in which functional groups are bonded to the 3rd and 4th positions of the thiophene ring.
  • a compound represented by the following formula (I) in which an oxygen atom is bonded to the 3rd and 4th carbon atoms is preferable.
  • R 1 and R 2 each independently represent a hydrogen element, an aliphatic chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclohexyl group, phenyl group and the like.
  • a polythiophene derivative represented by the following formula (II) may be used as an antistatic agent.
  • n is an integer of 1 to 4.
  • the antistatic layer contains a composition comprising the polythiophene and polyanion or a composition comprising the polythiophene derivative and polyanion.
  • the poly anion refers to “an acidic polymer in a free acid state”, and is preferably a polymer carboxylic acid or a polymer sulfonic acid.
  • Specific examples of the high-molecular carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid.
  • Specific examples of the polymer sulfonic acid include polystyrene sulfonic acid and polyvinyl sulfonic acid. Among these, polystyrene sulfonic acid is most preferable in terms of conductivity. In addition, you may take the form of the salt in which a part of free acid was neutralized.
  • the polymer carboxylic acid and polymer sulfonic acid can also be used in the form of copolymerization with other copolymerizable monomers such as acrylate, methacrylate and styrene.
  • the molecular weight of the polymer carboxylic acid or polymer sulfonic acid used as the polyanion is not particularly limited, but the weight average molecular weight is preferably from 1,000 to 1,000,000, more preferably from the viewpoint of the stability and conductivity of the coating agent. ⁇ 150,000.
  • alkali salts such as lithium salts and sodium salts, ammonium salts, and the like may be partially included.
  • polystyrene sulfonic acid and ammonium salts which function as very strong acids, are known to shift to the acidic side due to the progress of the equilibrium reaction after neutralization. It is thought to act.
  • the polyanion is present in an excessive amount in terms of the solid content with respect to the polythiophene or polythiophene derivative, and the polyanion is 0.1% by weight relative to 1 part by weight of the polythiophene or polythiophene derivative. 5 to 5 parts by weight is preferable, 1 to 5 parts by weight is preferable, and 1 to 3 parts by weight is more preferable.
  • the composition comprising the above polythiophene or polythiophene derivative and polyanion for example, JP-A-6-295016, JP-A-7-292081, JP-A-1-135521, JP-A-2000-6324, Europe Although there are examples described in Patent EP602731, US Pat. No.
  • 3,4-ethylenedioxythiophene was obtained using an alkali metal salt of 3,4-dihydroxythiophene-2,5-dicarboxyester as a starting material, and then potassium peroxodisulfate was added to a polystyrenesulfonic acid aqueous solution.
  • Iron sulfate, and 3,4-ethylenedioxythiophene obtained above are introduced and reacted to form a polythiophene such as poly (3,4-ethylenedioxythiophene) and a polyanion such as polystyrene sulfonic acid.
  • An embodied composition is obtained.
  • composition comprising the polythiophene and the polyanion or the composition comprising the polythiophene derivative and the polyanion
  • Latest trend of conductive polymer technology published by Toray Research Center, Inc., June 1999.
  • the binder polymer that can constitute the antistatic layer is a number determined by gel permeation chromatography (GPC) measurement according to the “polymer compound safety evaluation flow scheme” (hosted by the Chemical Substance Council in November 1985). It is defined as a polymer compound having an average molecular weight (Mn) of 1000 or more and having a film-forming property. However, the poly anion is excluded.
  • GPC gel permeation chromatography
  • the binder polymer may be a thermosetting resin or a thermoplastic resin as long as it is compatible or mixed with polythiophene or a polythiophene derivative.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polyimide resins such as polyimide and polyamideimide
  • polyamide resins such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11
  • polyvinylidene fluoride, polyfluoride Fluorine resins such as vinyl, polytetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene
  • vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride
  • epoxy resins oxetane resins
  • Xylene resin aramid resin
  • polyimide silicone resin polyurethane resin
  • binder polymers may be dissolved in an organic solvent, or may be made into an aqueous solution by adding a functional group such as a sulfo group or a carboxy group.
  • a functional group such as a sulfo group or a carboxy group.
  • hardening agents such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc.
  • binder polymers at least one selected from polyester resins, acrylic resins, and polyurethane resins is preferable because mixing at the time of preparing the coating liquid is easy.
  • a polyurethane resin is preferable.
  • the polyester resin is defined as a linear polyester having a dicarboxylic acid component and a glycol component as constituent components.
  • Dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, phenylindanedicarboxylic acid, A dimer acid etc. can be illustrated. Two or more of these components can be used.
  • a small proportion of unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- ( ⁇ -hydroxyethoxy) benzoic acid, etc.
  • the proportion of the unsaturated polybasic acid component or the hydroxycarboxylic acid component is preferably 10 mol% or less, more preferably 5 mol% or less.
  • glycol component examples include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropionic acid.
  • glycol components ethylene glycol, bisphenol A ethylene oxide adduct and propylene oxide adduct, and 1,4-butanediol are preferable, and ethylene glycol and bisphenol A ethylene oxide adduct and propylene oxide adduct are more preferable.
  • the polyester resin can be copolymerized with a small amount of a compound having a sulfonate group or a compound having a carboxylic acid group in order to facilitate aqueous liquefaction, which is preferable.
  • Examples of the compound having a sulfonate group include 5-sodium sulfoisophthalic acid, 5-ammonium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 5-potassium Preferred examples include sulfonic acid alkali metal salt compounds or sulfonic acid amine salt compounds such as sulfoisophthalic acid, 4-potassium sulfoisophthalic acid, 2-potassium sulfoisophthalic acid, and sodium sulfosuccinic acid.
  • the acrylic resin is a polymer composed of polymerizable monomers including acrylic and methacrylic monomers. Either a homopolymer or a copolymer may be used. Further, not only a copolymer having a polymerizable monomer having a carbon-carbon double bond different from the polymerizable monomer, but also a copolymer of the polymer and another polymer (for example, polyester, polyurethane, etc.) is included. . For example, a block copolymer or a graft copolymer.
  • a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included.
  • a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included.
  • a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion is also included.
  • the polymerizable monomer having a carbon-carbon double bond is not particularly limited, but representative compounds such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid.
  • Various carboxy group-containing monomers and their salts 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyl fumarate, monobutylhydroxy
  • Various hydroxyl-containing monomers such as itaconate
  • various (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate Acid esters
  • (meth) acrylic Amides various nitrogen-containing vinyl monomers such as diacetone acrylamide, N- methylol acrylamide or (meth
  • polymerizable monomers as shown below can be copolymerized. That is, various styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyltoluene, various vinyl esters such as vinyl acetate and vinyl propionate; ⁇ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Various silicon-containing polymerizable monomers such as methacryloyl silicon macromer; phosphorus-containing vinyl monomers; vinyl chloride, biliden chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chlorotrifluoroethylene And various vinyl halides such as hexafluoropropylene; and various conjugated dienes such as butadiene.
  • styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene and vinyl
  • the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the coating layer is increased, problems such as easy blocking may occur.
  • Polyurethane resin refers to a polymer compound having a urethane bond in the molecule.
  • a water-dispersible or water-soluble polyurethane resin is preferable.
  • a hydrophilic group such as a hydroxyl group, a carboxy group, a sulfonic acid group, a sulfonyl group, a phosphoric acid group, or an ether group into the polyurethane resin.
  • a hydrophilic groups a carboxylic acid group or a sulfonic acid group is preferably used from the viewpoint of improving physical properties of the coating film and adhesion.
  • polyurethane resin for example, a method utilizing a reaction between a hydroxyl group and an isocyanate can be mentioned.
  • hydroxyl group used as the raw material polyol is preferably used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
  • Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides.
  • polycarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.
  • polyhydric alcohol ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl-1 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol 1,9-nonanediol, 2-
  • polycarbonate polyols examples include polycarbonate diols obtained by dealcoholization reaction from polyhydric alcohols and dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like, such as poly (1,6-hexylene) carbonate, poly ( And 3-methyl-1,5-pentylene) carbonate.
  • polyisocyanate compound used for obtaining the polyurethane resin examples include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′.
  • -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Meta Diisocyanate, cycloaliphatic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.
  • chain extender When synthesizing a polyurethane resin, a conventionally known chain extender may be used, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group.
  • a chain extender having two hydroxyl groups or two amino groups is generally used.
  • chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bis (hydroxyethoxy) benzene, and neopentyl glycol hydroxypivalate. It can be mentioned that glycols such as ester glycol are exemplified.
  • chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidine cyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1 , 3-Bis (aminomethyl) cyclohex Alicyclic diamines such as emissions and the like.
  • the blending ratio of the binder polymer in the antistatic layer is in the range of 10 to 80% by weight, more preferably in the range of 20 to 60% by weight.
  • the adhesiveness with respect to a polyester film may fall.
  • the amount exceeds 80% by weight the adhesion performance becomes saturated, and a significant effect may not be obtained even if the amount is further increased.
  • the coating liquid for the antistatic layer is coated with glycerin (C1), polyglycerin (C2), and glycerin or polyglycerin to improve the coatability. It is preferable to contain one or more compounds selected from the group consisting of alkylene oxide adducts (C3) or derivatives thereof.
  • Glycerin and polyglycerin are compounds represented by the following formula (III).
  • n in the formula (III) is preferably in the range of 1 to 20, more preferably in the range of 2 to 20.
  • polyglycerin is more preferable from the viewpoint of transparency of the antistatic layer.
  • alkylene oxide adduct to glycerin or polyglycerin has a structure in which alkylene oxide or a derivative thereof is added and polymerized to the hydroxy group of glycerin or polyglycerin represented by the formula (III).
  • the structure of the alkylene oxide added or its derivative may be different for each hydroxy group of the glycerin or polyglycerin skeleton. Moreover, it is sufficient that it is added to at least one hydroxy group in the molecule, and alkylene oxide or a derivative thereof need not be added to all hydroxy groups.
  • a preferable alkylene oxide or derivative thereof has a structure containing an ethylene oxide or propylene oxide skeleton. If the alkyl chain in the alkylene oxide structure becomes too long, the hydrophobicity becomes strong, the uniform dispersibility in the coating solution deteriorates, and the antistatic property and transparency of the coating film tend to deteriorate. Particularly preferred is ethylene oxide.
  • the copolymerization ratio of alkylene oxide or its derivative to the glycerin or polyglycerin skeleton is not particularly limited, but when the glycerin or polyglycerin moiety is 1 in terms of molecular weight, The alkylene oxide moiety is preferably 20 or less, more preferably 10 or less. When the ratio of alkylene oxide or its derivative to glycerin or polyglycerin skeleton is larger than this range, it may be close to the characteristics when ordinary polyalkylene oxide is used, and the desired performance may not be obtained.
  • particularly preferred embodiments include polyglycerol (C2) and alkylene oxide adduct (C3) to glycerol or polyglycerol.
  • the polyglycerin (C2) a compound in which n is 2 to 20 in the compound of the above formula (III) is particularly preferable.
  • the number of addition is particularly preferably in the range of 300 to 2000 in terms of the weight average molecular weight as the final compound (C3).
  • the weight of polythiophene or polythiophene derivative in the antistatic layer constituting the laminated polyester film is preferably 0.5 mg / m 2 or more, more preferably 1 mg / m 2 or more.
  • the upper limit is not particularly limited, but is preferably 100 mg / m 2 or less, more preferably 50 mg / m 2 or less.
  • the weight ratio of polythiophene or polythiophene derivative in 100% by weight of the antistatic layer is not limited, but the upper limit is preferably 90% by weight or less, more preferably 80% by weight or less, and most preferably 60% by weight or less. . When the weight ratio exceeds 90% by weight, the transparency of the coating film may be insufficient. On the other hand, the lower limit is preferably 1% or more, more preferably 2% by weight or more. When the weight ratio is less than 1% by weight, the antistatic performance may be insufficient.
  • the ratio of the polythiophene or polythiophene derivative to the binder polymer is preferably in the range of 90/10 to 1/99 by weight.
  • the range is more preferably 70/30 to 1/99, and most preferably 50/50 to 10/90.
  • the antistatic performance or the appearance of the coating tends to deteriorate.
  • a difference in density that is, color unevenness appears in the appearance of the laminated polyester film, which may cause a foreign object to be mistaken for inspection.
  • an antifoaming agent in the antistatic layer (coating layer 1) in the present invention, an antifoaming agent, a coating property improver, a thickener, an organic lubricant, a release agent, organic particles, inorganic particles, an antioxidant, an ultraviolet absorber, You may contain additives, such as a foaming agent, dye, and a pigment. These additives may be used independently and may use 2 or more types together as needed. Moreover, as these additives, it is more preferable to use those containing (poly) alkylene oxide, (poly) glycerin, or derivatives thereof in the structure without inhibiting the antistatic properties of the resulting antistatic layer. .
  • the coating solution for forming the antistatic layer (coating layer 1) in the present invention is preferably an aqueous solution or an aqueous dispersion from the viewpoint of handling, working environment, and stability of the coating solution composition.
  • an organic solvent may be contained.
  • the antistatic layer is provided by applying a coating solution containing a specific compound to the polyester film, and in particular in the present invention, it is preferably provided by in-line coating in which the application is performed during the formation of the polyester film.
  • the surface resistivity R of the antistatic layer surface of the laminated polyester film is preferably 1 ⁇ 10 9 ⁇ or less.
  • R is more preferably 1 ⁇ 10 8 ⁇ or less, and further preferably 1 ⁇ 10 7 ⁇ or less.
  • R is 1 ⁇ 10 9 ⁇ or less, when used as a surface protective film, it is possible to suppress problems such as the inclusion of foreign matters when the laminated polyester film is peeled off.
  • the polyester film has a three-layer structure in which the outermost layer (surface layer A), the intermediate layer, and the outermost layer (surface layer B) are laminated in this order, it is preferable to have an easy adhesion layer on the surface layer B in the polyester film.
  • the easy-adhesion layer preferably contains a binder polymer and a crosslinking agent.
  • the binder polymer constituting the easy-adhesion layer is not particularly limited, and the same binder polymer as that in the antistatic layer can be used. Among these, a polyester resin is a more preferable binder polymer.
  • the glass transition temperature (hereinafter sometimes abbreviated as Tg) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • Tg is less than 40 ° C., for the purpose of improving adhesiveness, when the coating thickness of the easy-adhesion layer is increased, problems such as easy blocking may occur.
  • a polymer other than the polyester resin is used in order not to impair the gist of the present invention in order to improve the coating appearance and the adhesion when the pressure-sensitive adhesive layer is formed on the easy-adhesion layer. It is also possible to use together.
  • polymer examples include acrylic resin, polyurethane resin, polyvinyl resin (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, and starches.
  • acrylic resin or a polyurethane resin from the viewpoint of improving adhesiveness.
  • crosslinking agents can be used as the crosslinking agent constituting the easy-adhesion layer, and examples thereof include oxazoline compounds, melamine compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, and silane coupling compounds.
  • oxazoline compounds especially when using for the use which provides a functional layer (for example, adhesion layer) on an easily bonding layer, an oxazoline compound is used suitably from a viewpoint of durable adhesive improvement.
  • the oxazoline compound is a compound having an oxazoline group in the molecule, and is particularly preferably a polymer containing an oxazoline group, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
  • alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene
  • Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alky
  • the amount of the oxazoline group of the oxazoline compound is preferably 0.5 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 5 mmol / g or more, and preferably 10 mmol / g or less, more preferably 9 mmol / g.
  • it is more preferably 8 mmol / g or less.
  • the melamine compound is a compound having a melamine structure in the compound, for example, an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used.
  • alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
  • a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
  • a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.
  • the epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and the like hydroxyl groups and amino groups, There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like.
  • polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
  • polyglycidyl ether and diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
  • Polypropylene glycol diglycidyl ether polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.
  • the isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
  • isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate
  • Alicyclic isocyanates such as bets are exemplified.
  • a carbodiimide-based compound is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule, but for better adhesion, etc., the polycarbodiimide having two or more in the molecule More preferred are system compounds.
  • the carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
  • the diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used.
  • tolylene diisocyanate xylylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate
  • examples include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
  • crosslinking agents may be used alone or in combination of two or more.
  • a component for promoting crosslinking at the same time for example, a crosslinking catalyst can be used in combination.
  • particles can be used in combination for the purpose of blocking and improving slipperiness in forming each coating layer (antistatic layer, easy adhesion layer).
  • the average particle size is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less, and particularly preferably 0.2 ⁇ m or less from the viewpoint of the transparency of the film.
  • the lower limit is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and particularly preferably a range larger than the film thickness of the coating layer in order to further improve the slipperiness.
  • Specific examples of the particles used include silica, alumina, kaolin, calcium carbonate, organic particles and the like.
  • each coating layer is formed as necessary with a defoaming agent, coating property improver, thickener, organic lubricant, antistatic agent, ultraviolet absorber, oxidation agent. It is also possible to use an inhibitor, a foaming agent, a dye, a pigment and the like in combination.
  • each coating layer constituting the laminated polyester film is usually 0.003 to 1 ⁇ m, preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.2 ⁇ m.
  • the thickness is less than 0.003 ⁇ m, the amount of ester cyclic trimer precipitated from the film may not be sufficiently reduced.
  • it is thicker than 1 ⁇ m, it may cause problems such as deterioration of the appearance of the coating layer and deterioration of blocking properties.
  • the thickness of the entire laminated polyester film of the present invention is not particularly limited as long as it can be formed into a film, but is preferably 12 ⁇ m or more, more preferably 25 ⁇ m or more, and preferably 250 ⁇ m or less, more Preferably it is 125 micrometers or less.
  • Examples of methods for applying a coating solution to a polyester film include air doctor coating, blade coating, rod coating, bar coating, knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, and kiss roll coating.
  • Conventional coating methods such as cast coating, spray coating, curtain coating, calendar coating, and extrusion coating can be used.
  • the polyester film may be subjected to chemical treatment, corona discharge treatment, plasma treatment or the like before coating.
  • the solid content concentration is about 0.1 to 50% by weight using the above series of compounds as an aqueous solution or water dispersion. It is preferable to produce a laminated polyester film in such a manner that a coating solution adjusted with reference to is applied onto the polyester film. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.
  • each coating layer on the polyester film is not particularly limited.
  • each coating layer is provided by off-line coating, it is usually 80 to 200 ° C. for 3 to 40 seconds.
  • the heat treatment is performed at 100 to 180 ° C. for 3 to 40 seconds as a guide.
  • each coating layer is provided by in-line coating, it is usually preferable to perform heat treatment at 70 to 280 ° C. for 3 to 200 seconds as a guide.
  • the haze of the laminated polyester film of the present invention is preferably 2% or less. More preferably, it is 1% or less, and most preferably 0.6% or less. When the haze of the laminated polyester film exceeds 2%, it may cause trouble when used as a constituent unit of the surface protective film in an inspection involving optical evaluation.
  • the surface protective film of the present invention is sufficient if it has at least the laminated polyester film of the present invention described above, and may be the laminated polyester film of the present invention alone. A structure having a layer is preferable.
  • the surface protective film refers to one aspect of the use of the laminated polyester film of the present invention, but the layer structure itself in which an adhesive layer is provided on the above-described laminated polyester film of the present invention, the laminated polyester film of the present invention. It is one mode.
  • Adhesive layer Next, the adhesive layer in the present invention will be described below.
  • the surface protective film it is preferable to provide an adhesive layer on the easy adhesion layer of the laminated polyester film.
  • the adhesive layer may be provided only on one side of the laminated polyester film or on both sides, but it is preferably provided on one side. When it is provided on one side, it may be provided on either side of the antistatic layer or the easy adhesion layer, but it is preferably provided on the easy adhesion layer.
  • the pressure-sensitive adhesive layer in the present invention means a layer composed of a material having adhesiveness, and a conventionally known material such as a silicone pressure-sensitive adhesive or an acrylic pressure-sensitive adhesive is used within a range not impairing the gist of the present invention. be able to.
  • a conventionally known material such as a silicone pressure-sensitive adhesive or an acrylic pressure-sensitive adhesive is used within a range not impairing the gist of the present invention. be able to.
  • an acrylic pressure-sensitive adhesive is preferable because it has a wide adjustment range of pressure-sensitive adhesive properties and is widely used.
  • the case where an acrylic pressure-sensitive adhesive is used will be described below.
  • the acrylic pressure-sensitive adhesive means a pressure-sensitive adhesive containing, as a base polymer, an acrylic polymer formed using an acrylic monomer as an essential monomer component.
  • the acrylic polymer has (meth) acrylic acid alkyl ester and / or (meth) acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as an essential monomer component (more preferably as a main monomer component). ) Is preferably formed.
  • the acrylic polymer is particularly preferably an acrylic polymer formed using (meth) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as essential monomer components.
  • the pressure-sensitive adhesive layer in the present invention was formed of an acrylic pressure-sensitive adhesive formed using (meth) acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester having a linear or branched alkyl group as essential monomer components.
  • a layer is particularly preferred.
  • the monomer component forming the acrylic polymer may further contain a polar group-containing monomer, a polyfunctional monomer, and other copolymerizable monomers as a copolymerization monomer component.
  • said "(meth) acryl” represents “acryl” and / or “methacryl”, and others are the same.
  • the content of the acrylic polymer as the base polymer in the adhesive layer is preferably 60% by weight or more, more preferably 80% by weight, based on the total weight (100% by weight) of the adhesive layer. That's it.
  • a crosslinking agent for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • a tackifier for example, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.
  • anti-aging agent filler, colorant (as required) Pigments, dyes, etc.), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc.
  • the cross-linking agent can control the gel fraction of the adhesive layer by crosslinking the base polymer of the adhesive layer.
  • the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, and the like, and isocyanate crosslinking agents and epoxy crosslinking agents can be suitably used.
  • a crosslinking agent may be used independently and may use 2 or more types together.
  • the thickness (after drying) of the pressure-sensitive adhesive layer of the surface protective film is 10 to 100 ⁇ m, preferably 20 to 50 ⁇ m.
  • the thickness of the adhesive layer (after drying) is less than 10 ⁇ m, it may be difficult to obtain a desired adhesive force.
  • the thickness (after drying) of the pressure-sensitive adhesive layer exceeds 100 ⁇ m, the pressure-sensitive adhesive layer is not sufficiently cured, and problems such as workability deterioration may occur.
  • the thickness of the entire surface protective film is not particularly limited as long as the adhesiveness and workability are sufficient, but it is preferably 22 to 350 ⁇ m, more preferably 45 to 175 ⁇ m.
  • a laminated polyester film having a laminate structure of at least three layers, one outermost layer (surface layer A) substantially containing no particles, and on the surface layer A, polythiophene or a polythiophene derivative and a binder polymer The laminated polyester film characterized by the above-mentioned.
  • ⁇ A2> The laminated polyester film according to ⁇ A1>, wherein a titanium-based polymerization catalyst is included.
  • ⁇ A3> The laminated polyester film according to ⁇ A1> or ⁇ A2>, in which a coating layer 2 containing a polyester resin and a crosslinking agent is provided on the other outermost layer (surface layer B).
  • ⁇ A4> The laminated polyester film according to ⁇ A3>, further including an adhesive layer on the coating layer 2.
  • ⁇ A5> The laminated polyester film according to ⁇ A4>, wherein the adhesive layer is made of an acrylic adhesive.
  • a surface protective film comprising the laminated polyester film according to ⁇ A4> or ⁇ A5>.
  • ⁇ B1> It has a multilayer polyester film having a laminate structure of at least three layers, the intermediate layer of the multilayer polyester film contains an ultraviolet absorber, and one outermost layer (surface layer A) of the multilayer polyester film is A coating film characterized by containing substantially no particles and having a coating layer 1 containing an antistatic agent and a binder polymer on the outermost layer (surface layer A).
  • ⁇ B2> The coated film according to ⁇ B1>, wherein the antistatic agent is polythiophene or a polythiophene derivative.
  • ⁇ B3> The coated film according to ⁇ B1> or ⁇ B2>, wherein the multilayer polyester film contains a titanium-based polymerization catalyst.
  • ⁇ B4> Any one of the above ⁇ B1> to ⁇ B3>, wherein a coating layer 2 containing a polyester resin and a crosslinking agent is provided on the other outermost layer (surface layer B) of the multilayer polyester film.
  • ⁇ B5> The coating film according to ⁇ B4>, wherein an adhesive layer is provided on the surface of the coating layer 2.
  • ⁇ B6> The coated film according to ⁇ B5>, wherein the adhesive layer is formed of an acrylic adhesive.
  • a surface protective film comprising the coated film according to any one of the above ⁇ B1> to ⁇ B6>.
  • the measuring method used in the present invention is as follows.
  • Average particle diameter (d50) The particle size with an integrated volume fraction of 50% in the equivalent spherical distribution measured using a centrifugal sedimentation type particle size distribution measuring device (“SA-CP3 type” manufactured by Shimadzu Corporation) was defined as the average particle size d50.
  • Ester cyclic trimer content contained in polyester raw material
  • 20 mL of chloroform was added, and 10 mL of methanol was added little by little.
  • the precipitate was removed by filtration, and the precipitate was further washed with a mixed solvent having a volume ratio of chloroform / methanol of 2: 1.
  • the filtrate and the washing solution were collected, concentrated by an evaporator, and then dried.
  • Light transmittance The light transmittance at a wavelength of 350 nm was measured with a spectrophotometer (U-3310 manufactured by Hitachi High-Tech Fielding Co., Ltd.). Thereafter, the determination was made according to the following criteria. (Criteria) A: Light transmittance is 7% or less (particularly good) B: Light transmittance exceeds 7% and is 10% or less (good) C: Light transmittance exceeds 10% (may cause practical problems)
  • Adhesive evaluation with adhesive layer The acrylic adhesive comprised from the following adhesive composition was apply
  • Peeling force uses a tensile tester “Intesco model 2001 type” (manufactured by Intesco Co., Ltd.) and peels 180 ° at the interface between the untreated PET film and the adhesive layer under the condition of a tensile speed of 300 mm / min. Adhesion was evaluated according to the following criteria.
  • the surface protection film is very transparent and inspection is particularly easy (no problem in practical use)
  • B The polarizing plate can be inspected with the surface protective film attached. Visible even in the dark and easy to inspect (no problem in practice)
  • C The polarizing plate can be inspected while the surface protective film is bonded, but the inspection may be slightly difficult. (There may be practical problems)
  • D It is difficult to inspect the polarizing plate while the surface protective film is still bonded. (There are practical problems)
  • the polyester used in the examples and comparative examples was prepared as follows.
  • the obtained polyester (A) had an intrinsic viscosity of 0.63 dL / g and an ester cyclic trimer content of 0.97% by weight.
  • polyester (B) ⁇ Method for producing polyester (B)>
  • the polyester (A) is pre-crystallized at 160 ° C. in advance, and then solid-phase polymerized in a nitrogen atmosphere at a temperature of 220 ° C., the intrinsic viscosity is 0.75 dL / g, and the ester cyclic trimer content is 0.46. A weight percent of polyester (B) was obtained.
  • 50 ppm of tetrabutyl titanate was added to the produced polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to 0.3 kPa in absolute pressure, and melt polycondensation was further carried out for 80 minutes.
  • 0.61 dL / g and an ester cyclic trimer content of 1.02% by weight was obtained.
  • polyester (C) is pre-crystallized at 160 ° C. in advance, and then solid-phase polymerized in a nitrogen atmosphere at a temperature of 210 ° C., the intrinsic viscosity is 0.71 dL / g, and the ester cyclic trimer content is 0.50. A weight percent of polyester (D) was obtained.
  • polyester (E) ⁇ Method for producing polyester (E)> Except for adding 0.03 parts by weight of silica particles having an average particle diameter (d50) of 2.3 ⁇ m to 100 parts by weight of polyester (C), the same method as the method for producing polyester (D) is performed. Polyester (E) was obtained using the method. The obtained polyester (E) had an intrinsic viscosity of 0.72 dL / g and an ester cyclic trimer content of 0.50% by weight.
  • polyester (F) ⁇ Method for producing polyester (F)> Except for adding 1.5 parts by weight of aluminum oxide particles having an average particle size (d50) of 0.3 ⁇ m to 100 parts by weight of polyester (C), the same as the method for producing polyester (D) Polyester (F) was obtained by using the method.
  • the obtained polyester (F) had an intrinsic viscosity of 0.72 dL / g and an ester cyclic trimer content of 0.50% by weight.
  • polyester (G) ⁇ Method for producing polyester (G)> To 100 parts by weight of polyester (C), 2,2- (1,4-phenylene) bis [4H-3,1-benzoxazin-4-one] as a UV absorber is adjusted to a concentration of 10% by weight.
  • a polyester (G) was obtained using the same method as the method for producing the polyester (D) except that the addition and melt-kneading were performed.
  • the obtained polyester (G) had an intrinsic viscosity of 0.72 dL / g and an ester cyclic trimer content of 0.52% by weight.
  • polyester (H) ⁇ Method for producing polyester (H)> To 100 parts by weight of polyester (C), 2,2′-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol] is added as a UV absorber so as to have a concentration of 10% by weight.
  • a polyester (H) was obtained using the same method as the production method of the polyester (D) except that melt kneading was performed.
  • the obtained polyester (H) had an intrinsic viscosity of 0.72 dL / g and an ester cyclic trimer content of 0.52% by weight.
  • (B2): A water dispersion of a polyester resin copolymerized with the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid sodium // (diol component) ethylene glycol / 1,4-butanediol / Diethylene glycol 56/40/4 // 70/20/10 (mol%)
  • (B3): Aqueous dispersion of acrylic resin polymerized with the following composition: Emulsion weight of ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid 65/21/10/2/2 (% by weight) Combined (emulsifier: anionic surfactant)
  • (C2): Polyglycerin in which n 2 in the formula (III)
  • (C3): Polyglycerin in which n 2 in the
  • Example A1 Manufacture of laminated polyester film F1a
  • Polyester (D) 100% by weight of raw material for surface layer A, polyester (D) and (F) blended in proportions of 90% by weight and 10% by weight, respectively, for raw material of surface layer B, polyester (C) 100% by weight of the raw material as an intermediate layer raw material is supplied to three vented extruders, melt extruded at 290 ° C., and then on a cooling roll whose surface temperature is set to 40 ° C. using an electrostatic application adhesion method.
  • the coating solution 1-1 for the antistatic layer is formed on the surface layer A
  • the coating solution 2-1 for the easy adhesion layer is coated on the surface layer B
  • the thicknesses (after drying) of the antistatic layer and the easy adhesion layer are each. It apply
  • the film was guided to a tenter, stretched 4.0 times in the transverse direction at 100 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 2% in the transverse direction, and a thickness of 75 ⁇ m (thickness composition ratio: surface layer A / intermediate)
  • Layer / surface layer B 6 ⁇ m / 63 ⁇ m / 6 ⁇ m) to obtain a laminated polyester film F1a.
  • a pressure-sensitive adhesive layer composed of the following pressure-sensitive adhesive layer composition is applied to the surface of the easy-adhesion layer of the laminated polyester film F1a so that the thickness (after drying) is 25 ⁇ m and dried at 100 ° C. for 5 minutes to obtain a surface protective film. It was.
  • Adhesive layer composition >> A solution of an acrylic copolymer having a weight average molecular weight of 600,000 (polystyrene conversion) by copolymerizing butyl acrylate (100 parts by weight) and acrylic acid (6 parts by weight) in ethyl acetate by a conventional method (solid content: 30% by weight) %).
  • Tetrad C manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Examples A2 to A6 and A9 to A23 Manufacture of laminated polyester films F2a to F6a and F9a to F23a
  • the production method of the laminated polyester film F1a it was produced in the same manner as the laminated polyester film F1a except that the type of polyester and the coating solution composition of the antistatic layer and the easy adhesion layer were changed as shown in Tables 4 to 5.
  • Laminated polyester films F2a to F6a and F9a to F23a were obtained.
  • a surface protective film was obtained in the same manner as in Example A1 except that the laminated polyester films F2a to F6a or F9a to F23a were used in place of the laminated polyester film F1a.
  • Examples A7 and A8 Manufacture of laminated polyester films F7a and F8a
  • Example A1 except that instead of the laminated polyester film F1a, the laminated polyester film F7a or F8a was used, respectively, and the type of adhesive layer was changed to a silicone adhesive (“SD4580” manufactured by Toray Dow Corning). It manufactured similarly and obtained the surface protection film.
  • Comparative Example A1 Manufacture of laminated polyester film F24a
  • the laminated polyester film F1a In the production method of the laminated polyester film F1a, it was produced in the same manner as the laminated polyester film F1a except that the antistatic layer was not provided to obtain a laminated polyester film F24a.
  • a surface protective film was obtained in the same manner as in Example A1, except that the laminated polyester film F24a was used instead of the laminated polyester film F1a.
  • Comparative Example A2 Manufacture of laminated polyester film F25a
  • the manufacturing method of the laminated polyester film F1a it manufactured like the laminated polyester film F1a except having changed the kind of polyester as shown in Table 6, and obtained the laminated polyester film F25a.
  • a surface protective film was obtained in the same manner as in Example A1 except that the laminated polyester film F25a was used instead of the laminated polyester film F1a.
  • Comparative Examples A3 and A4 Manufacture of laminated polyester films F26a and F27a
  • the laminated polyester film F1a was produced in the same manner as the laminated polyester film F1a except that the coating solution composition of the antistatic layer was changed as shown in Table 6 to obtain laminated polyester films F26a and F27a.
  • a surface protective film was obtained in the same manner as in Example A1, except that the laminated polyester film F26a or F27a was used instead of the laminated polyester film F1a.
  • Example B1 Manufacture of laminated polyester film F1b
  • Polyester (D) 100% by weight as raw material for surface layer A, polyester (D), (F) blended at a ratio of 90% by weight and 10% by weight, respectively, as raw material for surface layer B, polyester (C), (G) and (H) were blended in proportions of 50% by weight, 25% by weight, and 25% by weight, respectively, as intermediate layer raw materials, supplied to three vented extruders, and melt extruded at 290 ° C. Then, it cooled and solidified on the cooling roll which set surface temperature to 40 degreeC using the electrostatic application adhesion method, and the amorphous film with a thickness of about 1500 micrometers was obtained. This film was stretched 3.4 times in the machine direction at 85 ° C.
  • the coating solution 1-1 for the antistatic layer is formed on the surface layer A
  • the coating solution 2-1 for the easy adhesion layer is coated on the surface layer B
  • the thicknesses (after drying) of the antistatic layer and the easy adhesion layer are each. It apply
  • the film was guided to a tenter, stretched 4.0 times in the transverse direction at 100 ° C., heat treated at 230 ° C., and then subjected to a relaxation treatment of 2% in the transverse direction, and a thickness of 75 ⁇ m (thickness composition ratio: surface layer A / intermediate)
  • Layer / surface layer B 6 ⁇ m / 63 ⁇ m / 6 ⁇ m) to obtain a laminated polyester film F1b.
  • a pressure-sensitive adhesive layer composed of the following pressure-sensitive adhesive layer composition is applied to the surface of the easy-adhesion layer of the laminated polyester film F1b so that the thickness (after drying) is 25 ⁇ m and dried at 100 ° C. for 5 minutes to obtain a surface protective film. It was.
  • Adhesive layer composition >> A solution of an acrylic copolymer having a weight average molecular weight of 600,000 (polystyrene conversion) by copolymerizing butyl acrylate (100 parts by weight) and acrylic acid (6 parts by weight) in ethyl acetate by a conventional method (solid content: 30% by weight) %).
  • Tetrad C manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Examples B2 to B6 and B9 to B28 Manufacture of laminated polyester films F2b to F6b and F9b to F28b
  • the laminated polyester film F1b it was produced in the same manner as the laminated polyester film F1b except that the type of polyester and the coating solution composition of the antistatic layer and the easy adhesion layer were changed as shown in Tables 7 to 9, Laminated polyester films F2b to F6b and F9b to F28b were obtained.
  • a surface protective film was obtained in the same manner as in Example B1, except that the laminated polyester films F2b to F6b or F9b to F28b were used in place of the laminated polyester film F1b.
  • Examples B7 and B8 Manufacture of laminated polyester films F7b and F8b Manufactured in the same manner as the laminated polyester film F1b to obtain a laminated polyester film F7b. Moreover, in the manufacturing method of laminated polyester film F1b, it manufactured similarly to laminated polyester film F1b except having changed the coating liquid composition of the easily bonding layer as shown in Table 7, and obtained laminated polyester film F8b. (Manufacture of surface protection film)
  • Example B1 except that instead of the laminated polyester film F1b, the laminated polyester film F7b or F8b was used, and the type of the adhesive layer was changed to a silicone adhesive (“SD4580” manufactured by Toray Dow Corning). It manufactured similarly and obtained the surface protection film.
  • Comparative Example B1 Manufacture of laminated polyester film F29b
  • the laminated polyester film F1b In the production method of the laminated polyester film F1b, it was produced in the same manner as the laminated polyester film F1b except that the antistatic layer was not provided to obtain a laminated polyester film F29b.
  • a surface protective film was obtained in the same manner as in Example B1 except that the laminated polyester film F29b was used instead of the laminated polyester film F1b.
  • Comparative Example B2 Manufacture of laminated polyester film F30b
  • the manufacturing method of the laminated polyester film F1b it manufactured like the laminated polyester film F1b except having changed the kind of polyester as shown in Table 10, and obtained the laminated polyester film F30b.
  • a surface protective film was obtained in the same manner as in Example B1 except that the laminated polyester film F30b was used instead of the laminated polyester film F1b.
  • Comparative examples B3 and B4 Manufacture of laminated polyester films F31b and F32b
  • a laminated polyester film F1b was produced in the same manner as the laminated polyester film F1b except that the coating solution composition of the antistatic layer was changed as shown in Table 10 to obtain laminated polyester films F31b and F32b.
  • a surface protective film was obtained in the same manner as in Example B1 except that the laminated polyester film F31b or F32b was used instead of the laminated polyester film F1b.
  • Comparative Example B5 Also listed as prior art. In the laser processing evaluation, a small amount of foreign matter derived from the surface protective film was adhered to the cut surface because the surface protective film itself did not have a laser light absorption function.
  • the laminated polyester film of the present invention is for surface protection of various adherends such as synthetic resin plates, glass plates, metal plates, optical members, automobile members, electrical or electronic members, building material members, stationery or office supplies members. Can be suitably used. Among them, for protecting the surface of optical members that require particularly high visibility, for example, glass substrates, light diffusion films, liquid crystal displays (polarizing plates, retardation plates, light guide plates, prism plates, etc.), touch panels, etc. In the case of using for the surface protection film, it is easy to inspect with optical evaluation, has good antistatic property, and has a laser light absorption function. Laser processing (cutting, marking, trimming, drilling, etc.) with minimal adhesion or member burr generation is possible, and its industrial value is high.
  • adherends such as synthetic resin plates, glass plates, metal plates, optical members, automobile members, electrical or electronic members, building material members, stationery or office supplies members.
  • for protecting the surface of optical members that require particularly high visibility for example, glass substrates, light diffusion

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Abstract

La présente invention concerne un film de polyester stratifié qui comporte une couche antistatique sur au moins une surface du film de polyester, et est caractérisé en ce que la couche antistatique contient un polythiophène ou un dérivé de polythiophène, et la couche la plus à l'extérieur du film de polyester en contact avec la couche antistatique ne contient pas de particules.
PCT/JP2017/036194 2016-10-05 2017-10-04 Film de polyester stratifié Ceased WO2018066618A1 (fr)

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CN201780060353.2A CN109789691B (zh) 2016-10-05 2017-10-04 层叠聚酯薄膜
CN202210037345.9A CN114407470B (zh) 2016-10-05 2017-10-04 层叠聚酯薄膜
KR1020197008934A KR102359332B1 (ko) 2016-10-05 2017-10-04 적층 폴리에스테르 필름

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