CN113365818A - Laminated film for reinforcement - Google Patents

Laminated film for reinforcement Download PDF

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Publication number
CN113365818A
CN113365818A CN202080010171.6A CN202080010171A CN113365818A CN 113365818 A CN113365818 A CN 113365818A CN 202080010171 A CN202080010171 A CN 202080010171A CN 113365818 A CN113365818 A CN 113365818A
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China
Prior art keywords
layer
reinforcing
adhesive
film
base material
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Pending
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CN202080010171.6A
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Chinese (zh)
Inventor
佐佐木翔悟
林圭治
仲野武史
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Nitto Denko Corp
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Nitto Denko Corp
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    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • 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
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The invention provides a laminated film for reinforcement, which has a surface protection film and a separator and can be smoothly picked up piece by piece from a stacked state. The laminated film for reinforcement of the present invention comprises a separator, an adhesive layer (1), a base material for reinforcement, and a surface protective film in this order, the separator comprises a release layer (B1), a base material layer (B2) and an antistatic layer (B3) in this order, the surface protection film comprises an adhesive layer (C1), a base material layer (C2) and an antistatic layer (C3) in sequence, the release layer (B1) and the adhesive layer (1) are directly laminated, the reinforcing base material and the adhesive layer (C1) are directly laminated, two reinforcing laminated films are laminated so that the antistatic layer (B3) side of one reinforcing laminated film (A1) and the antistatic layer (C3) side of the other reinforcing laminated film (A2) overlap each other, the electrostatic voltage of the surface of the reinforcing laminated film (A1) on the antistatic layer (B3) side when the film is picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH is 10kV or less.

Description

Laminated film for reinforcement
Technical Field
The present invention relates to a reinforcing laminate film.
Background
In order to impart rigidity and impact resistance to an optical member, an electronic member, or the like, a reinforcing film (a reinforcing base material provided with an adhesive layer) may be bonded in advance to an exposed surface side of the optical member, the electronic member, or the like for reinforcement (patent document 1). Such a reinforcing film usually has an adhesive layer for bonding, and in order to protect the surface of the adhesive layer, a separator is usually provided on the surface of the adhesive layer until the time of use.
Further, in order to prevent damage to the surface of the reinforcing film during processing, assembly, inspection, transportation, or the like, the processing, assembly, inspection, transportation, or the like may be performed in a state in which a surface protective film is attached to the exposed surface of the reinforcing film in advance. When surface protection is not required, such a surface protection film is peeled from the reinforcing film (patent document 2).
Such a reinforcing laminate film having a surface protecting film and a separator is generally stacked in the same direction when holding a tube or the like. However, when the reinforcing laminated films stacked in the same direction are picked up one by one, electrostatic attraction is generated between the reinforcing laminated films to cause blocking, and the sheets cannot be picked up smoothly one by one.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6366199
Patent document 2: japanese patent laid-open publication No. 2016-
Disclosure of Invention
Problems to be solved by the invention
The invention provides a laminated film for reinforcement, which has a surface protection film and a separator and can be smoothly picked up piece by piece from a stacked state.
Means for solving the problems
The laminated film for reinforcement of the present invention comprises a separator, an adhesive layer (1), a base material for reinforcement, and a surface protective film in this order,
the separator comprises a release layer (B1), a base material layer (B2) and an antistatic layer (B3) in this order,
the surface protection film comprises an adhesive layer (C1), a base material layer (C2) and an antistatic layer (C3) in sequence,
the release layer (B1) is directly laminated with the adhesive layer (1),
the reinforcing base material is directly laminated with the adhesive layer (C1),
two sheets of the reinforcing laminated film were laminated so that the antistatic layer (B3) side of one sheet of the reinforcing laminated film (a1) and the antistatic layer (C3) side of the other sheet of the reinforcing laminated film (a2) overlapped with each other, and the electrostatic voltage on the surface of the reinforcing laminated film (a1) on the antistatic layer (B3) side was 10kV or less when the film was picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH.
In one embodiment, the antistatic layer (B3) has a surface resistance of 1.0X 10 at 23 ℃ and 50% RH4Ω～1.0×109Ω。
In one embodiment, the antistatic layer (C3) has a surface resistance of 1.0X 10 at 23 ℃ and 50% RH4Ω～1.0×109Ω。
In one embodiment, the antistatic layer (B3) includes a conductive polymer.
In one embodiment, the antistatic layer (C3) includes a conductive polymer.
In one embodiment, the reinforcing base material is a plastic film.
In one embodiment, the adhesive layer (1) is composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.
In one embodiment, the adhesive layer (C1) is composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.
In one embodiment, the acrylic adhesive is formed from an acrylic adhesive composition comprising: the composition (A) comprises (a) an alkyl (meth) acrylate in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms and (b) at least one member selected from the group consisting of (meth) acrylate having an OH group and (meth) acrylic acid.
In one embodiment, the pressure-sensitive adhesive layer (1) exposed by peeling the separator at a temperature of 23 ℃, a humidity of 50% RH, a peeling angle of 150 ℃ and a peeling speed of 10 m/min has an initial adhesive force of 1.0N/25mm or more to a glass plate under conditions of 23 ℃, a humidity of 50% RH, a peeling angle of 180 ℃ and a peeling speed of 300 mm/min.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a reinforcing laminate film which has a surface protective film and a separator and can be smoothly picked up piece by piece from a stacked state.
Drawings
Fig. 1 is a schematic cross-sectional view of one embodiment of a reinforcing laminated film of the present invention.
Fig. 2 is a schematic explanatory view of a method of measuring an electrostatic voltage by picking up one reinforcing laminated film from two superimposed films.
Detailed Description
When the expression "weight" is given in the present specification, it can be replaced with "mass" which is usually used as an SI-based unit indicating weight.
In the present specification, the expression "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and the expression "(meth) acrylate" means "acrylate and/or methacrylate", and the expression "(meth) allyl" means "allyl and/or methallyl", and the expression "(meth) acrolein" means "acrolein and/or methacrolein".
< laminated film for reinforcing > >)
The laminate film for reinforcement comprises a separator, an adhesive layer (1), a base material for reinforcement, and a surface protective film in this order. The reinforcing laminate film of the present invention may have any other suitable layer within a range that impairs the effects of the present invention, as long as it comprises a separator, an adhesive layer (1), a reinforcing substrate, and a surface protecting film in this order.
In the reinforcing laminate film of the present invention, the separator includes a release layer (B1), a base layer (B2), and an antistatic layer (B3) in this order.
In the reinforcing laminate film of the present invention, the surface protective film comprises an adhesive layer (C1), a base layer (C2), and an antistatic layer (C3) in this order.
In the reinforcing laminate film of the present invention, the release layer (B1) and the adhesive layer (1) are directly laminated.
In the reinforcing laminate film of the present invention, the reinforcing base material and the pressure-sensitive adhesive layer (C1) are directly laminated.
The thickness of the entire reinforcing laminate film of the present invention is preferably 80 μm to 600 μm, more preferably 90 μm to 500 μm, still more preferably 95 μm to 400 μm, and particularly preferably 100 μm to 300 μm, from the viewpoint of further exhibiting the effects of the present invention.
Fig. 1 is a schematic cross-sectional view of one embodiment of a reinforcing laminated film of the present invention. In fig. 1, a reinforcing laminate film 1000 of the present invention includes a separator 100, an adhesive layer (1)200, a reinforcing base material 300, and a surface protection film 400 in this order, the separator 100 including a release layer (B1)110, a base material layer (B2)120, and an antistatic layer (B3)130 in this order, and the surface protection film 400 including an adhesive layer (C1)410, a base material layer (C2)420, and an antistatic layer (C3)430 in this order.
In one embodiment of a method of using the reinforcing laminate film 1000 of the present invention, as shown in fig. 1, first, the separator 100 is peeled off to expose the adhesive layer (1)200, and the resultant is bonded to an exposed surface side of an optical member, an electronic member, or the like, thereby reinforcing the optical member and the electronic member. The surface protection film 400 is attached to prevent damage to the surface of the reinforcing base material 300 when the product in this state is processed, assembled, inspected, transported, or the like, and is peeled from the reinforcing base material 300 when surface protection is not necessary.
In the reinforcing laminated film of the present invention, by appropriately designing the electrostatic property of the separator and the electrostatic property of the surface protection film, when picking up reinforcing laminated films stacked in the same orientation one by one, the electrostatic attraction generated between the reinforcing laminated films can be suppressed, the blocking can be suppressed, and the picking up can be performed smoothly one by one.
As the above-described design, in the reinforcing laminated film of the present invention, it is preferable that: two reinforcing laminated films are laminated so that the antistatic layer (B3) side of one reinforcing laminated film (A1) overlaps the antistatic layer (C3) side of the other reinforcing laminated film (A2), and the electrostatic voltage on the surface of the reinforcing laminated film (A1) on the antistatic layer (B3) side is 10kV or less when the film is picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH. Specifically, as shown in fig. 2, the reinforcing laminate film (a1) and the reinforcing laminate film (a2) were laminated in the same direction with the spacer side facing upward, so that the antistatic layer (B3) side of the reinforcing laminate film (a1) and the antistatic layer (C3) side of the reinforcing laminate film (a2) were superposed on each other, the reinforcing laminate film (a2) was picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH, and the electrostatic voltage on the surface of the reinforcing laminate film (a1) on the antistatic layer (B3) side was measured. The above-mentioned electrostatic voltage measurement method is described in detail below. Fig. 2 is a schematic explanatory view only, and the reinforcing laminated film (a2) is picked up by peeling the reinforcing laminated film (a2) from the end portion so as to be rolled up when the reinforcing laminated film (a1) is picked up from the reinforcing laminated film (a1) at a peeling angle of 150 degrees and a peeling speed of 10 m/min.
The electrostatic voltage is preferably 9.0kV or less, more preferably 8.5kV or less, further preferably 8.0kV or less, and particularly preferably 7.5kV or less, from the viewpoint that the effect of the present invention can be further exhibited. The lower limit of the electrostatic voltage is preferably smaller, and is preferably 0kV or more.
The reinforcing laminate film of the present invention can be produced by any suitable method within a range not impairing the effects of the present invention. For example, it can be produced by: the adhesive layer (1) is formed on the reinforcing base material, the separator is bonded to the adhesive layer (1) thus formed, and the surface protective film is bonded to the surface of the reinforcing base material opposite to the adhesive layer (1).
Separate body
The separator includes a release layer (B1), a base material layer (B2), and an antistatic layer (B3) in this order. The separator may have any other suitable layer as long as it includes the release layer (B1), the base layer (B2), and the antistatic layer (B3) in this order, within a range not impairing the effects of the present invention.
The release layer (B1) of the separator is directly laminated on the adhesive layer (1). The reinforcing laminated film of the present invention is preferably used in that: first, the separator is peeled off to expose the adhesive layer (1), and the adhesive layer is bonded to the exposed surface side of the optical member, the electronic member, and the like, thereby reinforcing the optical member and the electronic member.
The thickness of the separator is preferably 1 μm to 100 μm, more preferably 5 μm to 90 μm, still more preferably 10 μm to 80 μm, and particularly preferably 20 μm to 75 μm, from the viewpoint of further exhibiting the effects of the present invention.
< Release layer (B1) >)
The release layer (B1) is provided to improve the releasability from the adhesive layer (1). The material for forming the release layer (B1) may be any suitable material within a range not impairing the effects of the present invention. Examples of such a forming material include: silicone release agents, fluorine release agents, long chain alkyl release agents, fatty acid amide release agents, and the like. Among these, silicone-based release agents are preferred. The release layer (B1) may be formed in the form of a coating layer.
The thickness of the release layer (B1) may be any suitable thickness according to the purpose within the range not impairing the effects of the present invention. The thickness is preferably 10nm to 2000nm, more preferably 10nm to 1500nm, still more preferably 10nm to 1000nm, and particularly preferably 10nm to 500 nm.
The release layer (B1) may be only 1 layer, or may be 2 or more layers.
Examples of the silicone-based release layer include addition reaction type silicone resins. Specific examples of the addition reaction type silicone resin include: KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T manufactured by shin Etsu chemical industry; TPR-6700, TPR-6710 and TPR-6721 manufactured by Toshiba Silicone; manufactured by Dow Corning ToraySD7220, SD7226, etc. The amount of the silicone-based release layer applied (after drying) is preferably 0.01g/m2～2g/m2More preferably 0.01g/m2～1g/m2More preferably 0.01g/m2～0.5g/m2。
The release layer (B1) can be formed, for example, as follows: the above-mentioned forming material is applied to an arbitrary suitable layer by a conventionally known coating method such as reverse gravure coating, bar coating, die coating, etc., and then cured by heat treatment at a temperature of usually about 120 to 200 ℃. Further, heat treatment and irradiation with active energy rays such as ultraviolet irradiation may be used in combination as necessary.
< substrate layer (B2) >)
As the base layer (B2), any suitable material may be used as long as the effects of the present invention are not impaired. Examples of such materials include: plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, laminates of these (particularly laminates comprising plastic films), and the like.
Examples of the plastic film include: plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); plastic films made of olefin resins containing α -olefin as a monomer component, such as Polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymers, and ethylene-vinyl acetate copolymers (EVA); a plastic film composed of polyvinyl chloride (PVC); a plastic film made of a vinyl acetate resin; a plastic film composed of Polycarbonate (PC); a plastic film made of polyphenylene sulfide (PPS); plastic films made of amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film made of a polyimide resin; a plastic film composed of polyether ether ketone (PEEK); plastic films made of olefin resins such as Polyethylene (PE) and polypropylene (PP); and plastic films made of fluorine-based resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and chlorofluoroethylene-vinylidene fluoride copolymers.
Examples of the nonwoven fabric include: nonwoven fabrics made of heat-resistant natural fibers, such as nonwoven fabrics made of manila hemp; and synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics, and ester resin nonwoven fabrics.
The base material layer (B2) may have only 1 layer, or may have 2 or more layers.
The thickness of the base material layer (B2) is preferably 4 to 500. mu.m, more preferably 10 to 400. mu.m, still more preferably 15 to 350. mu.m, and particularly preferably 20 to 300. mu.m, from the viewpoint of further exhibiting the effects of the present invention.
The base material layer (B2) may be subjected to surface treatment. Examples of the surface treatment include: corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, coating treatment with a primer, and the like.
The base layer (B2) may contain any other suitable additive within a range not impairing the effects of the present invention.
< antistatic layer (B3) >)
As for the thickness of the antistatic layer (B3), any suitable thickness may be adopted according to the purpose within the range not impairing the effects of the present invention. The thickness is preferably 1nm to 1000nm, more preferably 5nm to 900nm, still more preferably 7.5nm to 800nm, and particularly preferably 10nm to 700 nm.
The antistatic layer (B3) may be 1 layer only, or may be 2 or more layers.
As for the antistatic layer (B3), any suitable antistatic layer can be used as long as it can exert an antistatic effect within a range not impairing the effects of the present invention. The antistatic layer is preferably formed by applying a conductive coating solution containing a conductive polymer on an arbitrary suitable base layer. Specifically, for example, the antistatic layer is formed by applying a conductive coating liquid containing a conductive polymer on the base layer (B2). Specific coating methods include: roll coating, bar coating, gravure coating, and the like.
As the conductive polymer, any suitable conductive polymer can be used within a range not impairing the effects of the present invention. Examples of such a conductive polymer include a conductive polymer in which a polyanion is doped in a pi-conjugated conductive polymer. Examples of the pi-conjugated conductive polymer include: chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include: polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polymethacrylic acid, and the like.
The surface resistance value of the antistatic layer (B3) is preferably 1.0X 10 at 23 ℃ and 50% RH4Ω～1.0×109Omega, more preferably 1.0X 104Ω～5.0×108Ω, more preferably 5.0 × 104Ω～1.0×108Omega, particularly preferably 1.0X 105Ω～5.0×107Omega. When the surface resistance value of the antistatic layer (B3) is within the above range, the effects of the present invention can be further exhibited.
Adhesive layer (1)
The adhesive layer (1) may be any suitable adhesive layer within a range not impairing the effects of the present invention. The pressure-sensitive adhesive layer (1) may be only 1 layer or 2 or more layers.
The thickness of the pressure-sensitive adhesive layer (1) is preferably 0.5 to 150. mu.m, more preferably 1 to 100. mu.m, still more preferably 3 to 80 μm, particularly preferably 5 to 50 μm, and most preferably 10 to 30 μm, from the viewpoint of further exhibiting the effects of the present invention.
When the reinforcing laminate film of the present invention is used for the pressure-sensitive adhesive layer (1), the pressure-sensitive adhesive layer (1) is preferably peeled off from the separator to expose the pressure-sensitive adhesive layer (1), and the pressure-sensitive adhesive layer is bonded to the exposed surface side of an optical member, an electronic member, or the like to reinforce the optical member or the electronic member. That is, after the pressure-sensitive adhesive layer (1) is bonded to the exposed surface side of an optical member, an electronic member, or the like, peeling is not premised on the surface protection film or the like. Therefore, the adhesive layer (1) is preferably designed to have an adhesive force of a certain degree or more. Specifically, the adhesive layer (1) exposed by peeling the separator at a temperature of 23 ℃, a humidity of 50% RH, a peeling angle of 150 ℃ and a peeling speed of 10 m/min has an initial adhesive force to the glass plate of preferably 1.0N/25mm or more, more preferably 2.0N/25mm or more, further preferably 3.0N/25mm or more, particularly preferably 4.0N/25mm or more, and most preferably 4.5N/25mm or more under the conditions of a temperature of 23 ℃, a humidity of 50% RH, a peeling angle of 180 ℃ and a peeling speed of 300 mm/min. The upper limit of the initial adhesive force is preferably 5.0N/25mm or less.
The pressure-sensitive adhesive layer (1) is preferably composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive.
The adhesive layer (1) may be formed by any suitable method. Examples of such a method include the following: an adhesive layer is formed on any suitable substrate by applying an adhesive composition (at least one selected from the group consisting of an acrylic adhesive composition, a urethane adhesive composition, a rubber adhesive composition, and a silicone adhesive composition) on the substrate, heating and drying the composition as needed, and curing the composition as needed. Examples of such coating methods include: gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, roll brush coater, and the like.
< acrylic adhesive >
The acrylic adhesive is formed from an acrylic adhesive composition.
The acrylic adhesive composition preferably contains an acrylic polymer and a crosslinking agent in terms of further exhibiting the effects of the present invention.
Acrylic polymers are known in the field of acrylic adhesives as so-called base polymers. The number of the acrylic polymer may be only 1, or may be 2 or more.
The content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, even more preferably 70 to 100% by weight, particularly preferably 80 to 100% by weight, and most preferably 90 to 100% by weight, in terms of solid content.
As the acrylic polymer, any suitable acrylic polymer can be used within a range not impairing the effects of the present invention.
The weight average molecular weight of the acrylic polymer is preferably 100,000 to 3,000,000, more preferably 150,000 to 2,000,000, even more preferably 200,000 to 1,500,000, and particularly preferably 250,000 to 1,000,000, from the viewpoint of further exhibiting the effects of the present invention.
The acrylic polymer is preferably an acrylic polymer formed by polymerization from a composition (a) containing (a) an alkyl (meth) acrylate in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms and (b) at least one selected from the group consisting of a (meth) acrylate having an OH group and a (meth) acrylic acid, from the viewpoint of further exhibiting the effects of the present invention. The number of the (a) component and the (b) component may be 1 or 2 or more, independently.
Examples of the alkyl (meth) acrylate (component a) having an alkyl group of an alkyl ester moiety with 4 to 12 carbon atoms include: n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, from the viewpoint of further exhibiting the effect of the present invention.
Examples of the at least one (b component) selected from the group consisting of (meth) acrylates and (meth) acrylic acids having OH groups include: (meth) acrylic acid esters having an OH group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and (meth) acrylic acid. Among these, hydroxyethyl (meth) acrylate and (meth) acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint of further exhibiting the effects of the present invention.
The composition (A) may contain a copolymerizable monomer other than the components (a) and (b). The number of the copolymerizable monomer may be only 1, or may be 2 or more. Examples of such copolymerizable monomers include: carboxyl group-containing monomers (excluding (meth) acrylic acid) such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride); amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; heterocyclic ring-containing vinyl monomers such as N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine and vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloylphosphate; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth) acrylates having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; aromatic hydrocarbon group-containing (meth) acrylates such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride, and the like.
As the copolymerizable monomer, a polyfunctional monomer may be used. The polyfunctional monomer is a monomer having 2 or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group may be employed within a range not impairing the effects of the present invention. Examples of such ethylenically unsaturated groups include: and a radical polymerizable functional group such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include: hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Such polyfunctional monomers may be 1 type or 2 or more types.
As the copolymerizable monomer, alkoxyalkyl (meth) acrylate may also be used. Examples of alkoxyalkyl (meth) acrylates include: 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, and the like. The number of the alkoxyalkyl (meth) acrylates may be only 1, or may be 2 or more.
The content of the alkyl (meth) acrylate (component a) having an alkyl group of an alkyl ester moiety having 4 to 12 carbon atoms is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, even more preferably 70% by weight to 100% by weight, and particularly preferably 80% by weight to 100% by weight, based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer, from the viewpoint of further exhibiting the effects of the present invention.
The content of at least one (b component) selected from the group consisting of (meth) acrylates having OH groups and (meth) acrylic acids is preferably 0.1% by weight or more, more preferably 1.0% by weight to 50% by weight, even more preferably 1.5% by weight to 40% by weight, and particularly preferably 2.0% by weight to 30% by weight, based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer, from the viewpoint of further exhibiting the effects of the present invention.
The composition (a) may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include: polymerization initiators, chain transfer agents, solvents, and the like. The content of these other components may be any suitable content within a range not impairing the effect of the present invention.
The polymerization initiator may be a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like, depending on the type of polymerization reaction. The number of polymerization initiators may be only 1, or may be 2 or more.
The thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization. Examples of such thermal polymerization initiators include: azo polymerization initiators, peroxide polymerization initiators (e.g., dibenzoyl peroxide, t-butyl peroxymaleate, etc.), redox polymerization initiators, and the like. Among these thermal polymerization initiators, the azo-based initiators disclosed in Japanese patent application laid-open No. 2002-69411 are particularly preferable. Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a part that causes generation of gas (outgas) by heating. Examples of the azo polymerization initiator include: 2,2 '-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2' -azobis-2-methylbutyronitrile (hereinafter, sometimes referred to as AMBN), dimethyl 2,2 '-azobis (2-methylpropionate), 4' -azobis-4-cyanovaleric acid, and the like. The amount of the azo polymerization initiator used is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 4.0 parts by weight, still more preferably 0.1 to 3.0 parts by weight, particularly preferably 0.15 to 3.0 parts by weight, and most preferably 0.20 to 2.0 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer.
The photopolymerization initiator can be preferably used when an acrylic polymer is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include: benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α -ketol-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzil-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, and the like.
Examples of the benzoin ether-based photopolymerization initiator include: benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethane-1-one, anisole methyl ether, and the like. Examples of the acetophenone photopolymerization initiator include: 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4- (tert-butyl) dichloroacetophenone and the like. Examples of the α -ketol photopolymerization initiator include: 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl ] -2-methylpropan-1-one, and the like. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include: 2-naphthalenesulfonyl chloride, and the like. Examples of the photoactive oxime-based photopolymerization initiator include: 1-phenyl-1, 1-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. Examples of the benzoin-based photopolymerization initiator include: benzoin, and the like. Examples of the benzil-based photopolymerization initiator include: benzil, and the like. Examples of benzophenone-based photopolymerization initiators include: benzophenone, benzoylbenzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α -hydroxycyclohexyl phenyl ketone and the like. Examples of the ketal photopolymerization initiator include: benzil dimethyl ketal, and the like. Examples of the thioxanthone photopolymerization initiator include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
The amount of the photopolymerization initiator used is preferably 0.01 to 3.0 parts by weight, more preferably 0.015 to 2.0 parts by weight, still more preferably 0.02 to 1.5 parts by weight, particularly preferably 0.025 to 1.0 part by weight, and most preferably 0.03 to 0.50 part by weight, based on the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer.
The acrylic adhesive composition may also include a crosslinking agent. By using the crosslinking agent, the cohesive force of the acrylic adhesive can be increased, and the effects of the present invention can be further exhibited. The number of the crosslinking agents may be only 1, or may be 2 or more.
As the crosslinking agent, there may be mentioned: a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, and the like. Among these, at least one (component c) selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferable from the viewpoint that the effects of the present invention can be further exhibited.
Examples of the polyfunctional isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as 1, 2-ethylenediisocyanate, 1, 4-butylenediisocyanate and 1, 6-hexamethylenediisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include: trimethylolpropane/tolylene diisocyanate adduct (trade name "Coronate L" manufactured by Nippon polyurethane industries Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (trade name "Coronate HL" manufactured by Nippon polyurethane industries Co., Ltd.), trade name "Coronate HX" (Nippon polyurethane industries Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (trade name "Takenate 110N" manufactured by Mitsui chemical Co., Ltd.) and the like are commercially available.
Examples of the epoxy crosslinking agent (polyfunctional epoxy compound) include: n, N, N ', N' -tetraglycidyl m-xylylenediamine, diglycidylaniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol anhydride polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, triglycidyl tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having 2 or more epoxy groups in the molecule. Examples of the epoxy crosslinking agent include: commercially available products such as "Tetrad C" (manufactured by Mitsubishi gas chemical Co., Ltd.).
The content of the crosslinking agent in the acrylic adhesive composition may be any suitable content within a range not impairing the effects of the present invention. Such a content is, for example, preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.5 parts by weight, further preferably 0.3 to 4.0 parts by weight, and particularly preferably 0.4 to 3.5 parts by weight, based on the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint of further exhibiting the effects of the present invention.
The acrylic adhesive composition may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include: a polymer component other than acrylic polymers, a crosslinking accelerator, a crosslinking catalyst, a silane coupling agent, a tackifier resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, and the like), an anti-aging agent, an inorganic filler, an organic filler, metal powder, a colorant (pigment, dye, and the like), a foil, an ultraviolet absorber, an antioxidant, a light stabilizer, a chain transfer agent, a plasticizer, a softener, a surfactant, an antistatic agent, a conductive agent, a stabilizer, a surface lubricant, a leveling agent, an anticorrosive agent, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.
< urethane-based adhesive >
The urethane adhesive is formed from a urethane adhesive composition.
From the viewpoint that the effects of the present invention can be further exhibited, the urethane adhesive composition preferably contains at least one selected from the group consisting of urethane prepolymer and polyol, and a crosslinking agent.
At least one selected from the group consisting of urethane prepolymers and polyols is referred to as a so-called base polymer in the field of urethane-based adhesives. The number of urethane prepolymers may be only 1, or may be 2 or more. The number of the polyhydric alcohols may be only 1, or may be 2 or more.
[ urethane prepolymer ]
The urethane prepolymer is preferably a polyurethane polyol, more preferably: a urethane prepolymer obtained by reacting a polyester polyol (a1) or a polyether polyol (a2) with an organic polyisocyanate compound (a3) either alone or as a mixture of (a1) and (a2) in the presence or absence of a catalyst.
For the polyester polyol (a1), any suitable polyester polyol can be used. Examples of such a polyester polyol (a1) include a polyester polyol obtained by reacting an acid component with a diol component. Examples of the acid component include: terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the diol component include: ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3' -dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1, 4-butanediol, neopentyl glycol, butylethylpentanediol, and the polyol component may be: glycerin, trimethylolpropane, pentaerythritol, and the like. As the polyester polyol (a1), there can be mentioned, in addition: polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β -methyl- γ -valerolactone) and polypentanolactone.
As for the molecular weight of the polyester polyol (a1), polyester polyols ranging from low molecular weight to high molecular weight can be used. The molecular weight of the polyester polyol (a1) is preferably 100 to 100000 in terms of further exhibiting the effects of the present invention. If the number average molecular weight is less than 100, the reactivity may be high and gelation may be likely to occur. If the number average molecular weight exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used is preferably 0 to 90 mol% in the polyol constituting the polyurethane polyol, from the viewpoint of further exhibiting the effect of the present invention.
For the polyether polyol (a2), any suitable polyether polyol may be used. Examples of such polyether polyol (a2) include: polyether polyols obtained by polymerizing an alkylene oxide (oxirane) compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using water, a low molecular weight polyol such as propylene glycol, ethylene glycol, glycerin, or trimethylolpropane, as an initiator. Specific examples of such polyether polyol (a2) include: polyether polyols having a functional group number of 2 or more such as polypropylene glycol, polyethylene glycol and polytetramethylene glycol.
As the molecular weight of the polyether polyol (a2), polyether polyols of from low molecular weight to high molecular weight can be used. The polyether polyol (a2) preferably has a number average molecular weight of 100 to 100000 in terms of further exhibiting the effects of the present invention. If the number average molecular weight is less than 100, the reactivity may be high and gelation may be likely to occur. If the number average molecular weight exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used is preferably 0 to 90 mol% in the polyol constituting the polyurethane polyol, from the viewpoint of further exhibiting the effect of the present invention.
The polyether polyol (a2) may be used in combination with, if necessary, a polyol such as ethylene glycol, 1, 4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, etc., a polyamine such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, etc., in which a part thereof is substituted.
The polyether polyol (a2) may be a difunctional polyether polyol alone, or a polyether polyol having a number average molecular weight of 100 to 100000 and at least 3 or more hydroxyl groups in one molecule may be partially or entirely used. When a polyether polyol having a number average molecular weight of 100 to 100000 and at least 3 hydroxyl groups in one molecule is partially or entirely used as the polyether polyol (a2), not only the effects of the present invention can be further exhibited, but also the balance between the adhesive force and the peelability becomes good. If the number average molecular weight of such polyether polyol is less than 100, the reactivity may be high and gelation may be easily caused. When the number average molecular weight of such a polyether polyol exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such polyether polyol is more preferably 100 to 10000 in view of further exhibiting the effect of the present invention.
As the organic polyisocyanate compound (a3), any suitable organic polyisocyanate compound can be used. Examples of such an organic polyisocyanate compound (a3) include: aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like.
Examples of the aromatic polyisocyanate include: 1, 3-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -toluidine diisocyanate, 2,4, 6-triisocyanatotoluene, 1,3, 5-triisocyanatobenzene, dimethoxybenzidine diisocyanate, 4' -diphenylether diisocyanate, 4',4 ″ -triphenylmethane triisocyanate, and the like.
Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propane diisocyanate, 2, 3-butane diisocyanate, 1, 3-butane diisocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include: omega, omega '-diisocyanato-1, 3-dimethylbenzene, omega' -diisocyanato-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include: 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane and the like.
As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a biuret obtained by reaction with water, a trimer having an isocyanurate ring, and the like can be used in combination.
As the catalyst usable in obtaining the polyurethane polyol, any suitable catalyst can be used. Examples of such catalysts include: tertiary amine compounds, organometallic compounds, and the like.
Examples of the tertiary amine compound include: triethylamine, triethylenediamine, 1, 8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.
Examples of the organometallic compound include: tin-based compounds, non-tin-based compounds, and the like.
Examples of the tin-based compound include: dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin acetate, tributyltin acetate, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, and the like.
Examples of the non-tin compound include: titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, etc.; lead compounds such as lead oleate, lead 2-ethylhexoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium compounds such as zirconium naphthenate.
When a catalyst is used for obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, the problem of gelation or turbidity of a reaction solution is likely to occur in a system in which one type of catalyst is used alone due to the difference in reactivity. Therefore, by using two catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, and the like can be easily controlled, and these problems can be solved. Examples of the combination of the two catalysts include: tertiary amine/organic metal system, tin system/non-tin system, tin system/tin system, preferably tin system/tin system, more preferably a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The compounding ratio thereof is preferably less than 1, more preferably 0.2 to 0.6, in terms of weight ratio, of tin 2-ethylhexanoate/dibutyltin dilaurate. If the compounding ratio is 1 or more, gelation may be caused by the balance of catalytic activity.
When a catalyst is used to obtain the polyurethane polyol, the amount of the catalyst used is preferably 0.01 to 1.0% by weight based on the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a 3).
When a catalyst is used for obtaining the polyurethane polyol, the reaction temperature is preferably less than 100 ℃, and more preferably 85 ℃ to 95 ℃. When the temperature is 100 ℃ or higher, it is difficult to control the reaction rate and the crosslinked structure, and it is difficult to obtain a polyurethane polyol having a specific molecular weight.
The polyurethane polyols can also be obtained without catalysts. In this case, the reaction temperature is preferably 100 ℃ or higher, more preferably 110 ℃ or higher. When the polyurethane polyol is obtained without a catalyst, the reaction is preferably carried out for 3 hours or more.
Examples of the method for obtaining the polyurethane polyol include: 1) a method in which the polyester polyol, the polyether polyol, the catalyst and the organic polyisocyanate are all added to the flask; 2) a method in which the polyester polyol, the polyether polyol and the catalyst are added to a flask and then the organic polyisocyanate is added. From the viewpoint of reaction control, the method of 2) is preferable as the method for obtaining a polyurethane polyol.
Any suitable solvent may be used in obtaining the polyurethane polyol. Examples of such solvents include: methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, and the like. Among these solvents, toluene is preferable.
[ polyhydric alcohol ]
Examples of the polyol include: polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and castor oil polyol. The polyol is more preferably a polyether polyol.
The polyester polyol is obtained, for example, by esterification of a polyol component with an acid component.
Examples of the polyol component include: ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like. Examples of the acid component include: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, acid anhydrides of these acids, and the like.
Examples of polyether polyols include: polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide using water, low-molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol a, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.), etc. as initiators. Specific examples thereof include: polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Examples of polycaprolactone polyols include: caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as epsilon-caprolactone and sigma-valerolactone.
Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; polycarbonate polyols obtained by subjecting the polyol component to ester exchange condensation with a carbonic acid diester such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, or dibenzyl carbonate; a copolymerized polycarbonate polyol obtained by using 2 or more of the above polyol components in combination; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a carboxyl group-containing compound to an esterification reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to etherification reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and an ester compound to an ester exchange reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to an ester exchange reaction; a polyester polycarbonate polyol obtained by subjecting the above-mentioned various polycarbonate polyols and a dicarboxylic acid compound to a polycondensation reaction; and a copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with an alkylene oxide.
Examples of the castor oil-based polyol include: castor oil-based polyol obtained by reacting castor oil fatty acid with the above polyol component. Specific examples thereof include: castor oil-based polyol obtained by reacting castor oil fatty acid with polypropylene glycol.
The number average molecular weight Mn of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000, from the viewpoint of further exhibiting the effects of the present invention.
The polyol preferably contains, from the viewpoint of further exhibiting the effect of the present invention: a polyol (A1) having 3 OH groups and a number average molecular weight Mn of 300 to 100000. The number of the polyhydric alcohols (A1) may be only 1, or may be 2 or more.
The content ratio of the polyol (a1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and still more preferably 50% by weight to 100% by weight, from the viewpoint of further exhibiting the effects of the present invention.
From the viewpoint of further exhibiting the effect of the present invention, the number average molecular weight Mn of the polyol (a1) is preferably 1000 to 100000, more preferably more than 1000 and 80000 or less, further preferably 1100 to 70000, further preferably 1200 to 60000, further preferably 1300 to 50000, further preferably 1400 to 40000, further preferably 1500 to 35000, particularly preferably 1700 to 32000, and most preferably 2000 to 30000.
The polyol may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 20000 or less. The number of the polyhydric alcohols (A2) may be only 1, or may be 2 or more. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20000, more preferably 150 to 10000, still more preferably 200 to 7500, particularly preferably 300 to 6000, and most preferably 300 to 5000, from the viewpoint of further exhibiting the effects of the present invention. As the polyol (a2), from the viewpoint that the effects of the present invention can be further exhibited, preferable examples include: polyols having 3 OH groups (triols), polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentaols), polyols having 6 OH groups (hexaols).
From the viewpoint that the effect of the present invention can be further exhibited, the total amount of the polyol (a2) which is a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol (hexaol) having 6 OH groups is preferably 70% by weight or less, more preferably 60% by weight or less, further preferably 40% by weight or less, and particularly preferably 30% by weight or less, in terms of the content ratio in the polyol.
The content ratio of the polyol (a2) in the polyol is preferably 95% by weight or less, and more preferably 0% by weight to 75% by weight, from the viewpoint of further exhibiting the effects of the present invention.
From the viewpoint that the effect of the present invention can be further exhibited, the content ratio of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less as the polyol (a2) is preferably less than 70% by weight, more preferably 60% by weight or less, further preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less, based on the entire polyol.
[ crosslinking agent ]
The urethane adhesive composition preferably contains a crosslinking agent in order to further exhibit the effects of the present invention.
The urethane prepolymer and the polyol as the base polymer may be combined with a crosslinking agent, respectively, as components of the urethane adhesive composition.
The crosslinking agent to be combined with the urethane prepolymer and the polyol as the base polymer is preferably a polyfunctional isocyanate-based crosslinking agent in view of further exhibiting the effects of the present invention.
As the polyfunctional isocyanate-based crosslinking agent, any suitable polyfunctional isocyanate-based crosslinking agent usable in the urethanization reaction can be used. Examples of such a polyfunctional isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as 1, 2-ethanediisocyanate, 1, 4-butanediisocyanate and 1, 6-hexanediisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include: trimethylolpropane/tolylene diisocyanate adduct (trade name "Coronate L" manufactured by Nippon polyurethane industries Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (trade name "Coronate HL" manufactured by Nippon polyurethane industries Co., Ltd.), trade name "Coronate HX" (Nippon polyurethane industries Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (trade name "Takenate 110N" manufactured by Mitsui chemical Co., Ltd.) and the like are commercially available.
[ urethane adhesive composition ]
The urethane adhesive composition may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include: a polymer component other than urethane prepolymer and polyol, a crosslinking accelerator, a crosslinking catalyst, a silane coupling agent, a tackifier resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, and the like), an anti-aging agent, an inorganic filler, an organic filler, a metal powder, a colorant (pigment, dye, and the like), a foil, an anti-deterioration agent, a chain transfer agent, a plasticizer, a softener, a surfactant, an antistatic agent, a conductive agent, a stabilizer, a surface lubricant, a leveling agent, an anticorrosive agent, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.
The urethane adhesive composition preferably contains a deterioration inhibitor in order to further exhibit the effects of the present invention. The number of the deterioration preventing agents may be only 1, or may be 2 or more.
As the deterioration preventing agent, from the viewpoint that the effect of the present invention can be further exhibited, preferable examples include: antioxidants, ultraviolet absorbers, light stabilizers.
Examples of the antioxidant include: radical chain inhibitors, peroxide decomposers, and the like.
Examples of the radical chain inhibitor include: phenol-based antioxidants, amine-based antioxidants, and the like.
Examples of the phenolic antioxidant include: monophenol antioxidants, bisphenol antioxidants, high-molecular phenol antioxidants, and the like. Examples of the monophenol-based antioxidant include: 2, 6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. Examples of the bisphenol antioxidant include: 2,2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2,4,8, 10-tetraoxaspiro [5,5] undecane and the like. Examples of the polymeric phenol antioxidant include: 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [ methylene-3- (3',5' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane, bis [3,3' -bis- (4' -hydroxy-3 ' -t-butylphenyl) butanoic acid ] diol ester, 1,3, 5-tris (3',5' -di-t-butyl-4 ' -hydroxybenzyl) -s-triazine-2, 4,6- (1H,3H,5H) trione, tocopherol, and the like.
Examples of the peroxide decomposer include: sulfur-based antioxidants, phosphorus-based antioxidants, and the like. Examples of the sulfur-based antioxidant include: dilauryl 3,3' -thiodipropionate, dimyristyl 3,3' -thiodipropionate, distearyl 3,3' -thiodipropionate, and the like. Examples of the phosphorus-based antioxidant include: triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, and the like.
Examples of the ultraviolet absorber include: benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like.
Examples of the benzophenone-based ultraviolet absorber include: 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2' -dihydroxy-4-dimethoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.
Examples of the benzotriazole-based ultraviolet absorber include: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-amylphenyl) benzotriazole, 2- (2 '-hydroxy-4' -octyloxyphenyl) benzotriazole, 2- [2 '-hydroxy-3' - (3 ", 4', 5', 6 ', -tetrahydrophthalimidomethyl) -5' -methylphenyl ] benzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], 2- (2' -hydroxy-5 ' -methacryloxyphenyl) -2H-benzotriazole and the like.
Examples of the salicylic acid-based ultraviolet absorber include: phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate-based ultraviolet absorber include: 2-ethylhexyl 2-cyano-3, 3 '-diphenylacrylate, ethyl 2-cyano-3, 3' -diphenylacrylate, and the like.
Examples of the light stabilizer include: hindered amine light stabilizers, ultraviolet light stabilizers, and the like. Examples of the hindered amine light stabilizer include: bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, methyl-1, 2,2,6, 6-pentamethyl-4-piperidyl sebacate, and the like. Examples of the ultraviolet stabilizer include: bis (octylphenyl) nickel sulfide, [2,2' -thiobis (4-tert-octylphenol) ] n-butylamine nickel, 3, 5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester nickel complex, benzoate-type quencher, nickel dibutyldithiocarbamate, and the like.
[ urethane polymer formed from urethane adhesive composition containing urethane prepolymer and polyfunctional isocyanate crosslinking agent ]
The number of urethane prepolymers may be only 1, or may be 2 or more. The number of the polyfunctional isocyanate crosslinking agents may be only 1, or may be 2 or more.
As a method for forming a urethane polymer from a urethane adhesive composition containing a urethane prepolymer and a polyfunctional isocyanate crosslinking agent, any suitable production method can be employed as long as the method is a method for producing a urethane polymer using a so-called "urethane prepolymer" as a raw material.
The number average molecular weight Mn of the urethane prepolymer is preferably 3000 to 1000000 in order to further exhibit the effect of the present invention.
In order to further exhibit the effects of the present invention, the equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate crosslinking agent is preferably 5.0 or less, more preferably 0.01 to 4.75, even more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, and most preferably 0.05 to 4.0 in terms of NCO groups/OH groups.
The content ratio of the polyfunctional isocyanate-based crosslinking agent is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 25 parts by weight, even more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 17.5 parts by weight, and most preferably 1 to 15 parts by weight, based on 100 parts by weight of the urethane prepolymer, from the viewpoint of further exhibiting the effects of the present invention.
[ urethane polymer formed from urethane adhesive composition containing polyol and polyfunctional isocyanate crosslinking agent ]
The number of the polyhydric alcohols may be only 1, or may be 2 or more. The number of the polyfunctional isocyanate crosslinking agents may be only 1, or may be 2 or more.
In order to further exhibit the effects of the present invention, the equivalent ratio of NCO groups to OH groups in the polyol and the polyfunctional isocyanate crosslinking agent is preferably 5.0 or less, more preferably 0.1 to 3.0, further preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0 in terms of NCO groups/OH groups.
The content ratio of the polyfunctional isocyanate-based crosslinking agent is preferably 1.0 to 30 parts by weight, more preferably 1.5 to 27 parts by weight, even more preferably 2.0 to 25 parts by weight, particularly preferably 2.3 to 23 parts by weight, and most preferably 2.5 to 20 parts by weight, based on 100 parts by weight of the polyol, from the viewpoint of further exhibiting the effects of the present invention.
The urethane polymer formed from the urethane adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent is specifically preferably: the adhesive composition is formed by curing a urethane adhesive composition containing a polyol and a polyfunctional isocyanate crosslinking agent. As a method for forming a urethane polymer by curing a urethane adhesive composition containing a polyol and a polyfunctional isocyanate crosslinking agent, any suitable method such as a urethanization reaction method using bulk polymerization, solution polymerization, or the like can be employed within the range not impairing the effects of the present invention.
In order to cure the urethane adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent, a catalyst is preferably used. Examples of such catalysts include: organometallic compounds, tertiary amine compounds, and the like.
Examples of the organometallic compound include: iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction rate and pot life of the pressure-sensitive adhesive layer.
Examples of the iron-based compound include: iron acetylacetonate, iron 2-ethylhexanoate,
Figure BDA0003172636560000261
Iron, and the like.
Examples of the tin-based compound include: dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, and the like.
Examples of the titanium-based compound include: dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and the like.
Examples of the zirconium-based compound include: zirconium naphthenate, zirconium acetylacetonate, and the like.
Examples of the lead-based compound include: lead oleate, lead 2-ethylhexoate, lead benzoate, lead naphthenate, and the like.
Examples of the cobalt-based compound include: cobalt 2-ethylhexanoate, cobalt benzoate, and the like.
Examples of the zinc-based compound include: zinc naphthenate, zinc 2-ethylhexanoate, and the like.
Examples of the tertiary amine compound include: triethylamine, triethylenediamine, 1, 8-diazabicyclo (5,4,0) -undecene-7, and the like.
The number of the catalyst may be only 1, or may be 2 or more. Further, a catalyst may be used in combination with a crosslinking retarder or the like. The amount of the catalyst is preferably 0.005 to 1.00 parts by weight, more preferably 0.01 to 0.75 parts by weight, still more preferably 0.01 to 0.50 parts by weight, and particularly preferably 0.01 to 0.20 parts by weight, based on 100 parts by weight of the polyol, from the viewpoint of further exhibiting the effects of the present invention.
< rubber-based adhesive >
As the rubber-based adhesive, any suitable rubber-based adhesive such as a known rubber-based adhesive described in, for example, japanese patent application laid-open publication No. 2015-074771 can be used within a range not to impair the effects of the present invention. These may be 1 kind or 2 or more kinds. The rubber-based adhesive may contain any suitable component within a range not impairing the effects of the present invention.
< Silicone-based adhesive >
As the silicone-based adhesive, any suitable silicone-based adhesive such as the known silicone-based adhesive described in, for example, japanese patent application laid-open publication No. 2014-047280 can be used within the range not impairing the effects of the present invention. These may be 1 kind or 2 or more kinds. The silicone adhesive may contain any suitable component within a range not impairing the effects of the present invention.
Base material for Reinforcement
As the reinforcing base material, a reinforcing base material formed of any suitable material can be used within a range not impairing the effects of the present invention. Examples of such materials include: plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, laminates of these (particularly laminates comprising plastic films), and the like.
The reinforcing base material is preferably a plastic film in view of further exhibiting the effects of the present invention.
Examples of the plastic film include: plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); plastic films made of olefin resins containing α -olefin as a monomer component, such as Polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymers, and ethylene-vinyl acetate copolymers (EVA); a plastic film composed of polyvinyl chloride (PVC); a plastic film made of a vinyl acetate resin; a plastic film composed of Polycarbonate (PC); a plastic film made of polyphenylene sulfide (PPS); plastic films made of amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film made of a polyimide resin; a plastic film composed of polyether ether ketone (PEEK); plastic films made of olefin resins such as Polyethylene (PE) and polypropylene (PP); and plastic films made of fluorine-based resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and chlorofluoroethylene-vinylidene fluoride copolymers.
The thickness of the reinforcing base material may be any suitable thickness according to the purpose within the range not impairing the effects of the present invention. Such a thickness is preferably 25 to 500 μm, more preferably 25 to 400 μm, still more preferably 25 to 300 μm, particularly preferably 25 to 200 μm, and most preferably 25 to 150 μm, from the viewpoint of further exhibiting the effects of the present invention.
The reinforcing base material may be 1 layer only, or may be 2 or more layers.
The reinforcing base material may be subjected to surface treatment. Examples of the surface treatment include: corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, coating treatment with a primer, and the like.
The reinforcing base material may contain any suitable additive according to the purpose within a range not impairing the effect of the present invention.
Surface protective film
The surface protection film comprises an adhesive layer (C1), a base material layer (C2), and an antistatic layer (C3) in this order. The surface protection film may have any suitable other layer within a range not impairing the effects of the present invention, as long as it includes the pressure-sensitive adhesive layer (C1), the base material layer (C2), and the antistatic layer (C3) in this order.
The pressure-sensitive adhesive layer (C1) was directly laminated on the reinforcing base material.
The thickness of the surface protecting film is preferably 5 to 500. mu.m, more preferably 10 to 400. mu.m, still more preferably 20 to 300. mu.m, particularly preferably 30 to 200. mu.m, and most preferably 40 to 100. mu.m, from the viewpoint of further exhibiting the effects of the present invention.
The surface protective film can be produced by any suitable method. Such a production method can be carried out, for example, by any suitable production method as follows:
(1) a method of applying a solution or hot melt of a material for forming the adhesive layer (C1) on the surface of the base layer (C2) provided with the antistatic layer (C3) on the side opposite to the antistatic layer (C3);
(2) a method of transferring an adhesive layer (C1) formed by coating a solution or a hot melt of a material for forming the adhesive layer (C1) on the separator, onto a surface of the base layer (C2) provided with the antistatic layer (C3) on the opposite side of the antistatic layer (C3);
(3) a method of extruding a material for forming the adhesive layer (C1) onto a surface of the base material layer (C2) provided with the antistatic layer (C3) on the opposite side of the antistatic layer (C3) to form a coating;
(4) a method of extruding the base material layer (C1), the base material layer (C2), and the antistatic layer (C3) in a multilayer form;
(5) a method of single-layer laminating the adhesive layer (C1) on the surface of the base material layer (C2) provided with the antistatic layer (C3) on the opposite side to the antistatic layer (C3), or a method of double-layer laminating the adhesive layer (C1) together with the laminated layer;
(6) a method of laminating the adhesive layer (C1) and a base material layer (C2) such as a film or a laminated layer, and an antistatic layer (C3) in two or more layers, and the like.
Examples of the coating method include roll coating, comma coating, die coating, reverse coating, screen printing, and gravure coating.
< adhesive layer (C1) >)
The adhesive layer (C1) may be any suitable adhesive layer within a range not impairing the effects of the present invention. The pressure-sensitive adhesive layer (C1) may be 1 layer only, or may be 2 or more layers.
The thickness of the pressure-sensitive adhesive layer (C1) is preferably 0.5 to 150. mu.m, more preferably 1 to 100. mu.m, still more preferably 3 to 80 μm, particularly preferably 5 to 50 μm, and most preferably 10 to 30 μm, from the viewpoint of further exhibiting the effects of the present invention.
The adhesive layer (C1) is preferably composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.
The adhesive layer (C1) may be formed by any suitable method. Examples of such a method include the following: an adhesive layer is formed on any suitable substrate by applying an adhesive composition (at least 1 selected from the group consisting of an acrylic adhesive composition, a urethane adhesive composition, a rubber adhesive composition, and a silicone adhesive composition) on the substrate, heating and drying the composition as needed, and curing the composition as needed. Examples of such coating methods include: gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, roll brush coater, and the like.
As for the detailed description of the acrylic adhesive, urethane adhesive, rubber adhesive, and silicone adhesive, the detailed description of the acrylic adhesive, urethane adhesive, rubber adhesive, and silicone adhesive in the description of the adhesive layer (1) can be cited as it is.
< substrate layer (C2) >)
The base material layer (C2) may be only 1 layer, or may be 2 or more layers. The substrate layer (C2) may also be extended.
The thickness of the base material layer (C2) is preferably 4 to 450 μm, more preferably 8 to 350 μm, still more preferably 12 to 250 μm, particularly preferably 16 to 150 μm, and most preferably 20 to 100 μm, from the viewpoint of further exhibiting the effects of the present invention.
As the base layer (C2), any suitable material may be used as long as the effects of the present invention are not impaired. Examples of such materials include: plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, laminates of these (particularly laminates comprising plastic films), and the like.
The base layer (C2) is preferably a plastic film in view of further exhibiting the effects of the present invention.
Examples of the plastic film include: plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); plastic films made of olefin resins containing α -olefin as a monomer component, such as Polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymers, and ethylene-vinyl acetate copolymers (EVA); a plastic film composed of polyvinyl chloride (PVC); a plastic film made of a vinyl acetate resin; a plastic film composed of Polycarbonate (PC); a plastic film made of polyphenylene sulfide (PPS); plastic films made of amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film made of a polyimide resin; a plastic film composed of polyether ether ketone (PEEK); plastic films made of olefin resins such as Polyethylene (PE) and polypropylene (PP); and plastic films made of fluorine-based resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and chlorofluoroethylene-vinylidene fluoride copolymers.
The base layer (C2) may contain any suitable additive according to the purpose within a range not impairing the effects of the present invention.
< antistatic layer (C3) >)
As for the thickness of the antistatic layer (C3), any suitable thickness may be adopted according to the purpose within the range not impairing the effects of the present invention. The thickness is preferably 1nm to 1000nm, more preferably 5nm to 900nm, still more preferably 7.5nm to 800nm, and particularly preferably 10nm to 700 nm.
The antistatic layer (C3) may be 1 layer only, or may be 2 or more layers.
As for the antistatic layer (C3), any suitable antistatic layer can be used as long as it can exert an antistatic effect, within a range not impairing the effects of the present invention. The antistatic layer is preferably formed by applying a conductive coating solution containing a conductive polymer on an arbitrary suitable base layer. Specifically, for example, the antistatic layer is formed by applying a conductive coating liquid containing a conductive polymer on a base material layer (C2). Specific coating methods include: roll coating, bar coating, gravure coating, and the like.
As the conductive polymer, any suitable conductive polymer can be used within a range not impairing the effects of the present invention. Examples of such a conductive polymer include a conductive polymer in which a polyanion is doped in a pi-conjugated conductive polymer. Examples of the pi-conjugated conductive polymer include: chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include: polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polymethacrylic acid, and the like.
The surface resistance value of the antistatic layer (C3) is preferably 1.0X 10 at 23 ℃ and 50% RH4Ω～1.0×109Omega, more preferably 1.0X 104Ω～5.0×108Ω, more preferably 5.0 × 104Ω～1.0×108Omega, particularly preferably 1.0X 105Ω～5.0×107Omega. If the surface resistance value of the antistatic layer (C3) is within the above range, the effects of the present invention can be further exhibited.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The test and evaluation methods in examples and the like are as follows. In the case of "part(s)", the term "part(s)" means "part(s) by weight unless otherwise specified, and in the case of"% "means"% by weight "unless otherwise specified.
< determination of weight average molecular weight >
The weight average molecular weight was measured by a Gel Permeation Chromatography (GPC) method. Specifically, the GPC measurement apparatus used was the product "HLC-8120 GPC" (manufactured by Tosoh corporation), and the measurement was performed under the following conditions, and the value was calculated from the standard polystyrene conversion value.
(conditions for measuring molecular weight)
Sample concentration: 0.2 wt% (tetrahydrofuran solution)
Sample injection amount: 10 μ L
Column: the trade name is "TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)" (manufactured by Tosoh Co., Ltd.)
Reference column: the trade name "TSKgel SuperH-RC (1 root)" (manufactured by Tosoh corporation)
Eluent: tetrahydrofuran (THF)
Flow rate: 0.6mL/min
The detector: differential Refractometer (RI)
Column temperature (measurement temperature): 40 deg.C
< measurement of surface resistance value >
The surface resistance value of the object to be measured was measured by MODEL152-1(152P-2P Probe) manufactured by TREK corporation. The measurement was carried out under the conditions of voltage 10V, time 10 seconds, temperature 23 ℃ and humidity 50% RH.
< measurement of Electrostatic Voltage at pickup >
Two sheets of films (reinforcing laminated film (a1) and reinforcing laminated film (a2)) were prepared, each of which was obtained by cutting a reinforcing laminated film subjected to electrostatic treatment in advance into a size of 70mm in width and 130mm in length. As shown in fig. 2, the reinforcing laminated film (a1) and the reinforcing laminated film (a2) were laminated in the same direction as the spacer side and so that the antistatic layer (B3) side of the reinforcing laminated film (a1) and the antistatic layer (C3) side of the reinforcing laminated film (a2) overlapped with each other, the reinforcing laminated film (a2) was picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH, and the ELECTROSTATIC voltage on the surface of the reinforcing laminated film (a1) on the antistatic layer (B3) side was measured by an ELECTROSTATIC potential measuring instrument (shidido ELECTROSTATIC ic, STATIRON DZ4) fixed at a position spaced by 30 mm. The measurement was carried out at a temperature of 23 ℃ and a humidity of 50% RH.
< measurement of initial adhesion of adhesive layer (1) to glass plate >
The reinforcing laminate film was cut into a width of 25mm and a length of 150mm to obtain a sample for evaluation.
The adhesive layer surface of the sample for evaluation was attached to a glass plate (trade name: MICRO SLIDE GLASS S, manufactured by Sonlang Nitri K.K.) by reciprocating a 2.0kg roller once under an atmosphere of 23 ℃ C.. times.50% RH. After aging at 23 ℃ C.. times.50% RH for 30 minutes, the adhesive force was measured by peeling the film at a peeling angle of 180 ℃ and a tensile rate of 300 mm/minute using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea corporation).
< evaluation of pickup Property >
With respect to a reinforcing laminate film having a surface protective film and a separator, whether or not the reinforcing laminate film stacked in the same direction can be picked up one by one smoothly was evaluated.
Good: when the reinforcing laminated films stacked in the same direction are picked up piece by piece, the reinforcing laminated films can be picked up piece by piece smoothly.
X: when reinforcing laminated films stacked in the same direction are picked up one by one, blocking occurs, and the sheets cannot be smoothly picked up one by one.
[ production example 1 ]: production of acrylic adhesive composition (1)
Butyl acrylate (manufactured by japan catalyst corporation): 95 parts by weight of acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 5 parts by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of an acrylic polymer solution (40% by weight) having a weight average molecular weight of 70 ten thousand was prepared by conducting polymerization for 10 hours while introducing nitrogen gas with gentle stirring while maintaining the liquid temperature in the flask at about 63 ℃.
Then, to the obtained acrylic polymer solution, 0.1 parts by weight of TETRAD-C (manufactured by mitsubishi gas chemical corporation) as a crosslinking agent was added in terms of solid content per 100 parts by weight of the solid content, and the resultant was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain the acrylic pressure-sensitive adhesive composition (1).
[ production example 2 ]: production of acrylic adhesive composition (2)
2-ethylhexyl acrylate (manufactured by Nippon catalyst Co., Ltd.) was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Toyo Synthesis Co., Ltd.): 4 parts by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of an acrylic polymer solution (40% by weight) having a weight average molecular weight of 55 ten thousand was prepared by conducting polymerization for 6 hours while introducing nitrogen gas with gentle stirring while maintaining the liquid temperature in the flask at about 65 ℃.
Next, to the obtained acrylic polymer solution, Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent was added in an amount of 4 parts by weight in terms of solid content and EMBILIZER OL-1 (manufactured by Tokyo Fine Chemical co., ltd.) as a crosslinking catalyst in an amount of 0.03 parts by weight in terms of solid content, based on 100 parts by weight of the solid content thereof, and the resultant was diluted with ethyl acetate so that the total solid content became 25% by weight and stirred with a disperser to obtain the acrylic pressure-sensitive adhesive composition (2).
[ production example 3 ]: production of urethane adhesive composition (3)
PREMINOL S3011 (Mn: 10000, manufactured by Asahi glass Co., Ltd.) as a polyfunctional polyol was added in an amount of 100 parts by weight in terms of solid content, and the mixture was changed to solid contentCalculated as 18 parts by weight of Coronate HX (manufactured by Nippon polyurethane industries Co., Ltd.) as a crosslinking agent and 0.04 parts by weight in terms of solid content as a crosslinking catalyst
Figure BDA0003172636560000351
Iron (manufactured by japan chemical industry corporation) and Irganox1010 (manufactured by BASF corporation) as a deterioration inhibitor in an amount of 0.5 parts by weight in terms of solid content were diluted with ethyl acetate so that the total solid content became 35% by weight, and stirred with a disperser to obtain a urethane adhesive composition (3).
[ production example 4 ]: production of laminate of [ antistatic layer X ]/[ base Material layer ]
As the conductive coating agent, S-948 (manufactured by kyoto grease corporation) was prepared using a mixed solution of pure water and Ekinen F6 (manufactured by Japan Alcohol tracing co., ltd.): 100 parts by weight of P-795 (manufactured by Chijing fat Ltd.): 10 parts by weight was diluted to 0.3% by weight to obtain a conductive coating liquid (a). The obtained conductive coating liquid (a) was applied to a polyester resin substrate "lumiror S10" (thickness 38 μm, manufactured by TORAY corporation) by a wire bar coater so that the thickness after drying became 40nm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes to produce a laminate of [ antistatic layer X ]/[ base layer ].
[ production example 5 ]: production of laminate of [ antistatic layer Y ]/[ base Material layer ]
As the conductive coating agent, a main agent of BONDEIP PA-100 (manufactured by Konishi corporation): 50 parts by weight of curing agent: 50 parts by weight were diluted to 5% by weight to obtain a conductive coating liquid (b). The obtained conductive coating liquid (b) was applied to a polyester resin substrate "lumiror S10" (thickness 38 μm, manufactured by TORAY corporation) by a wire bar coater so that the thickness after drying became 500nm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes to produce a laminate of [ antistatic layer Y ]/[ base layer ].
[ production example 6 ]: production of insulating bodies (1)
A silicone mold release agent (KS-847, manufactured by shin-Etsu chemical industries Co., Ltd.) was mixed with toluene: 100 parts by weight of a catalyst (CATPL-50T, manufactured by shin-Etsu chemical Co., Ltd.): 1.0 part by weight was diluted to 1.0% by weight to obtain an organosilicon release agent treating solution. The obtained silicone release agent treatment liquid was applied to the surface of the base material layer of the laminate of [ antistatic layer X ]/[ base material layer ] obtained in production example 4 by a wire bar coater so that the thickness after drying became 100nm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes, to produce a separator (1) comprising the laminate of [ release layer ]/[ base material layer ]/[ antistatic layer X ].
[ production example 7 ]: production of the separator (2)
A silicone mold release agent (KS-847, manufactured by shin-Etsu chemical industries Co., Ltd.) was mixed with toluene: 100 parts by weight of a catalyst (CAT PL-50T, manufactured by shin-Etsu chemical Co., Ltd.): 1.0 part by weight was diluted to 1.0% by weight to obtain an organosilicon release agent treating solution. The obtained silicone release agent treatment liquid was applied to the surface of the base material layer of the laminate of [ antistatic layer Y ]/[ base material layer ] obtained in production example 5 by a wire bar coater so that the thickness after drying became 100nm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes, to produce a separator (2) comprising the laminate of [ release layer ]/[ base material layer ]/[ antistatic layer Y ].
[ production example 8 ]: production of the separator (3)
A silicone mold release agent (KS-847, manufactured by shin-Etsu chemical industries Co., Ltd.) was mixed with toluene: 100 parts by weight of a catalyst (CAT PL-50T, manufactured by shin-Etsu chemical Co., Ltd.): 1.0 part by weight was diluted to 1.0% by weight to obtain an organosilicon release agent treating solution. The obtained silicone release agent treatment liquid was applied to the surface of a polyester resin substrate "lumiror S10" (thickness 38 μm, manufactured by TORAY corporation) by a wire bar coater so that the thickness after drying became 100nm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes to produce a separator (3) comprising a laminate of [ release layer ]/[ base layer ].
[ production example 9 ]: production of surface protective film (A)
The acrylic pressure-sensitive adhesive composition (2) obtained in production example 2 was applied to the surface of the base layer of the laminate of [ antistatic layer X ]/[ base layer ] obtained in production example 4 using a Fountain roll (Fountain roll) so that the thickness after drying became 23 μm, and cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds. Thereby, an adhesive layer was produced on the base layer. Next, the release layer side of the separator (3) obtained in production example 8 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (a).
[ production example 10 ]: production of surface protective film (B)
The urethane adhesive composition (3) obtained in production example 3 was applied to the surface of the base layer of the laminate of [ antistatic layer X ]/[ base layer ] obtained in production example 4 by a fountain roll so that the thickness after drying became 12 μm, and cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds. Thereby, an adhesive layer was produced on the base layer. Next, the release layer side of the separator (3) obtained in production example 8 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (B).
Production example 11: production of surface protective film (C)
The acrylic pressure-sensitive adhesive composition (2) obtained in production example 2 was applied to the surface of the base layer of the laminate of [ antistatic layer Y ]/[ base layer ] obtained in production example 5 by a fountain roll so that the thickness after drying became 23 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. Thereby, an adhesive layer was produced on the base layer. Next, the release layer side of the separator (3) obtained in production example 8 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (C).
[ production example 12 ]: production of surface protective film (D)
The urethane adhesive composition (3) obtained in production example 3 was applied to the surface of the base layer of the laminate of [ antistatic layer Y ]/[ base layer ] obtained in production example 5 by a fountain roll so that the thickness after drying was 12 μm, and cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds. Thereby, an adhesive layer was produced on the base layer. Next, the release layer side of the separator (3) obtained in production example 8 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (D).
[ example 1]
The acrylic adhesive composition (1) obtained in production example 1 was applied to "lumiror S10" (manufactured by TORAY) having a thickness of 75 μm, which is a reinforcing base material made of a polyester resin, using a fountain roll so that the thickness after drying became 25 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. Thereby, the adhesive layer is formed on the reinforcing base material.
Next, the release layer side of the separator (1) obtained in production example 6 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a laminate of [ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer X ].
Next, the separator (3) was peeled from the surface protective film (a) obtained in production example 9 to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer side was bonded to the surface of the reinforcing base material of the obtained laminate.
Thus, a reinforcing laminated film (1) having a structure including [ antistatic layer X ]/[ base material layer ]/[ adhesive layer ]/[ reinforcing base material layer ]/[ adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer X ] was obtained.
The results are shown in Table 1.
[ examples 2 to 3]
Laminated films (2) to (3) for reinforcement were obtained in the same manner as in example 1, except that the thickness of the pressure-sensitive adhesive layer formed by applying the acrylic pressure-sensitive adhesive composition (1) to the substrate for reinforcement was changed as shown in table 1.
The results are shown in Table 1.
[ examples 4 to 6]
Laminated films (4) to (6) for reinforcement were obtained in the same manner as in examples 1 to 3, except that the thickness of "lumiror S10" (manufactured by TORAY corporation) as the reinforcing base material was changed as shown in table 1.
The results are shown in Table 1.
[ example 7]
The acrylic adhesive composition (1) obtained in production example 1 was applied to "lumiror S10" (manufactured by TORAY) having a thickness of 75 μm, which is a reinforcing base material made of a polyester resin, using a fountain roll so that the thickness after drying became 25 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. Thereby, the adhesive layer is formed on the reinforcing base material.
Next, the release layer side of the separator (1) obtained in production example 6 was bonded to the surface of the pressure-sensitive adhesive layer to obtain a laminate of [ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer X ].
Next, the separator (3) was peeled from the surface protective film (B) obtained in production example 10 to expose the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer side was bonded to the surface of the reinforcing base material of the obtained laminate.
Thus, a reinforcing laminated film (7) having a structure including [ antistatic layer X ]/[ base material layer ]/[ adhesive layer ]/[ reinforcing base material layer ]/[ adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer X ] was obtained.
The results are shown in Table 1.
[ example 8]
A reinforcing laminated film (8) was obtained in the same manner as in example 7, except that the thickness of "lumiror S10" (manufactured by TORAY corporation) as the reinforcing base material was changed as shown in table 1.
The results are shown in Table 1.
Comparative example 1
A reinforcing laminated film (C1) having a structure comprising [ antistatic layer X ]/[ base material layer ]/[ adhesive layer ]/[ reinforcing base material ]/[ adhesive layer ]/[ release layer ]/[ base material layer ] was obtained in the same manner as in example 1, except that the separator (3) obtained in production example 8 was used instead of the separator (1) obtained in production example 6.
The results are shown in Table 1.
Comparative example 2
A reinforcing laminated film (C2) including a configuration of [ antistatic layer X ]/[ base material layer ]/[ pressure-sensitive adhesive layer ]/[ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ] was obtained in the same manner as in comparative example 1, except that the surface-protecting film (B) obtained in production example 10 was used instead of the surface-protecting film (a) obtained in production example 9.
The results are shown in Table 1.
Comparative example 3
A reinforcing laminated film (C3) having a structure including [ antistatic layer X ]/[ base material layer ]/[ adhesive layer ]/[ reinforcing base material ]/[ adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer Y ] was obtained in the same manner as in example 1, except that the separator (2) obtained in production example 7 was used instead of the separator (1) obtained in production example 6.
The results are shown in Table 1.
Comparative example 4
A reinforcing laminated film (C4) having a structure including [ antistatic layer X ]/[ base material layer ]/[ pressure-sensitive adhesive layer ]/[ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer Y ] was obtained in the same manner as in comparative example 3, except that the surface-protecting film (B) obtained in production example 10 was used instead of the surface-protecting film (a) obtained in production example 9.
The results are shown in Table 1.
Comparative example 5
A reinforcing laminated film (C5) having a structure including [ antistatic layer Y ]/[ base material layer ]/[ pressure-sensitive adhesive layer ]/[ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer Y ] was obtained in the same manner as in comparative example 3, except that the surface protection film (C) obtained in production example 11 was used instead of the surface protection film (a) obtained in production example 9.
The results are shown in Table 1.
Comparative example 6
A reinforcing laminated film (C6) having a structure including [ antistatic layer Y ]/[ base material layer ]/[ pressure-sensitive adhesive layer ]/[ reinforcing base material ]/[ pressure-sensitive adhesive layer ]/[ release layer ]/[ base material layer ]/[ antistatic layer Y ] was obtained in the same manner as in comparative example 3, except that the surface protection film (D) obtained in production example 12 was used instead of the surface protection film (a) obtained in production example 9.
The results are shown in Table 1.
[ Table 1]
Figure BDA0003172636560000411
Industrial applicability
The reinforcing laminated film of the present invention can be picked up smoothly from a stacked state piece by piece, and therefore, can be preferably used for manufacturing optical members, electronic members, and the like.
Description of the reference numerals
Reinforcing laminate film 1000
Separator 100
Adhesive layer (1)200
Reinforcing base material 300
Surface protective film 400
Release layer (B1)110
Substrate layer (B2)120
Antistatic layer (B3)130
Adhesive layer (C1)410
Substrate layer (C2)420
Antistatic layer (C3)430

Claims (10)

1. A reinforcing laminate film comprising a separator, an adhesive layer (1), a reinforcing base material, and a surface protective film in this order,
the separator comprises a release layer (B1), a base material layer (B2) and an antistatic layer (B3) in this order,
the surface protection film comprises an adhesive layer (C1), a base material layer (C2) and an antistatic layer (C3) in sequence,
the release layer (B1) is directly laminated with the adhesive layer (1),
the reinforcing base material is directly laminated with the adhesive layer (C1),
two sheets of the reinforcing laminated film were laminated so that the antistatic layer (B3) side of one sheet of the reinforcing laminated film (a1) and the antistatic layer (C3) side of the other sheet of the reinforcing laminated film (a2) overlapped with each other, and the electrostatic voltage on the surface of the reinforcing laminated film (a1) on the antistatic layer (B3) side was 10kV or less when the film was picked up at a peeling angle of 150 degrees and a peeling speed of 10 m/min at a temperature of 23 ℃ and a humidity of 50% RH.
2. The reinforcing laminate film according to claim 1, wherein the antistatic layer (B3) has a surface resistance value of 1.0X 10 at a temperature of 23 ℃ and a humidity of 50% RH4Ω～1.0×109Ω。
3. The reinforcing laminate film according to claim 1 or 2, wherein the antistatic layer (C3) has a surface resistance value of 1.0X 10 at a temperature of 23 ℃ and a humidity of 50% RH4Ω～1.0×109Ω。
4. The laminated reinforcing film according to any one of claims 1 to 3, wherein the antistatic layer (B3) comprises a conductive polymer.
5. The laminated reinforcing film according to any one of claims 1 to 4, wherein the antistatic layer (C3) comprises a conductive polymer.
6. The reinforcing laminate film according to any one of claims 1 to 5, wherein the reinforcing base material is a plastic film.
7. The reinforcing laminate film according to any one of claims 1 to 6, wherein the adhesive layer (1) is composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.
8. The reinforcing laminate film according to any one of claims 1 to 6, wherein the adhesive layer (C1) is composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.
9. The reinforcing laminate film according to claim 7 or 8, wherein the acrylic adhesive is formed from an acrylic adhesive composition comprising: the composition (A) comprises (a) an alkyl (meth) acrylate in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms, and (b) at least one member selected from the group consisting of (meth) acrylate having an OH group and (meth) acrylic acid.
10. The laminate film for reinforcement according to any one of claims 1 to 9, wherein the adhesive layer (1) exposed by peeling the separator at a temperature of 23 ℃, a humidity of 50% RH, a peeling angle of 150 ℃, and a peeling speed of 10 m/min has an initial adhesive force to a glass plate of 1.0N/25mm or more under conditions of 23 ℃, a humidity of 50% RH, a peeling angle of 180 ℃, and a peeling speed of 300 mm/min.
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