CN117545629A - Antistatic film and protective film - Google Patents

Antistatic film and protective film Download PDF

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Publication number
CN117545629A
CN117545629A CN202280044847.2A CN202280044847A CN117545629A CN 117545629 A CN117545629 A CN 117545629A CN 202280044847 A CN202280044847 A CN 202280044847A CN 117545629 A CN117545629 A CN 117545629A
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China
Prior art keywords
less
film
polyester film
mass
antistatic layer
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CN202280044847.2A
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Chinese (zh)
Inventor
杉本由佳
中谷充晴
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Toyobo Co Ltd
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Toyobo Co Ltd
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Publication of CN117545629A publication Critical patent/CN117545629A/en
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    • 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
    • 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
    • B32B27/36—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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

[ problem ]]An antistatic film and a protective film are provided in which an antistatic layer laminated on the opposite surface of the protective film from an adhesive layer has good releasability from an adhesion roller. Means for solving the problems]A laminated polyester film having an antistatic layer on at least one side of a substrate, wherein the antistatic layer is obtained by curing a composition comprising a conductive polymer, a crosslinking agent (A), and a binder resin (B), and the binder resin (B) is a long-chain alkyl-containing compound having at least 1 reactive group, and the antistatic layer satisfies the following (1) to (3): (1) surface resistivity: 3[ log Ω/≡]Above 9[ log Ω/≡]The following are set forth; (2) static contact angle of water: 70-95 degrees; (3) adhesion energy of water: 3.5mJ/m 2 The following is given.

Description

Antistatic film and protective film
Technical Field
The present invention relates to a laminated polyester film and a protective film formed by laminating an adhesive layer on the laminated polyester film, and particularly relates to a protective film for an optical member (for example, a constituent member of an organic EL or a liquid crystal display) or the like.
Background
Films formed by laminating an adhesive layer on a base film are used as protective films for respective members in the production process of optical members and the like. The protective film is bonded to each member as an adherend via an adhesive layer, and plays a role in suppressing scratches and dirt adhesion during processing and conveyance of each member. As a base film used for these protective films, an antistatic film having an antistatic layer laminated on at least one side thereof is used. The antistatic layer is provided to prevent foreign matter such as dust or the like from adhering to the protective film and to suppress static electricity generated when the protective film is peeled from the adherend (see patent document 1).
As an antistatic film, a film containing PEDOT: PSS is used as an antistatic film of an antistatic agent (see patent document 2).
Prior art literature
Patent literature
Patent document 1: international publication 2018/012545
Patent document 2: japanese patent laid-open publication No. 2018-172473
Disclosure of Invention
Problems to be solved by the invention
The protective film having an antistatic layer can be used as a protective film for optical members and the like, particularly in a process for manufacturing a constituent member of a display. In recent years, it has also been increasingly used in the process of manufacturing members of organic EL displays (particularly OLED displays). In the step of bonding the protective film to the optical member, the protective film is bonded by pressing the surface of the protective film opposite to the lamination surface of the adhesive layer with a bonding roller or the like so that the adhesive surface of the protective film contacts the optical member.
When the laminating roller is used for laminating the protective film in the above manner, there are cases where: the interaction between the opposite surface of the protective film to the lamination surface of the adhesive layer and the laminating roller becomes strong, so that the releasability of the laminating roller from the protective film is lowered, and the protective film cannot be uniformly laminated. In particular, in recent years, in order to reduce the adhesiveness of an adhesive even when a fragile and easily scratched precision member is peeled off while the deformation of the member can be suppressed, the releasability between the laminating roller and the protective film is particularly problematic in such applications.
The present invention addresses the problem of the protective film and provides an antistatic film and a protective film which have excellent releasability between an antistatic layer laminated on the surface of the protective film opposite to the adhesive layer and a laminating roller.
Solution for solving the problem
That is, the present invention includes the following constitution.
[1] A laminated polyester film having an antistatic layer on at least one side of a base material,
the antistatic layer is a layer obtained by curing a composition containing a conductive polymer, a crosslinking agent (A), and a binder resin (B),
the binder resin (B) is a long-chain alkyl group-containing compound having at least 1 reactive group,
the above antistatic layer satisfies the following (1) to (3):
(1) Surface resistivity: 3[ log Ω/≡ ] or more and 9[ log Ω/≡ ] or less;
(2) Contact angle of water: 70 DEG to 95 DEG;
(3) Adhesion energy of water: 3.5mJ/m 2 The following is given.
[2] In one embodiment, the laminated polyester film has a total light transmittance of 80% or more and a haze of 3.0% or less.
[3] In one embodiment, the haze of the laminated polyester film after heating at 140 ℃ for 10 minutes is 1.5 times or less the haze before heating.
[4] In one embodiment, the surface resistivity of the antistatic layer after the wiping test with alcohol changes 1.3 times or less the surface resistivity before the test.
[5] In one embodiment, the conductive polymer is contained in an amount of 5 mass% to 50 mass% with respect to 100 mass% of the total solid content in the antistatic layer.
[6] In one embodiment, the laminated polyester film according to any one of claims 1 to 5, comprising the crosslinking agent (a) and the binder resin (B) in the following ranges, relative to 100 mass% of the total solid content in the antistatic layer.
(A) 15 mass% or more and 75 mass% or less
(B) 10 mass% or more and 70 mass% or less
[7] In one embodiment, the binder resin (B) has a hydroxyl value of 20mgKOH/g or more and 300mgKOH/g or less.
[8] In one embodiment, the binder resin (B) contains carboxyl groups.
[9] In one embodiment, the crosslinking agent comprises at least 1 selected from the group consisting of acrylamide, melamine resin, carbodiimide, oxazoline, isocyanate, and aziridine.
[10] In one embodiment, the laminated polyester film contains substantially no organosilicon compound.
[11] In one embodiment, a protective film is provided in which an adhesive layer is laminated on at least one side of the laminated polyester film.
Here, 100% by mass of the total solid content means the total mass% of the electric polymer, the crosslinking agent (a), and the binder resin (B).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, by providing an antistatic film in which an antistatic layer having low adhesion energy is laminated on at least one side of a polyester film, it is possible to provide: when the laminated polyester film of the present invention is used as a protective film by laminating an adhesive layer thereon, the protective film has good releasability from a laminating roller at the time of laminating the protective film and suppresses peeling electrification and adhesion of foreign matters at the time of peeling.
Detailed Description
The laminated polyester film (also referred to as antistatic film) of the present invention is a polyester film having an antistatic layer laminated on at least one side thereof. The antistatic film may be formed by laminating an adhesive layer on one surface thereof, and may be used as a protective film.
For example, in the case of using the laminating roller in laminating the protective film, the laminated polyester film of the present invention can suppress the interaction between the opposite surface of the protective film to the lamination surface of the adhesive layer and the laminating roller from becoming strong, and can avoid the lowering of the releasability between the laminating roller and the protective film. Further, the protective film can be uniformly bonded.
In particular, in recent years, in order to prevent a fragile and easily scratched precision member from peeling off the precision member while suppressing deformation of the precision member, the adhesion of the adhesive may be reduced, and even in such a use, the present invention can maintain good releasability between the bonding roller and the protective film.
The present invention will be described in detail below.
(polyester film)
The polyester film used as a substrate in the present invention is a film composed mainly of a polyester resin. The term "film mainly composed of a polyester resin" means a film formed from a resin composition containing 50% by mass or more of a polyester resin, and when blended with other polymers, it means a film containing 50% by mass or more of a polyester resin, and when copolymerized with other monomers, it means a film containing 50% by mole or more of a repeating structural unit of a polyester. The polyester film preferably contains 90 mass% or more, more preferably 95 mass% or more, and still more preferably 100 mass% of the polyester resin in the resin composition constituting the film.
The polyester resin is not particularly limited, and a copolymer obtained by polycondensation of a dicarboxylic acid component and a diol component, or a resin blend thereof may be used. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, diphenyl carboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl sulfone carboxylic acid, anthracene dicarboxylic acid, 1, 3-cyclopentane dicarboxylic acid, 1, 3-cyclohexane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, malonic acid, dimethyl malonic acid, succinic acid, 3-diethyl succinic acid, glutaric acid, 2-dimethyl glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, azelaic acid, dimer acid, sebacic acid, suberic acid, dodecanedicarboxylic acid, and the like.
Examples of the diol component constituting the polyester resin include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, decamethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone.
The dicarboxylic acid component and the diol component constituting the polyester resin may be used in an amount of 1 or 2 or more, respectively. In addition, other acid components such as trimellitic acid and other hydroxyl components such as trimethylolpropane may be suitably added.
Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and among these, polyethylene terephthalate is preferable in terms of balance between physical properties and cost.
In order to improve the handleability such as slidability and winding property of the polyester film, inactive particles may be contained in the film, but in the case of use for optical applications or the like, it is preferable that the polyester film contains substantially no particles. When the polyester film does not contain particles, it is preferable that the coating layer provided by in-line coating contains particles. The polyester film is preferably free of particles and the coating layer contains particles, because the transparency is improved and the appearance inspection and the like are easy to perform.
The haze of the polyester film used in the present invention is preferably 3% or less. More preferably 2.5% or less, and may be 2.0% or less. It may be 1.5% or less, more preferably 1.0% or less, and still more preferably 0.8% or less.
When the content is 3% or less, it is preferable to perform appearance inspection or the like in a state where the protective film is bonded to the adherend, and particularly preferable when the member for optical use is the adherend.
The area surface average roughness (Sa) of the surface of the polyester film used in the present invention is preferably in the range of 1 to 40nm, more preferably 1 to 30nm. Further preferably 1 to 10nm. The maximum protrusion height (P) of the surface of the polyester film used in the present invention is preferably 2 μm or less, more preferably 1.5 μm or less. More preferably 0.8 μm or less. When Sa is 40nm or less and P is 2 μm or less, there is no need to worry about roughening of the adhesive surface even when the adhesive layer is laminated and wound into a roll, and it is preferable.
In the present invention, the thickness of the polyester film is not particularly limited, and is preferably in the range of 12 to 188. Mu.m. More preferably 18 to 125. Mu.m, still more preferably 25 to 100. Mu.m. When the thickness is 12 μm or more, there is no fear of wrinkles when the protective film is bonded to an adherend, and when the thickness is 188 μm or less, the cost is advantageous.
The polyester film to be the base material may be a single layer or may be a laminate of 2 or more layers. In addition, if the effect of the present invention is exhibited, various additives may be contained in the film as required. Examples of the additives include antioxidants, photostable agents, antigelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, and surfactants. When the film has a laminated structure, it is preferable that the film contains additives according to the function of each layer.
The polyester film is obtained, for example, by the following method: the polyester resin was melt-extruded into a film, and cooled and solidified on a casting drum to form a film. The polyester film of the present invention may be a non-stretched film or a stretched film, and is preferably a stretched film in terms of durability such as mechanical strength and chemical resistance. In the case where the polyester film is a stretched film, the stretching method is not particularly limited, and a longitudinal uniaxial stretching method, a transverse uniaxial stretching method, a longitudinal and transverse sequential biaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, or the like may be used.
In order to improve the adhesion with the adhesion improving layer, the surface layer of the polyester film may be subjected to a surface treatment such as an anchor coating layer, corona treatment, plasma treatment, flame treatment, or the like. In the case of providing the anchor coat layer, it is preferable to perform it by in-line coating from the viewpoint of cost and the like.
(antistatic layer)
The laminated polyester film (antistatic film) of the present invention requires an antistatic layer to be laminated on at least one side of the polyester film. The antistatic layer may be laminated on only one side or on both sides. The lamination of the antistatic layer is preferable because peeling static electricity and foreign matter adhesion to an adherend can be suppressed even when the adhesive layer is laminated as a protective film.
The antistatic layer is a layer obtained by curing a composition containing a conductive polymer, a crosslinking agent (a), and a binder resin (B). Such a composition is sometimes referred to as an antistatic layer-forming composition.
The means for laminating the antistatic layer is not particularly limited, and known methods such as a coating method, a vacuum vapor deposition method, and lamination may be used, and from the viewpoint of cost, it is more preferable to provide a coating liquid containing an antistatic agent by coating.
(conductive Polymer)
The conductive polymer in the present invention is a polymer capable of imparting antistatic properties, and a polymer utilizing ion conduction such as a cationic compound, a pi-electron conjugated system conductive polymer, or the like can be used from the viewpoint of antistatic properties at low humidity. Preferably, a pi-electron conjugated conductive polymer is used. In addition, the pi-electron conjugated conductive polymer is preferable because it can maintain antistatic performance at a high level regardless of moisture in the air and thus has good antistatic performance in various use environments of the protective film.
The antistatic agent may be used in combination within a range that does not impair the effect exerted by the conductive polymer of the present invention. The antistatic agent may be a polymer utilizing ion conduction such as a cationic compound other than the conductive polymer in the present invention, or a pi-electron conjugated system conductive polymer, and a surfactant, a silicon oxide compound, a conductive metal compound, or the like may be used.
Examples of the pi-electron conjugated conductive polymer include aniline polymers containing aniline or its derivative as a structural unit, pyrrole polymers containing pyrrole or its derivative as a structural unit, acetylene polymers containing acetylene or its derivative as a structural unit, thiophene polymers containing thiophene or its derivative as a structural unit, and the like. If high transparency is desired, a conductive polymer having no nitrogen atom as pi-electron conjugated system is preferable, and among them, a thiophene-based polymer containing thiophene or a derivative thereof as a structural unit is preferable from the viewpoint of transparency, and polyalkylene dioxythiophene is particularly preferable. Examples of the polyalkylene dioxythiophenes include polyethylene dioxythiophenes, polypropylene dioxythiophenes, and poly (ethylene/propylene) dioxythiophenes.
In a thiophene-based polymer containing thiophene or a derivative thereof as a structural unit, 0.1 parts by mass or more and 500 parts by mass or less of a dopant may be blended with 100 parts by mass of a polymer containing thiophene or a derivative thereof as a structural unit, for example, in order to improve antistatic properties. Many electrons are difficult to move, and thus there is a problem that antistatic performance is lowered, and conversely, there is a problem that dispersibility into a solvent is lowered in a small amount. Examples of the dopant include LiCl and R 1- 30 COOLi(R 1-30 : saturated hydrocarbon group having 1 to 30 carbon atoms), R 1-30 SO 3 Li、R 1-30 COONa、R 1-30 SO 3 Na、R 1- 30 COOK、R 1-30 SO 3 K. Tetraethylammonium, I 2 、BF 3 Na、BF 4 Na、HClO 4 、CF 3 SO 3 H、FeCl 3 Tetracyanoquinoline (TCNQ), na 2 B 10 Cl 10 Phthalocyanine, porphyrin, glutamic acid, alkyl sulfonate, polystyrene sulfonate Na (K, li) salt, styrene-styrene sulfonate Na (K, li) salt copolymer, polystyrene sulfonate anion, styrene sulfonate-styrene sulfonate anion copolymer, and the like.
In the present invention, the conductive polymer contained in the antistatic layer preferably contains 5 mass% or more, more preferably 10 mass% or more, with respect to 100 mass% of the solid content in the antistatic layer. When the pi-electron conjugated conductive polymer is used as the antistatic agent, the content of the antistatic layer of the pi-electron conjugated conductive polymer defined in the present application is the total amount of the conductive polymer and the dopant.
By containing the antistatic agent in such an amount, good antistatic properties can be imparted.
In the present invention, the conductive polymer contained in the antistatic layer is preferably 50 mass% or less, more preferably 30 mass% or less, based on 100 mass% of the total solid content in the antistatic layer. When the pi-electron conjugated conductive polymer is used as the antistatic agent, the content of the pi-electron conjugated conductive polymer in the antistatic layer defined in the present application is the total amount of the conductive polymer and the dopant.
By containing the antistatic agent in such an amount, interaction with the binder resin (B) or the like is less likely to occur, the coating liquid is less likely to aggregate, the disadvantage of the antistatic layer is less, and high transparency can be maintained.
[ Binder resin (B) ]
The antistatic layer of the present invention contains a binder resin (B). The binder resin is not particularly limited, and specific examples thereof include polyester resins, acrylic resins, urethane resins, polyolefin resins, polyvinyl resins (polyvinyl alcohol and the like), polyalkylene glycols, polyalkyleneimines, methylcellulose, hydroxycellulose, starches and the like. Among these, polyester resins, acrylic resins, and urethane resins are preferably used from the viewpoint of adhesion to polyester films. Acrylic resins are more preferably used in terms of easiness of molecular design and molecular weight design.
In order to improve the releasability between the surface of the antistatic layer and the laminating roller, the binder resin (B) preferably has a component capable of reducing the adhesive energy of the surface of the antistatic layer. The component preferably includes a silicone component, a long-chain alkyl component, a fluorine component, and the like. In view of migration to an adherend or the like, a long-chain alkyl component is more preferable, and the binder resin (B) is a long-chain alkyl-containing compound. The binder resin (B) is preferably a long-chain alkyl group-containing compound having at least 1 reactive group, as will be described later.
When the laminating polyester film of the present invention contains a long-chain alkyl compound, for example, when the laminating roller is used for laminating the protective film, the interaction between the opposite surface of the protective film to the lamination surface of the adhesive layer and the laminating roller can be suppressed from becoming strong, and the lowering of the releasability of the laminating roller from the protective film can be avoided. Further, the protective film can be uniformly bonded.
In particular, in recent years, in order to reduce the adhesiveness of an adhesive in order to be able to peel off a precision member that is fragile and easily scratched while suppressing deformation of the member, the present invention can maintain good releasability between a bonding roller and a protective film even in such applications.
The binder resin (B) preferably has at least 1 reactive group. The binder resin (B) preferably has a hydroxyl group, a carboxyl group, an amino group, an acrylate group, an epoxy group, or the like, and more preferably has a hydroxyl group or a carboxyl group, although not particularly limited thereto.
As the binder resin (B) of the present invention, an acrylic resin is preferable. Acrylic resins containing long chain alkyl groups, also having at least 1 reactive functional group, are particularly preferred.
The acrylic resin is preferably an acrylic resin having a hydroxyl group and a carboxyl group in the molecule. It is more preferable that the structural unit having a hydroxyl group is contained in an amount of 15 to 90 mol% based on 100 mol% of the total structural units. When the structural unit having a hydroxyl group is 20 mol% or more, the water solubility of the acrylic resin can be kept moderate, which is preferable. On the other hand, if the amount is 90 mol% or less, the ratio of the low adhesion energy component can be kept moderate, which is preferable.
For introducing a hydroxyl group into an acrylic resin, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and a ring-opened adduct of gamma-butyrolactone, epsilon-caprolactone to 2-hydroxyethyl (meth) acrylate may be used as a copolymerization component. Among them, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of not interfering with water solubility. It should be noted that 2 or more kinds of these may be used in combination.
The hydroxyl value of the binder resin (B), for example, the hydroxyl value of the acrylic resin is preferably 20mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 70mgKOH/g or more, for example, 120mgKOH/g or more. When the hydroxyl value of the binder resin (B), for example, the hydroxyl value of the acrylic resin is 20mgKOH/g or more, the water solubility of the acrylic resin is preferable. Although the acrylic resin is exemplified as the hydroxyl value, the resin that can be used for the binder resin (B) of the present invention can exhibit the effects described in the present specification by having the hydroxyl value in the above range.
The hydroxyl value of the binder resin (B), for example, the hydroxyl value of the acrylic resin is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, and still more preferably 200mgKOH/g or less. When the hydroxyl value of the binder resin (B), for example, the hydroxyl value of the acrylic resin is 300mgKOH/g or less, the hydroxyl group of the acrylic resin does not extremely interact with the antistatic component such as polythiophene, and the coating solution is preferably less likely to aggregate.
The acrylic resin used in the present invention is preferably a resin having a carboxyl group. By having a carboxyl group, a crosslinked structure can be formed with a crosslinking agent, and water solubility can be easily imparted. Examples thereof include carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; monomers having an acid anhydride group such as maleic anhydride and itaconic anhydride.
For example, the binder resin (B) may have a carboxyl group alone or together with the hydroxyl group.
The monomer having a carboxyl group is preferably 2 mol% or more, more preferably 5 mol% or more, of 100 mol% or more of the total structural units of the acrylic resin. When the amount is 4 mol% or more, it is preferable that a crosslinked structure is formed in the antistatic layer and water solubility is easily imparted. The monomer having a carboxyl group is preferably 65 mol% or less, more preferably 50 mol% or less. When the Tg of the coating film is 65 mol% or less, the Tg of the resulting coating film is preferably excellent in film forming property without being excessively high from the preferable range described later.
In order to exhibit good water solubility, it is preferable to neutralize carboxyl groups introduced into the acrylic resin by copolymerization of acrylic acid and methacrylic acid. The alkaline neutralizing agent includes amine compounds such as ammonia, trimethylamine, triethylamine, and dimethylaminoethanol; among them, amine compounds are preferably used as the neutralizing agent in order to facilitate volatilization of the neutralizing agent and formation of a crosslinked structure. The neutralization rate is preferably 30 to 95 mol%, more preferably 40 to 90 mol%. When the neutralization degree is 30 mol% or more, the water solubility of the acrylic resin is sufficient, and the acrylic resin is more easily dissolved in the preparation of the coating liquid, and the dried coating film surface is preferably free from the concern of whitening. On the other hand, when the neutralization rate is 95 mol% or less, the water solubility is not excessively high, and mixing of alcohols and the like in the preparation of the coating liquid is easy, which is preferable.
The acid value of the binder resin (B), for example, the acid value of the acrylic resin is preferably 40mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 60mgKOH/g or more. When the acid value of the acrylic resin is 40mgKOH/g or more, the crosslinking point with the crosslinking agent increases, and thus a strong coating film having a higher crosslinking density is obtained, which is preferable.
Although the acrylic resin is exemplified as the acid value, the resin that can be used for the binder resin (B) of the present invention can also exhibit the effects of the present specification by having an acid value in the above-described range.
The acid value of the binder resin (B), for example, the acid value of the acrylic resin is preferably 400mgKOH/g or less, more preferably 350mgKOH/g or less, and still more preferably 300mgKOH/g or less. When the acid value of the acrylic resin is 400mgKOH/g or less, the carboxyl group of the acrylic resin and the antistatic agent such as polythiophene do not extremely interact with each other, and aggregation is not likely to occur, which is preferable. When aggregation occurs in the coating liquid, the uniformity of the antistatic layer is lowered, and the antistatic property and transparency are lowered, so that the binder resin (B) of the present invention is preferable to avoid such a problem.
Regarding the long-chain alkyl group in the binder resin (B), it is preferable that the resin has an alkyl group having 8 to 25 carbon atoms in a side chain.
In one embodiment, the acrylic resin having a long-chain alkyl group introduced therein is preferably an acrylic resin having an alkyl group having 8 to 25 carbon atoms in a side chain thereof, more preferably an alkyl group having 12 to 22 carbon atoms, and still more preferably an alkyl group having 16 to 20 carbon atoms. In addition, a copolymer having a long-chain alkyl group having 8 to 20 carbon atoms in the transesterified portion, which contains a (meth) acrylate as a main repeating unit, may be preferably used. Examples thereof include lauryl (meth) acrylate and stearyl (meth) acrylate. Among them, stearyl methacrylate is preferably used from the viewpoints of starting easiness, cost, and low adhesion energy.
Among the monomers to be copolymerized, the monomer having a long-chain alkyl group is preferably 50 mol% or less, more preferably 40 mol% or less, of 100 mol% or less of the total structural units of the binder resin (B), for example, the acrylic resin. When 50 mol% or less, the adhesion energy of the surface of the coating film of the antistatic layer can be effectively reduced, and the Tg of the obtained coating film is preferably maintained high without excessively lowering the Tg of the coating film relative to the preferable range. In the present invention, the monomer having a long chain alkyl group is preferably 5% or more of 100 mol% of the total structural units of the acrylic resin. When the amount is 5% or more, the adhesion energy of the surface of the coating film of the antistatic layer can be reduced, which is preferable.
The glass transition temperature (Tg) of the binder resin (B), for example, the acrylic resin, is preferably 50 ℃ or higher, more preferably 55 ℃ or higher, and still more preferably 60 ℃ or higher. When the glass transition temperature of the acrylic resin is 50 ℃ or higher, the change with time of the antistatic layer is suppressed, which is preferable.
The glass transition temperature (Tg) of the binder resin (B), for example, the acrylic resin, is preferably 110 ℃ or less, more preferably 105 ℃ or less, and further preferably 100 ℃ or less. When the glass transition temperature of the acrylic resin is 110 ℃ or lower, the coating film is preferably not excessively brittle, and the antistatic layer is less likely to crack.
As the Tg-adjusting monomer copolymerized so as to have Tg in the above range, (meth) acrylic monomers and non-propylene vinyl monomers can be used. Specific examples of the (meth) acrylic monomer include (meth) acrylic alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, and the like; nitrogen-containing acrylic monomers such as (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide, and (meth) acrylonitrile; vinyl methacrylate, etc., and 1 or 2 or more kinds of these may be used.
Further, as the non-acrylic vinyl monomer, styrene monomers such as styrene, α -methylstyrene, vinyltoluene (a mixture of meta-methylstyrene and para-methylstyrene), chlorostyrene and the like; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl caprylate, vinyl monochloroacetate, divinyl adipate, vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate; vinyl halide monomers such as vinyl chloride and vinylidene chloride may be used in an amount of 1 or 2 or more.
The monomer for Tg adjustment is preferably set as the balance thereof after determining the appropriate amounts of the hydroxyl group-containing monomer and the carboxyl group-containing monomer. Tg of the copolymer was determined by the following Fox formula.
W n : percentage by mass of each monomer (mass%)
Tg n : tg (K) of homopolymers of the respective monomers
The acrylic resin used in the present invention can be obtained by known radical polymerization. Emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and the like may be employed. From the viewpoint of handling properties, solution polymerization is preferred. Examples of the water-soluble organic solvent which can be used for the solution polymerization include ethylene glycol N-butyl ether, isopropyl alcohol, ethanol, N-methylpyrrolidone, tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxolane, methyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like. These may be used in combination with water.
The polymerization initiator may be any known compound that generates a radical, and for example, a water-soluble azo-based polymerization initiator such as 2, 2-azobis-2-methyl-N-2-hydroxyethyl propionamide is preferable. The temperature, time, etc. of polymerization may be appropriately selected.
The mass average molecular weight (Mw) of the binder resin (B) is preferably about 10,000 ～ 200,000. A more preferred range is 20,000 ～ 150,000. When the Mw is 10,000 or more, the toughness of the coating film is improved, and the strength of the coating film is improved, which is preferable. When the Mw is 200,000 or less, the viscosity of the coating liquid does not significantly increase, and the coating property is preferable.
The antistatic layer of the present invention preferably contains 10 mass% or more of the binder resin (B), more preferably 40 mass% or more, relative to 100 mass% of the total solid content in the antistatic layer. When the amount is 10% by mass or more, the static water contact angle is preferably high.
In the antistatic layer of the present invention, the binder resin (B) is preferably 70 mass% or less, more preferably 60 mass% or less, relative to 100 mass% of the total solid content in the antistatic layer. When the binder resin (B) is 70 mass% or less, it is preferable that the binder resin does not interact with an antistatic agent such as polythiophene and is not easily aggregated. In addition, aggregation in the antistatic layer forming composition to be formed with the antistatic layer can be suppressed, and deterioration in uniformity of the antistatic layer can be avoided, and further, improvement in antistatic property and improvement in transparency can be brought about.
(crosslinking agent (A))
In the present invention, in order to form a crosslinked structure in the antistatic layer, the antistatic layer is formed of a composition containing a crosslinking agent (a). The inclusion of the crosslinking agent (a) is preferable because the durability is improved and the decrease in antistatic performance during the treatment under high-temperature and high-humidity conditions is suppressed. Specific examples of the crosslinking agent include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, carbodiimide-based, and aziridine-based. In one embodiment, the crosslinking agent (a) contains at least 1 selected from the group consisting of acrylamide, melamine resin, carbodiimide, oxazoline, isocyanate, and aziridine. The crosslinking agent (a) is particularly preferably a melamine system, an oxazoline system, a carbodiimide system or an aziridine system. In order to promote the crosslinking reaction, a catalyst or the like may be used as needed.
The crosslinking agent (a) contained in the antistatic layer of the present invention is preferably contained in an amount of 15 mass% or more, more preferably 20 mass% or more, and still more preferably 25 mass% relative to 100 mass% of the total solid content in the antistatic layer. When the amount is 15% by mass or more, the crosslinking point with the binder increases, so that a strong coating film having a higher crosslinking density is obtained, and heat resistance and alcohol resistance are preferable.
The crosslinking agent (a) is preferably 75 mass% or less, for example 65 mass% or less, and may be 55 mass% or less, relative to 100 mass% of the total solid content in the antistatic layer. When the amount is 75 mass% or less, heat resistance and alcohol resistance can be maintained while maintaining the static contact angle within the target range.
In the antistatic layer of the present invention, a surfactant may be used in order to improve the appearance. As the surfactant, for example, nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, fluorine-based surfactants such as fluoroalkyl carboxylic acid, perfluoroalkyl benzenesulfonic acid, perfluoroalkyl quaternary ammonium, perfluoroalkyl polyoxyethylene ethanol, and silicone-based surfactants can be used.
In addition to the above, the antistatic layer may be mixed with a lubricant, a pigment, an ultraviolet absorber, a silane coupling agent, or the like as necessary within a range that does not inhibit the object of the present invention.
In one embodiment, the laminated polyester film contains substantially no organosilicon compound. Preferably, the antistatic layer is substantially free of organosilicon compounds.
In the present invention, the "substantially no organosilicon compound" is defined by a content of 50ppm or less, preferably 10ppm or less, and most preferably a detection limit or less when the Si element is quantified by fluorescent X-ray analysis. This is because, even if the silicone component is not actively added to the film, there are cases where a contaminant component derived from foreign matter, a raw material resin, or dirt attached to a production line or a device in a process of producing the film are peeled off and mixed into the film.
By making the laminated polyester film substantially free of an organosilicon compound, migration of the organosilicon compound to the protected product can be avoided even when the present antistatic film is used as a protective film, and adverse effects on the final product can be reduced.
The thickness of the antistatic layer of the present invention is preferably 0.005 μm or more and 1 μm or less. More preferably from 0.01 μm to 0.5 μm, still more preferably from 0.01 μm to 0.2 μm. When the film thickness of the antistatic layer is 0.005 μm or more, an antistatic effect can be obtained, which is preferable. On the other hand, if it is 1 μm or less, the coloring is less and the transparency is high, so that it is preferable.
The surface resistivity of the antistatic layer of the present invention is 9[ log Ω/≡s ] or less. Further preferably 8[ log Ω/≡ ] or less, and further preferably 7[ log Ω/≡ ] or less. By setting the surface resistivity to 9[ log Ω/≡ ] or less, electrification of the protective film can be suppressed, adhesion of foreign matter in the process can be prevented, and further, adverse influence of electrification of the protective film on the electrical properties of the product to be protected can be suppressed.
The lower limit of the surface resistivity of the antistatic film is not particularly limited, and is preferably 3[ log Ω/≡s ] or more. When the surface resistivity of the antistatic film is less than 3[ log Ω/≡ ], the processing cost of the antistatic layer increases, and thus it is not preferable.
The adhesion energy of water on the surface of the antistatic layer of the antistatic film of the present invention was 3.5mJ/m 2 The following is given. Further preferably 3.2mJ/m 2 Hereinafter, for example, it is 2.9mJ/m 2 The following is given.
The adhesion energy of water was 3.5mJ/m 2 In the following, when the adhesive film is used as a protective film, the releasability between the adhesive roller and the protective film is preferably improved when the adhesive roller is used to adhere an adherend. In order to make the adhesion energy of water 3.5mJ/m 2 The antistatic layer can be obtained by adding a low surface free energy component to the antistatic layer in an appropriate amount, and the binder resin can be obtained by using a polymer containing a low surface free energy componentIt is preferable to provide a protective film which has reduced adhesion and does not migrate to an adherend.
For example, in the present invention, the polymer containing a low surface free energy component may be a conductive polymer, may be the binder resin (B), or may be a polymer both containing a low surface free energy component.
The adhesion energy of water on the surface of the antistatic layer of the antistatic film of the present invention is preferably 1.1mJ/m 2 The above is more preferably 1.3mJ/m 2 The above. When the adhesion of water is within such a range, the adhesive layer and the like are processed on the antistatic layer, and the adhesive layer is excellent in wettability, and the adhesive layer is less likely to be repelled.
The antistatic film of the present invention has a static contact angle of water of 70 ° or more and 95 ° or less, for example, 75 ° or more and 95 ° or less, and may have 80 ° or more and 95 ° or less.
By setting the static contact angle of water to such a range, the interaction between the bonding roller and the opposite surface of the adhesive layer lamination surface of the protective film can be suppressed from becoming stronger.
In the present invention, it is important to set the static contact angle and adhesion energy of water within the above-mentioned ranges.
For example, the adhesive energy using water is 3.5mJ/m 2 In the case of a film having a static contact angle of water of more than 95 °, the release property of the bonding roller is good, but the coating property is poor when the adhesive layer is processed on the antistatic layer, and a protective film having many defects tends to be formed. In particular, if the static contact angle of water greatly exceeds 95 °, the tendency is stronger.
The laminated polyester film of the present invention is characterized in that,
(1) Surface resistivity: 3[ log Ω/≡ ] or more and 9[ log Ω/≡ ] or less;
(2) Static contact angle of water: 70 DEG to 95 DEG;
(3) Adhesion energy of water: 3.5mJ/m 2 The following is given.
By providing all of these (1) to (3), when the antistatic film is used as a protective film by laminating an adhesive layer thereon, a protective film having good releasability from a laminating roller at the time of laminating the protective film, peeling electrification at the time of peeling, and suppressed adhesion of foreign matters can be provided.
By using an antistatic film satisfying the above ranges of the static contact angle and the adhesion energy of water as a protective film, a protective film having good workability (for example, good wettability and less defects) of an adhesive layer on an antistatic layer, suppressing electrification of the protective film, having good releasability from a laminating roller, and excellent lamination can be provided.
The haze of the laminated polyester film of the present invention is preferably 3.0% or less. More preferably 2.5% or less, still more preferably 2.0% or less, for example 1.5% or less. More preferably 1.0% or less. When the content is 3.0% or less, it is preferable that the protective film and the adherend be bonded to each other, since appearance inspection or the like can be performed, and particularly preferable when the member for optical use is an adherend. The haze may be 0, for example, 0.1% or more.
The haze of the laminated polyester film of the present invention after heating at 140℃for 10 minutes is preferably 1.5 times or less the haze before heating. More preferably 1.3 times or less, and still more preferably 1.2 times or less. When the ratio is 1.5 times or less, it is preferable that the protective film and the adherend be bonded to each other, since appearance inspection or the like can be performed, and particularly preferable when the member for optical use is an adherend.
The total light transmittance of the laminated polyester film (antistatic film) used in the present invention is preferably 80% or more. More preferably 85% or more, still more preferably 88% or more. When the content is 90% or more, it is particularly preferable. When the content is 80% or more, it is preferable to use an optically-used member as an adherend because it is possible to perform appearance inspection or the like in a state where the protective film is bonded to the adherend.
The change in surface resistivity of the antistatic layer after the wiping test with alcohol is preferably 1.3 times or less the surface resistivity before the test. More preferably 1.2 times or less, and still more preferably 1.1 times or less. When the ratio is 1.3 times or less, the initial surface resistivity is maintained when the protective film is formed even if alcohol is used in the steps such as the adhesion process.
The area surface average roughness (Sa) of the surface of the antistatic layer is preferably in the range of 1 to 40nm, more preferably 1 to 30nm. Further preferably 1 to 10nm. The maximum protrusion height (P) of the surface of the antistatic film used in the present invention is preferably 2 μm or less, more preferably 1.5 μm or less. More preferably 0.8 μm or less. When Sa is 40nm or less and P is 2 μm or less, there is no need to worry about roughening of the adhesive surface even when the adhesive layer is laminated and wound into a roll, and it is preferable.
As a method of coating the surface of the base film with the laminated antistatic layer, there are methods of coating a coating liquid obtained by dispersing/dissolving the antistatic agent, the binder resin, and the like in a solvent by a gravure roll coating method, a reverse roll coating method, an air knife coating method, a dip coating method, a bar coating method, a spin coating method, and the like, and a coating method suitable for the conductive composition is not particularly limited. The coating layer may be provided by an in-line coating method in which a coating layer is provided in the film manufacturing process, or an off-line coating method in which a coating layer is provided after the film is manufactured.
The drying temperature of the antistatic layer formed by the above method is usually 60 ℃ or higher and 150 ℃ or lower, preferably 90 ℃ or higher and 140 ℃ or lower. The temperature is preferably 60℃or higher, from the viewpoint of enabling a short-time treatment and improving productivity. In addition, when the crosslinking agent is contained, the crosslinking reaction proceeds sufficiently, and is therefore preferable. On the other hand, when the temperature is 150 ℃ or lower, the flatness of the film is maintained, and thus it is preferable.
The adhesive layer may be laminated by applying an adhesive to the laminated polyester film of the present invention and curing it. The adhesive may be used without particular limitation, and the resulting laminated film may be used as a protective film. The surface of the laminated adhesive layer may be either side of the antistatic film. When an antistatic film having an antistatic layer on only one side is used, the antistatic film preferably has an antistatic layer on the surface opposite to the surface on which the adhesive layer is laminated.
In addition, a ceramic green sheet, a resin film, or the like may be laminated on the antistatic layer in the laminated polyester film of the present invention.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The evaluation method used in the present invention is as follows.
(NMR measurement)
The ratio of the copolymerization component to be introduced into the long-chain alkyl group-containing compound having at least 1 reactive group was confirmed by nuclear magnetic resonance spectroscopy (1H-NMR, 13C-NMR: varian Unity 400, manufactured by Agilent). The solvent in the synthesized acrylic resin was removed by a vacuum dryer, and then the dry solid was dissolved in deuterated chloroform for measurement. From the obtained NMR spectrum, peaks ascribed to the sites of each group were identified as chemical shifts δ (ppm). The integrated intensity of each peak obtained was obtained, and the composition ratio (mol%) of the copolymerization component introduced into the acrylic resin was confirmed from the hydrogen number and the integrated intensity of each group site.
(confirmation of Tg)
The Tg of each long-chain alkyl group-containing compound was determined from the composition ratio of the copolymer component determined by the NMR measurement and the Fox formula.
(surface resistivity)
The surface resistivity of the surface of the antistatic film of the present invention was measured by a surface resistance meter (manufactured by SIMCO JAPAN corporation, worksurface Tester ST-3) after humidity was adjusted at 23 ℃ for 24 hours, and evaluated according to the following criteria.
And (3) the following materials: the surface resistivity is 3 to 6 [ log Ω/≡
O: surface resistivity exceeding 6 and 9 or less [ log Ω/≡
Delta: surface resistivity exceeding 9 and 12 or less [ log Ω/≡
X: surface resistivity exceeding 12[ log Ω/≡ ]
(static contact angle of Water)
The contact angle after 30 seconds was measured by dropping water (drop amount: 1.8. Mu.L) onto the antistatic layer of the antistatic film using a contact angle meter (manufactured by Kyowa interface science Co., ltd.: full-automatic contact angle meter DM-701) at 25℃and 50% RH. The measurement was performed on 5 spots, and an average value was used.
(adhesion energy of Water)
The contact angle per 1℃was measured by dropping water (drop amount: 15. Mu.L) onto the antistatic layer of the antistatic film using a contact angle meter (manufactured by Kyowa interface science Co., ltd.: full-automatic contact angle meter DM-701) at 25℃and 50% RH for 2 seconds and continuously tilting the stage. Further, the inclination angle when moving 5 ° from the droplet position of 0 ° was determined as the slip angle, and the adhesion energy was calculated therefrom. The calculations were performed using analysis software within the present contact angle meter software (FAMES). The measurement was performed on 5 spots, and an average value was used.
(total light transmittance, haze)
The total light transmittance and haze of the film of the present invention were measured on the film before and after the heat treatment at 140℃for 10 minutes using a haze meter (manufactured by Nippon Denshoku Kogyo Co., ltd., NDH7000 II) based on JIS K7136.
(glass transition temperature)
Based on JIS K7121, 10mg of the resin sample was heated at 20℃per minute in a temperature range of 25 to 350℃using a differential scanning calorimeter (DSC 6200, manufactured by Seiko Instruments Inc.), and the extrapolated glass transition onset temperature obtained from the DSC curve was used as the glass transition temperature.
(alcohol resistance)
The surface resistivity of the film of the present invention was measured before and after 10 times of the treatment by wiping back and forth using a paper towel immersed in ethanol. The appearance change after the above-described processing was evaluated by the following determination criteria.
And (3) the following materials: almost no change
And (2) the following steps: slightly varied
Delta: with variations
X: variation of mottled shedding degree with antistatic layer
(production of Long-chain alkyl group-containing Compound b-1 having at least 1 reactive group)
231 parts by mass of Methyl Methacrylate (MMA), 130 parts by mass of Stearyl Methacrylate (SMA), 100 parts by mass of hydroxyethyl methacrylate (HEMA), 33 parts by mass of methacrylic acid (MAA) and 1153 parts by mass of isopropyl alcohol (IPA) were added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, and the inside of the flask was heated to 80℃while stirring. After stirring was performed for 3 hours while maintaining the temperature in the flask at 80 ℃, 0.5 parts by mass of 2, 2-azobis-2-methyl-N-2-hydroxyethyl propionamide was added to the flask. After nitrogen substitution while heating the flask to 120 ℃, the mixture was stirred at 120 ℃ for 2 hours.
Then, the unreacted raw material and the solvent were removed by a pressure reduction operation at 120℃under 1.5kPa to obtain an acrylic resin containing a long-chain alkyl group. The flask was returned to atmospheric pressure, cooled to room temperature, and 1592 parts by mass of an aqueous IPA solution (water content 50% by mass) was added and mixed. Then, ammonia was added to the long-chain alkyl group-containing acrylic resin with stirring using a dropping funnel to neutralize the long-chain alkyl group-containing acrylic resin so that the pH of the solution would fall within the range of 5.5 to 7.5, thereby obtaining a long-chain alkyl group-containing acrylic resin (b-1) having a solid content concentration of 20% by mass. The composition ratio, tg and acid value of the long-chain alkyl group-containing compound (b-1) having at least 1 reactive group, as determined by NMR, are shown in Table 1.
Example 1
Antistatic layer coating liquids were obtained in the compounding amounts shown in table 2.
(antistatic layer coating liquid)
The antistatic layer coating liquid was applied to one side of a4360 film (cosmosfine (registered trademark), manufactured by eastern spinning corporation) having a thickness of 75 μm by a gravure coater so that the wet film thickness was 4.5 μm, and dried and cured at 140℃for 30 seconds by a hot air drying oven to obtain a polyester film having an antistatic layer.
Examples 2, 14 and 15
An antistatic layer was formed in the same manner as in example 1 except that the composition was changed to the composition of table 2.
Example 3
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-2 (blocked isocyanate, solid content concentration 40% by mass, manufactured by Baxenden corporation) was set in accordance with the composition shown in table 2.
Example 4 and 13
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-3_1 (carbodiimide, 40% by mass in solid content concentration, manufactured by Niqing textile chemical Co., ltd.) was set in accordance with the composition shown in Table 2.
Example 5
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-3_2 (carbodiimide, 41% by mass in solid content concentration, manufactured by Niqing textile chemical Co., ltd.) was set in accordance with the composition shown in Table 2.
Examples 6 to 7
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_2 (melamine resin, imino group, solid content concentration 80 mass%) was set in accordance with the composition shown in table 2.
Example 8
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_3 (melamine resin, imino group, solid content concentration 70 mass%) was set in accordance with the composition shown in table 2.
Example 9
An antistatic layer was formed in the same manner as in example 1, except that a crosslinking agent a-1_4 (melamine resin, iminomethylol group, solid content 70 mass%) was set in accordance with the composition shown in table 2.
Example 10
An antistatic layer was formed in the same manner as in example 1, except that a crosslinking agent a-1_5 (melamine resin, iminomethylol group, solid content 70 mass%) was set in accordance with the composition shown in table 2.
Example 11
An antistatic layer was formed in the same manner as in example 1, except that a crosslinking agent a-1_6 (melamine resin, holoether type, solid content concentration 70 mass%) was set in accordance with the composition shown in table 2.
Example 12
An antistatic layer was formed in the same manner as in example 1, except that a crosslinking agent a-1_7 (manufactured by japan, melamine resin, methylol group, and solid content concentration 70 mass%) was set in accordance with the composition shown in table 2.
Example 16
An antistatic layer was formed by the same procedure as in example 1, except that the crosslinking agent a-1_1 and the long-chain alkyl group-containing compound b-2 (solid content concentration: 20 mass%) in an amount different from that of stearyl methacrylate of b-1 were set in accordance with the composition shown in Table 2.
Example 17
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_1 and the long-chain alkyl group-containing compound b-3 (solid content concentration: 20 mass%) having a hydroxyl value different from that of b-1 were set in accordance with the compositions shown in Table 2.
Example 18
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_1 and the long-chain alkyl group-containing compound b-4 (solid content concentration: 20 mass%) having a hydroxyl value different from that of b-1 were set in accordance with the compositions shown in Table 2.
Comparative example 1
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_1 and the long-chain alkyl group-containing compound b-5 having no reactive group (Resem T-738, manufactured by Zhongjing oil and fat Co., ltd., solid content: 20% by mass) were set to the compositions shown in Table 2.
Comparative example 2
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_1 and the long-chain alkyl group-containing compound b-6 having no reactive group (lion specialty chemical system, peroyl 406, solid content 15 mass%) were set in accordance with the compositions shown in table 2.
Comparative example 3
An antistatic layer was formed in the same manner as in example 1, except that the crosslinking agent a-1_1 was used in the composition shown in table 2, and the long-chain alkyl group-containing acrylic resin was not contained.
Various compositions, measured values, and the like are shown in tables 2A to 3D below.
[ Table 1A ]
[ Table 1B ]
[ Table 2A ]
[ Table 2B ]
[ Table 2C ]
TABLE 2D
[ Table 3A ]
TABLE 3B
[ Table 3C ]
TABLE 3D
The presently disclosed embodiments and examples are considered in all respects as illustrative and not restrictive. The scope of the present invention is shown by the claims rather than the above embodiments, and is intended to include all modifications within the meaning and scope equivalent to the claims.
The laminated polyester film of the present invention obtained in the examples can provide: when the antistatic film is used as a protective film by laminating an adhesive layer thereon, the protective film has good releasability from a laminating roller when the protective film is laminated, and can suppress peeling electrification and foreign matter adhesion during peeling.
On the other hand, comparative example 1 does not contain a long-chain alkyl group-containing compound having at least 1 reactive group as the binder resin (B), and therefore the water contact angle deviates from the range of the present invention, in that the coatability is deteriorated when the adhesive layer is processed on the antistatic layer, resulting in a film having many disadvantages.
Comparative example 2 does not contain a long-chain alkyl group-containing compound having at least 1 reactive group as the binder resin (B), and therefore, the coating property is deteriorated when an adhesive layer is processed on an antistatic layer, resulting in a film having many disadvantages.
Comparative example 3 does not contain a long-chain alkyl group-containing compound having at least 1 reactive group as the binder resin (B), and therefore the water contact angle deviates from the range of the present invention in that the coatability is deteriorated when an adhesive layer is processed on an antistatic layer, resulting in a film having many disadvantages.
Industrial applicability
The present invention relates to an antistatic film and an adhesive film having an adhesive layer laminated on the antistatic film, and more particularly, to a protective film for optical members (for example, organic EL, constituent members of a liquid crystal display) and the like.

Claims (11)

1. A laminated polyester film having an antistatic layer on at least one side of a base material,
the antistatic layer is a layer obtained by curing a composition containing a conductive polymer, a crosslinking agent (A), and a binder resin (B),
the binder resin (B) is a long-chain alkyl group-containing compound having at least 1 reactive group,
the antistatic layer satisfies the following (1) to (3):
(1) Surface resistivity: 3[ log Ω/≡ ] or more and 9[ log Ω/≡ ] or less;
(2) Static contact angle of water: 70 DEG to 95 DEG;
(3) Adhesion energy of water: 3.5mJ/m 2 The following is given.
2. The laminated polyester film according to claim 1, wherein the laminated polyester film has a total light transmittance of 80% or more and a haze of 3.0% or less.
3. The laminated polyester film according to claim 1 or 2, wherein the haze of the laminated polyester film after heating at 140 ℃ for 10 minutes is 1.5 times or less of the haze before heating.
4. The laminated polyester film according to any one of claims 1 to 3, wherein the antistatic layer has a change in surface resistivity after a wiping test with alcohol of 1.3 times or less of the surface resistivity before the test.
5. The laminated polyester film according to any one of claims 1 to 4, wherein the conductive polymer is contained at 5 mass% or more and 50 mass% or less with respect to 100 mass% of the total solid content of the antistatic layer.
6. The laminated polyester film according to any one of claims 1 to 5, wherein the crosslinking agent (a) and the binder resin (B) are contained in the following ranges with respect to 100 mass% of the total solid content in the antistatic layer:
(A) 15 mass% or more and 75 mass% or less;
(B) 10 mass% or more and 70 mass% or less.
7. The laminated polyester film according to any one of claims 1 to 6, wherein the hydroxyl value of the binder resin (B) is 20mgKOH/g or more and 300mgKOH/g or less.
8. The laminated polyester film according to any one of claims 1 to 7, wherein the binder resin (B) contains a carboxyl group.
9. The laminated polyester film according to any one of claims 1 to 8, wherein the crosslinking agent (a) comprises at least 1 selected from the group consisting of acrylamide, melamine resin, carbodiimide, oxazoline, isocyanate, and aziridine.
10. The laminated polyester film according to any one of claims 1 to 9, wherein the laminated polyester film contains substantially no organosilicon compound.
11. A protective film comprising an adhesive layer laminated on at least one side of the laminated polyester film according to any one of claims 1 to 11.
CN202280044847.2A 2021-07-05 2022-07-04 Antistatic film and protective film Pending CN117545629A (en)

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