CN110121416B - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN110121416B
CN110121416B CN201780081268.4A CN201780081268A CN110121416B CN 110121416 B CN110121416 B CN 110121416B CN 201780081268 A CN201780081268 A CN 201780081268A CN 110121416 B CN110121416 B CN 110121416B
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meth
separator
film
acrylate
sensitive adhesive
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CN201780081268.4A
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CN110121416A (en
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渡部奈津子
三井数马
野中崇弘
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Nitto Denko Corp
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a surface protection film with a separator for an optical member, wherein when the surface protection film with the separator for the optical member is subjected to position adjustment by using an automatic laminating machine and the separator is peeled off from the surface of the optical member, the surface protection film for the optical member can be bonded on the surface of the optical member at an accurate position due to excellent position adjustment performance of the separator. The optical surface protection film with a separator of the present invention is characterized by comprising: the optical surface protection film comprises a base film and a separator, wherein the base film comprises a pressure-sensitive adhesive layer on at least one surface of the base film, the separator is arranged on the surface opposite to the surface of the base film in contact with the pressure-sensitive adhesive layer, the separator comprises a release layer and a base, and the haze of the separator is more than 90% and the total light transmittance of the separator is less than 50%.

Description

Surface protective film
Technical Field
The present invention relates to an optical surface protective film with a separator. In particular, it is useful that an optical surface protective film with a spacer for protecting the surface of an optical member (for example, a polarizing plate, a wavelength plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film, or the like used in a liquid crystal display or the like) can be accurately positioned on the surface of the optical member, and the spacer is peeled off after the positioning, whereby the optical surface protective film can be bonded to the surface of the optical member at an accurate position.
Background
The surface protective film generally has a structure in which an adhesive layer is provided on a film-like base film (support). The surface protective film is bonded to an optical member as an adherend via the pressure-sensitive adhesive layer, and thus is used to protect the optical member from damage and contamination of the surface during processing, transportation, inspection, and the like. For example, a panel of a liquid crystal display is formed by bonding an optical member such as a polarizing plate or a wavelength plate to a liquid crystal cell using an adhesive layer. The pressure-sensitive adhesive layer is protected and stored by a separator or the like subjected to a mold release treatment, for the purpose of protecting the pressure-sensitive adhesive layer from drying or the like until it is actually attached to the optical member (patent document 1).
Then, after the surface of the pressure-sensitive adhesive layer of the surface protecting film is actually stuck to an optical member and used, the surface protecting film is peeled off and removed at a stage where it is no longer necessary.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 224811
Disclosure of Invention
Problems to be solved by the invention
In order to bond the surface protective film with the spacer to the surface of the optical member at a precise position, the surface protective film is cut into a desired size without cutting the spacer, a hole is formed in the outer edge of the spacer, the hole portion is sensed by a sensor, position adjustment is performed by an automatic bonding machine, and the spacer is peeled off and then bonded to the surface of the optical member.
However, even if the position of the optical member is adjusted accurately by using the surface protecting film with a transparent spacer which is generally used, the hole portion cannot be sensed accurately, and a variation occurs, and when the spacer with the surface protecting film of a spacer is peeled off and attached to the optical member, inconvenience such as the attachment at an accurate position is caused, which causes a problem.
In view of the above circumstances, the present inventors have made extensive studies and, as a result, have an object to provide an optical surface protective film with a separator, which is excellent in position adjustability based on the separator and can be attached to the surface of an optical member at an accurate position when the optical surface protective film with a separator is subjected to position adjustment using an automatic attaching machine and is attached to the surface of the optical member after the separator is peeled off.
Means for solving the problems
That is, the optical surface protection film with a separator of the present invention is characterized by comprising: the optical surface protection film comprises a base film and a pressure-sensitive adhesive layer on at least one surface of the base film, and a separator on the surface opposite to the surface of the pressure-sensitive adhesive layer in contact with the base film, wherein the separator comprises a release layer and a base, and has a haze of 90% or more and a total light transmittance of 50% or less.
In the optical surface-protecting film with a separator of the present invention, the base film is preferably a polyester film.
In the optical surface-protecting film with a separator of the present invention, the pressure-sensitive adhesive layer is preferably formed from a pressure-sensitive adhesive composition containing at least 1 selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive and a silicone pressure-sensitive adhesive.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can obtain the following optical surface protection film with a separator by using a separator having specific optical characteristics: when the optical surface protective film with a spacer is subjected to position adjustment with respect to the surface of an optical member using an automatic laminating machine, and is laminated to the surface of the optical member after the spacer is peeled off, the optical surface protective film is excellent in position adjustment by the spacer, can be pasted to the surface of the optical member at an accurate position, and is useful.
Drawings
FIG. 1 is a schematic cross-sectional view showing one configuration example of a separator-equipped surface protective film of the present invention.
Fig. 2 is a schematic cross-sectional view showing one configuration example of the optical surface protective film with a separator of the present invention after position adjustment on an optical member.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
< integral Structure of optical surface protective film with separator >
The spacer-attached optical surface protection film (hereinafter, may be simply referred to as "surface protection film") disclosed herein is generally a film in which the surface of an adhesive layer in the form of an adhesive tape, a sticker label, an adhesive film, or the like is protected by a spacer, and is particularly suitable as a surface protection film for protecting the surface of an optical member (for example, an optical member used as a constituent element of a liquid crystal display panel such as a polarizing plate or a wavelength plate) during processing, inspection, or transportation of the optical member. The pressure-sensitive adhesive layer in the surface protective film is typically formed continuously, and is not limited to this form, and may be formed in a regular or irregular pattern such as dots or stripes. Further, the surface protective film disclosed herein may be in the form of a roll or a sheet.
< substrate film >
The optical surface protective film with a separator of the present invention is characterized by comprising a base film. In the technique disclosed herein, the resin material constituting the base film may be used without particular limitation, and for example, a material excellent in characteristics such as transparency, mechanical strength, thermal stability, water barrier property, isotropy, flexibility, and dimensional stability is preferably used. In particular, the base film is flexible, and therefore, the adhesive composition can be applied by a roll coater or the like, and can be wound into a roll.
As the base film (support), a plastic film made of a resin material containing, as a main resin component (a main component in the resin component, typically a component accounting for 50% by weight or more), for example, a polyester-based polymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate; cellulose polymers such as cellulose diacetate and cellulose triacetate; a polycarbonate-series polymer; acrylic polymers such as polymethyl methacrylate; and so on. As another example of the resin material, the following materials may be cited: styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide polymers such as nylon 6, and aromatic polyamide; and so on. Still other examples of the resin material include: imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aromatic ester polymers, polyoxymethylene polymers, epoxy polymers, and the like. May be a base film formed of a blend of 2 or more of the above polymers.
As the base film, a plastic film made of a transparent thermoplastic resin material can be preferably used. Among the above plastic films, a polyester film is more preferable. Here, the polyester film is a film containing, as a main resin component, a polyester-based polymer material (polyester resin) having a main skeleton based on ester bonds, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. The polyester film has properties preferable for a base film of a surface protective film, such as optical properties and excellent dimensional stability.
The resin material constituting the base film may contain various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (such as a pigment and a dye) as needed. For example, a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and coating with a primer can be performed. Such a surface treatment may be, for example, a treatment for improving adhesion between the base film and the adhesive layer (anchoring property of the adhesive layer).
As the base film, an antistatic-treated plastic film may also be used. The use of the base film is preferable because the electrification of the surface protective film itself at the time of peeling can be suppressed. Further, by using a plastic film as the base film and subjecting the plastic film to antistatic treatment, the electrification of the surface protective film itself can be reduced and antistatic performance to an adherend can be made excellent. The method for imparting the antistatic function is not particularly limited, and conventionally known methods can be used, and examples thereof include: a method of applying an antistatic resin comprising an antistatic agent and a resin component, a conductive polymer, and a conductive resin containing a conductive substance; a method of depositing or plating a conductive material; there are also methods of kneading an antistatic agent and the like.
The thickness of the base film is usually 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the base film is within the above range, the workability of bonding to an adherend, the releasability from an adherend, and the workability are excellent, and therefore, the base film is preferable.
The surface protective film disclosed herein may also be implemented in such a manner that other layers are further included in addition to the base film, the adhesive layer and the separator. Examples of the other layer include an undercoat layer (anchor layer) for improving the anchoring properties of the antistatic layer and the adhesive layer.
< adhesive layer >
The pressure-sensitive adhesive layer used in the present invention may be used without particular limitation if it is formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer having pressure-sensitive adhesiveness. As the pressure-sensitive adhesive composition, for example, an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a synthetic rubber pressure-sensitive adhesive, a natural rubber pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, or the like can be used, and among them, a pressure-sensitive adhesive composition containing (containing) at least 1 selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive is preferably used, and a pressure-sensitive adhesive composition (acrylic pressure-sensitive adhesive) using a (meth) acrylic polymer as the pressure-sensitive adhesive polymer is particularly preferably used.
When an acrylic pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer, a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms can be used as a main monomer as a raw material monomer constituting a (meth) acrylic polymer as a pressure-sensitive adhesive polymer constituting the acrylic pressure-sensitive adhesive. As the (meth) acrylic monomer, 1 or 2 or more species can be used. By using the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the peel strength (adhesive strength) to an adherend (protected object) can be easily controlled to be low, and a surface protection film having excellent light peelability and removability can be obtained. In the present invention, the (meth) acrylic polymer refers to an acrylic polymer and/or a methacrylic polymer, and the (meth) acrylic acid ester refers to an acrylic acid ester and/or a methacrylic acid ester.
Specific examples of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.
Among them, the surface protective film of the present invention includes (meth) acrylic monomers having an alkyl group having 4 to 14 carbon atoms such as n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate, which are particularly preferable examples. In particular, the use of a (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms makes it easy to control the peeling force (adhesive force) to an adherend low, and the removability is excellent.
In particular, the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably contained in an amount of 65% by weight or more, more preferably 75% by weight or more, further preferably 85 to 99.9% by weight, most preferably 90 to 99% by weight, based on 100% by weight of the total amount of the monomer components constituting the (meth) acrylic polymer. If the content is less than 65% by weight, the adhesive composition will have moderate wettability and the cohesive force of the adhesive layer will be poor, which is not preferable.
In addition, the (meth) acrylic polymer may use a hydroxyl group-containing (meth) acrylic monomer as a raw material monomer. As the hydroxyl group-containing (meth) acrylic monomer, 1 or 2 or more species can be used. By using the hydroxyl group-containing (meth) acrylic monomer, it is easy to control crosslinking and the like of the adhesive composition, and further, it is easy to control the balance between improvement of wettability by flow and reduction of peel force (adhesive force) in peeling.
Examples of the hydroxyl group-containing (meth) acrylic monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, and the like.
The hydroxyl group-containing (meth) acrylic monomer is contained in an amount of preferably 25% by weight or less, more preferably 15% by weight or less, and still more preferably 0.1 to 10% by weight, based on 100% by weight of the total amount of the monomer components constituting the (meth) acrylic polymer. If it is within the foregoing range, it is easy to control the balance between the wettability of the adhesive composition and the cohesive force of the resulting adhesive layer, and therefore it is preferable.
Further, as the other polymerizable monomer component, for the reason that the balance of the adhesive properties is easily obtained, a polymerizable monomer or the like for adjusting the glass transition temperature and the peelability of the (meth) acrylic polymer by setting Tg to 0 ℃ or less (usually-100 ℃ or more) may be used within a range not impairing the effect of the present invention.
In addition, the (meth) acrylic polymer may use a carboxyl group-containing (meth) acrylic monomer as a raw material monomer. By using the carboxyl group-containing (meth) acrylic monomer, the adhesive strength of the pressure-sensitive adhesive layer (surface protection film) can be inhibited from increasing with time, and the pressure-sensitive adhesive layer is excellent in removability, prevention of increase in adhesive strength, and workability. Further, the cohesive force and the shear force of the adhesive layer are also excellent, and are preferable.
Examples of the carboxyl group-containing (meth) acrylic monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
The carboxyl group-containing (meth) acrylic monomer is preferably 10% by weight or less, more preferably 0 to 8% by weight, and still more preferably 0 to 6% by weight, based on 100% by weight of the total amount of the monomer components constituting the (meth) acrylic polymer. If it is within the foregoing range, it is easy to control the balance between the wettability of the adhesive composition and the cohesive force of the resulting adhesive layer, and therefore it is preferable.
Further, the (meth) acrylic polymer may be used without particular limitation as long as the characteristics of the present invention are not impaired, and other polymerizable monomers than the raw material monomers may be used. For example, as the other polymerizable monomer, a component having a functional group which functions as a crosslinking base point and improves a peeling force (adhesive force) such as an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloylmorpholine, or a vinyl ether monomer, and a component having a cohesive force and heat resistance such as a cyano group-containing monomer, a vinyl ester monomer, or an aromatic vinyl monomer, can be suitably used. Among them, nitrogen-containing monomers such as a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and N-acryloylmorpholine are preferably used. The use of the nitrogen-containing monomer is useful because it can ensure an appropriate peeling force (adhesive force) without causing lifting, peeling, or the like, and can obtain a surface protective film having excellent shear force. These polymerizable monomers may be used in 1 kind or 2 or more kinds.
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
Examples of the amide group-containing monomer include: acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N-dimethylacrylamide, N-dimethylmethacrylamide, N-diethylacrylamide, N-diethylmethacrylamide, N' -methylenebisacrylamide, N-dimethylaminopropylacrylamide, N-dimethylaminopropylmethacrylamide, diacetoneacrylamide and the like.
Examples of the imide group-containing monomer include: cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, and the like.
Examples of the amino group-containing monomer include: aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, and the like.
Examples of the vinyl ester monomer include: vinyl acetate, vinyl propionate, vinyl laurate, and the like.
Examples of the aromatic vinyl monomer include: styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrenes, and the like.
Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether, and the like.
Examples of the vinyl ether monomer include: methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
In the present invention, the other polymerizable monomer is preferably 0 to 30% by weight, more preferably 0 to 10% by weight, based on 100% by weight of the total amount of the monomer components constituting the (meth) acrylic polymer. The other polymerizable monomers may be appropriately adjusted to obtain desired characteristics.
The (meth) acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.
The average molar number of addition of the oxyalkylene units of the alkylene oxide group-containing reactive monomer is preferably 1 to 40, more preferably 3 to 40, further preferably 4 to 35, and particularly preferably 5 to 30, from the viewpoint of compatibility with the oxyalkylene compound. When the average addition mole number is 1 or more, the effect of reducing contamination of an adherend (protected object) tends to be obtained efficiently. When the average addition mole number is more than 40, the interaction with the oxyalkylene-containing compound increases, and the viscosity of the adhesive composition tends to increase, so that the coating tends to be difficult, which is not preferable. The terminal of the oxyalkylene chain may be a hydroxyl group, or may be substituted with another functional group or the like.
The alkylene oxide group-containing reactive monomer may be used alone or in combination of 2 or more, and the total content is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, of the total amount of the monomer components of the (meth) acrylic polymer. If the content of the alkylene oxide group-containing reactive monomer exceeds 20% by weight, the staining property to an adherend is deteriorated, which is not preferable.
Examples of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer include units having an alkylene group having 1 to 6 carbon atoms, and examples thereof include oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like. The hydrocarbon group of the oxyalkylene chain may be a straight chain or may have a branch.
Further, the aforementioned alkylene oxide group-containing reactive monomer is more preferably a reactive monomer having an ethylene oxide group. By using a (meth) acrylic polymer containing a reactive monomer having an ethylene oxide group as a base polymer, the compatibility of the base polymer with the oxyalkylene group-containing compound is improved, bleeding out to an adherend can be suitably suppressed, and a pressure-sensitive adhesive composition with low staining can be obtained.
Examples of the alkylene oxide group-containing reactive monomer include: alkylene oxide (meth) acrylate adducts, reactive surfactants having a reactive substituent such as an acryloyl group, a methacryloyl group, or an allyl group in the molecule, and the like.
Specific examples of the alkylene oxide (meth) acrylate adduct include: polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauryloxypolyethylene glycol (meth) acrylate, stearyloxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, and the like.
Specific examples of the reactive surfactant include: an anionic reactive surfactant having a (meth) acryloyl group or allyl group, a nonionic reactive surfactant, a cationic reactive surfactant, and the like.
The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 10 to 500 ten thousand, more preferably 20 to 400 ten thousand, even more preferably 30 to 300 ten thousand, and most preferably 30 to 120 ten thousand. When the weight average molecular weight is less than 10 ten thousand, the cohesive force of the pressure-sensitive adhesive layer decreases, and adhesive residue tends to occur. On the other hand, when the weight average molecular weight exceeds 500 ten thousand, the fluidity of the polymer is lowered, and the wetting of the adherend (for example, polarizing plate) is insufficient, and the swelling tends to occur between the adherend and the pressure-sensitive adhesive layer of the surface-protecting film. The weight average molecular weight means a molecular weight measured by GPC (gel permeation chromatography).
The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ℃ or lower, more preferably-10 ℃ or lower (usually-100 ℃ or higher). When the glass transition temperature is higher than 0 ℃, the polymer is difficult to flow, and there is a tendency that, for example, the wetting of the polarizing plate as an optical member becomes insufficient, and a cause of swelling occurs between the polarizing plate and the pressure-sensitive adhesive layer of the surface protective film. In particular, by setting the glass transition temperature to preferably-40 ℃ or lower, more preferably-70 ℃ or lower, a pressure-sensitive adhesive layer having excellent wettability to a polarizing plate and light peelability can be easily obtained. The glass transition temperature of the (meth) acrylic polymer can be adjusted to fall within the above range by appropriately changing the monomer components and the composition ratio used.
The method of polymerization of the (meth) acrylic polymer is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization, and solution polymerization is a more preferable mode particularly from the viewpoint of workability and characteristics such as low staining property to an adherend (protected object). Further, the resulting polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
When a urethane adhesive is used for the adhesive layer, any suitable urethane adhesive can be used. As such a urethane adhesive, an adhesive comprising a urethane polymer as an adhesive polymer obtained by reacting a polyol with a polyisocyanate compound is preferably used. Examples of the polyhydric alcohol include: polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and the like. Examples of the polyisocyanate compound include: diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and the like.
When a silicone adhesive is used for the adhesive layer, any suitable silicone adhesive can be used. As such a silicone-based adhesive, an adhesive obtained by blending or aggregating a silicone-based polymer as an adhesive polymer can be preferably used.
Examples of the silicone-based pressure-sensitive adhesive include an addition reaction-curable silicone-based pressure-sensitive adhesive and a peroxide-curable silicone-based pressure-sensitive adhesive. Among these silicone-based adhesives, addition reaction curing type silicone-based adhesives are preferred because they do not use a peroxide (e.g., benzoyl peroxide) and do not generate decomposition products.
In the case where a polyalkyl silicone-based pressure-sensitive adhesive is obtained, for example, as the curing reaction of the addition reaction curable silicone-based pressure-sensitive adhesive, a method of curing a polyalkyl hydrosiloxane composition using a platinum catalyst is generally exemplified.
< oxyalkylene Compound >
The binder composition used in the present invention may also contain an oxyalkylene compound. The light peelability can be further exhibited by containing the oxyalkylene group-containing compound. Examples of the oxyalkylene group-containing compound include an organopolysiloxane having an oxyalkylene chain and an oxyalkylene group-containing compound containing no organopolysiloxane.
Specific examples of the organopolysiloxane having an oxyalkylene chain include commercially available organopolysiloxanes having an oxyalkylene chain in the main chain, such as X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889 (manufactured BY shin-Etsu chemical Co., Ltd.), BY16-201, SF8427 (manufactured BY Toyo Corning Co., Ltd.), IM22(WACKER ASAHIKASEI SILICONE Co., Ltd.). Further, examples of the organosiloxane having an oxyalkylene chain in a side chain include commercially available products of KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (manufactured by shin-Etsu chemical Co., Ltd.), SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, FZ-2110, L-7002, FZ-2122, FZ-2164, FZ-2203, FZ-7001, SH8400, SH 848700, SF8410, and SF8422 (manufactured by Dow Cory Co., Ltd.), TSF-4440, TSF-4441, TSF-4445, TSF-4450, TSF-4446, TSF-4452, TSF-4460 (manufactured by Momentive Performance Materials Inc.), BYK-333, BYK-307, BYK-377, BYK-UV3500, BYK-UV3570 (manufactured by BYK Japan KK), and the like. These compounds may be used alone, or 2 or more of them may be used in combination.
Specific examples of the oxyalkylene compound containing no organopolysiloxane include: nonionic surfactants such as polyoxyalkylene alkylamines, polyoxyalkylene diamines, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylallyl ethers, and polyoxyalkylene alkylphenyl allyl ethers; anionic surfactants such as polyoxyalkylene alkyl ether sulfate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, polyoxyalkylene alkyl phenyl ether sulfate ester salts, and polyoxyalkylene alkyl phenyl ether phosphate ester salts; in addition, cationic surfactants having a polyoxyalkylene chain (polyoxyalkylene chain), zwitterionic surfactants, polyether compounds having a polyoxyalkylene chain (including derivatives thereof), acrylic compounds having a polyoxyalkylene chain (including derivatives thereof), and the like are also mentioned. Further, a polyoxyalkylene chain-containing monomer may be compounded as the polyoxyalkylene chain-containing compound. The polyoxyalkylene chain-containing compound may be used alone or in combination of 2 or more.
Specific examples of the polyether compound having a polyoxyalkylene chain (polyether component) include: a block copolymer of polypropylene glycol (PPG) -polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, a block copolymer of PEG-PPG-PEG, and the like. Examples of the derivative of the polyether compound having a polyoxyalkylene chain include an oxypropylene compound whose terminal is etherified (such as a PPG monoalkyl ether or a PEG-PPG monoalkyl ether), and an oxypropylene compound whose terminal is acetylated (such as a terminal-acetylated PPG).
Further, specific examples of the acrylic compound having a polyoxyalkylene chain include (meth) acrylate polymers having an oxyalkylene group. The oxyalkylene group is preferably an oxyalkylene unit having an addition mole number of 1 to 50, more preferably 2 to 30, and further preferably 2 to 20. The terminal of the oxyalkylene chain may be a hydroxyl group, or may be substituted with an alkyl group, a phenyl group or the like.
The (meth) acrylate polymer having an oxyalkylene group is preferably a polymer containing an alkylene oxide of (meth) acrylic acid as a monomer component, and specific examples of the alkylene oxide of (meth) acrylic acid include ethylene glycol group-containing (meth) acrylates such as: methoxy-polyethylene glycol (meth) acrylate types such as methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (meth) acrylate, ethoxy-polyethylene glycol (meth) acrylate types such as ethoxy-diethylene glycol (meth) acrylate and ethoxy-triethylene glycol (meth) acrylate, butoxy-polyethylene glycol (meth) acrylate types such as butoxy-diethylene glycol (meth) acrylate and butoxy-triethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate types such as phenoxy-diethylene glycol (meth) acrylate and phenoxy-triethylene glycol (meth) acrylate, 2-ethylhexyl-polyethylene glycol (meth) acrylate and nonylphenol-polyethylene glycol (meth) acrylate types, and methoxy-polypropylene glycol (meth) acrylate type such as methoxy-dipropylene glycol (meth) acrylate.
Further, as the monomer component, other monomer components than the (meth) acrylic acid alkylene oxide may be used. Specific examples of the other monomer components include: acrylic esters and/or methacrylic esters having an alkyl group having 1 to 14 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, and n-tetradecyl (meth) acrylate.
Further, as the other monomer components other than the (meth) acrylic alkylene oxide, carboxyl group-containing (meth) acrylates, phosphoric group-containing (meth) acrylates, cyano group-containing (meth) acrylates, vinyl esters, aromatic vinyl compounds, acid anhydride group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, amide group-containing (meth) acrylates, amino group-containing (meth) acrylates, epoxy group-containing (meth) acrylates, N-acryloylmorpholine, vinyl ethers, and the like can be suitably used.
In a more preferred embodiment, the polyoxyalkylene chain-containing compound not containing an organopolysiloxane is a compound having a (poly) oxyethylene chain in at least a part thereof. By compounding the (poly) oxyethylene chain-containing compound, compatibility with the base polymer is improved, bleeding to an adherend can be suitably suppressed, and a pressure-sensitive adhesive composition with low staining can be obtained. Among them, particularly in the case of using a block copolymer of PPG-PEG-PPG, an adhesive excellent in low-fouling property can be obtained. The polyoxyethylene chain-containing compound preferably has a (poly) oxyethylene chain accounting for 5 to 90 wt%, more preferably 5 to 85 wt%, even more preferably 5 to 80 wt%, and most preferably 5 to 75 wt% of the total polyoxyalkylene chain-containing compound not containing organopolysiloxane.
Further, commercially available products of the polyoxyalkylene chain-containing compound containing no organopolysiloxane include, for example: adeka Pluronic 17R-4, Adeka Pluronic 25R-2 (all of which are manufactured by ADEKA Co., Ltd.), LATEMUL PD-420, LATEMUL PD-450, EMULGEN 120 (manufactured by Kao corporation), Aquaron HS-10, KH-10, NOIGEN EA-87, EA-137, EA-157, EA-167, EA-177 (which are manufactured by the first Industrial pharmaceutical Co., Ltd.), and the like.
The content of the oxyalkylene compound is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, further preferably 0.03 to 1.6 parts by weight, and most preferably 0.1 to 0.8 part by weight, based on 100 parts by weight of the adhesive polymer (which is a main polymer, for example, a (meth) acrylic polymer, a urethane polymer, a silicone polymer, or the like) constituting the adhesive composition. If the content is within the above range, the light peelability (removability) of the pressure-sensitive adhesive layer (surface protective film) used in the present invention is easily exhibited, and it is preferable.
< crosslinking agent >
The surface-protecting film of the present invention preferably contains a crosslinking agent in the adhesive composition. Further, in the present invention, the adhesive layer may be formed using the aforementioned adhesive composition. For example, when the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive containing the (meth) acrylic polymer, a pressure-sensitive adhesive layer (surface-protecting film) having more excellent heat resistance can be obtained by crosslinking the pressure-sensitive adhesive composition by appropriately adjusting the constituent unit and the constituent ratio of the (meth) acrylic polymer, the selection and addition ratio of the crosslinking agent, and the like.
As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine-based resin, an aziridine derivative, a metal chelate compound, and the like can be used, and particularly, an isocyanate compound or an epoxy compound is preferably used. These compounds may be used alone, or 2 or more of them may be used in combination.
Examples of the isocyanate compound include: aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene Diisocyanate (HDI) and dimer acid diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI) and 1, 3-bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and Xylylene Diisocyanate (XDI), and polyisocyanate modifications obtained by modifying the isocyanate compounds with allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond, uretonimine bond and oxadiazinetrione bond. Examples of commercially available products include: trade names TAKENATE 300S, TAKENATE 500, TAKENATE 600, TAKENATE D165N, TAKENATE D178N (manufactured by Takara pharmaceutical industries, Ltd.), SUMIDUR T80, SUMIDUR L, Desmodur N3400 (manufactured by Sumika Bayer Urethane Co., Ltd.), MILLONATE MR, MILLONATE MT, CORONATE L, CORONATE HL, CORONATE HX (manufactured by Nippon polyurethane industries, Ltd.), and the like. These isocyanate compounds may be used alone, or 2 or more kinds may be used in combination, or a 2-functional isocyanate compound and a 3-functional isocyanate compound may be used in combination. By using a crosslinking agent in combination, the adhesion and the repulsion resistance (adhesion to a curved surface) can be further achieved at the same time, and an adhesive layer (surface protection film) having more excellent adhesion reliability can be obtained.
Examples of the epoxy compound include N, N, N ', N' -tetraglycidyl-m-xylylenediamine (trade name TETRAD-X, manufactured by Mitsubishi gas chemical Co., Ltd.), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name TETRAD-C, manufactured by Mitsubishi gas chemical Co., Ltd.), and the like.
Examples of the melamine-based resin include hexamethylolmelamine. Examples of aziridine derivatives include commercially available products such as HDU, TAZM, and TAZO (these are manufactured by CRYPTOKI Co., Ltd.).
The metal chelate compound may include aluminum, iron, tin, titanium, nickel and the like as the metal component, and acetylene, methyl acetoacetate, ethyl lactate and the like as the chelate component.
The content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight, and most preferably 1 to 8 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. When the content is less than 0.01 part by weight, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the obtained pressure-sensitive adhesive layer decreases, and sufficient heat resistance may not be obtained, and the content tends to cause residual glue. On the other hand, when the content exceeds 20 parts by weight, the cohesive force of the polymer increases, the fluidity decreases, the wetting with an adherend (for example, a polarizing plate) becomes insufficient, and there is a tendency that a cause of the swelling occurs between the adherend and the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition layer). These crosslinking agents may be used alone, or 2 or more kinds may be used in combination.
< crosslinking catalyst >
The adhesive composition may further contain a crosslinking catalyst for allowing any of the above crosslinking reactions to proceed more efficiently. As the crosslinking catalyst, for example, there can be used: tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, iron tris (acetylacetonate), iron tris (hexane-2, 4-dione), iron tris (heptane-3, 5-dione), iron tris (5-methylhexane-2, 4-dione), iron tris (octane-2, 4-dione), iron tris (6-methylheptane-2, 4-dione), iron tris (2, 6-dimethylheptane-3, 5-dione), iron tris (nonane-2, 4-dione), iron tris (nonane-4, 6-dione), iron tris (2,2,6, 6-tetramethylheptane-3, 5-dione), iron tris (tridecane-6), 8-diketonate) iron, tris (1-phenylbutane-1, 3-diketonate) iron, tris (hexafluoroacetylacetonato) iron, tris (ethyl acetoacetate) iron, tris (n-propyl acetoacetate) iron, tris (isopropyl acetoacetate) iron, tris (n-butyl acetoacetate) iron, tris (sec-butyl acetoacetate) iron, tris (tert-butyl acetoacetate) iron, tris (methyl propionylacetate) iron, tris (ethyl propionylacetate) iron, tris (n-propyl propionylacetate) iron, iron catalysts such as iron tris (isopropyl propionylacetate), iron tris (n-butyl propionylacetate), iron tris (sec-butyl propionylacetate), iron tris (tert-butyl propionylacetate), iron tris (benzyl acetoacetate), iron tris (dimethyl malonate), iron tris (diethyl malonate), iron trimethoxy, iron triethoxide, iron triisopropoxide, and iron chloride. These crosslinking catalysts may be used in 1 kind, or 2 or more kinds may be used in combination.
The content of the crosslinking catalyst is not particularly limited, and is, for example, preferably about 0.0001 to 1 part by weight, and more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the (meth) acrylic polymer. When the content is within the above range, the crosslinking reaction speed after the formation of the adhesive layer is high, and the service life of the adhesive composition is prolonged, which is preferable.
The pressure-sensitive adhesive composition may contain other known additives, and may contain, for example, powders such as lubricants, colorants and pigments, plasticizers, tackifiers, low-molecular weight polymers, surface lubricants, leveling agents, antioxidants, anticorrosive agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, antistatic agents, inorganic or organic fillers, metal powders, particulates, and foils as appropriate depending on the application.
< optical surface protective film with separator >
The optical surface-protecting film with a separator (surface-protecting film) of the present invention is obtained by forming the pressure-sensitive adhesive layer on at least one side of a base film, and in this case, crosslinking of the pressure-sensitive adhesive composition is generally performed after application of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer formed from the crosslinked pressure-sensitive adhesive composition may be transferred to the base film or the like.
The method for forming the pressure-sensitive adhesive layer on the base film is not limited, and for example, the pressure-sensitive adhesive layer is formed on the base film by applying the pressure-sensitive adhesive composition (solution) to the base film, drying the base film to remove the polymerization solvent, and the like. Then, the curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like. In the case of preparing a surface-protecting film by applying the pressure-sensitive adhesive composition to a base film, one or more solvents other than the polymerization solvent may be newly added to the pressure-sensitive adhesive composition so as to be uniformly applied to the base film.
In addition, as a method for forming the pressure-sensitive adhesive layer in the production of the surface protection film of the present invention, a known method used for the production of pressure-sensitive adhesive tapes can be used. Specifically, examples thereof include: a roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, an air knife coating method, an extrusion coating method by a die coater or the like, and the like.
The surface protection film of the present invention is generally produced such that the thickness of the adhesive layer is about 3 to 100 μm, preferably about 5 to 50 μm. If the thickness of the pressure-sensitive adhesive layer is within the above range, a proper balance between removability and adhesiveness can be easily obtained, and therefore, the pressure-sensitive adhesive layer is preferable.
In addition, the total thickness of the surface protection film of the present invention is preferably 8 to 300 μm, more preferably 10 to 200 μm, and most preferably 20 to 100 μm. When the content is within the above range, the adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties are excellent, and this is a preferable embodiment. The total thickness is the sum of the thicknesses of all layers including the base film, the adhesive layer, the separator, and other layers.
< separator >
The surface protection film of the present invention is characterized by having a pressure-sensitive adhesive layer on at least one surface of a base film, a separator on the surface opposite to the surface of the pressure-sensitive adhesive layer in contact with the base film, the separator having a release layer and a base, and the separator having a haze of 90% or more and a total light transmittance of 50% or less. In the separator in which the separator is bonded to the surface of the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer, it is preferable that the optical surface protective film with the separator is accurately positioned on the optical member by giving the separator optical characteristics such as a specific haze and a specific total light transmittance, and that the optical surface protective film with the separator peeled off is bonded (laminated) to the surface of the optical member after the positioning.
The separator has a haze of 90% or more and a total light transmittance of 50% or less (0 to 50%), preferably a haze of 92% or more and a total light transmittance of 5 to 50%, more preferably a haze of 94% or more and a total light transmittance of 8 to 48%, further preferably a haze of 96% or more and a total light transmittance of 10 to 45%. The separator preferably has a haze of 90% or more and a total light transmittance of 50% or less, so that the optical surface protective film with the separator is excellent in positional adjustment with respect to the surface of the optical member, and after the positional adjustment, the separator can be peeled off to be bonded to the surface of the optical member at an accurate position. In particular, the total light transmittance is 50% or less (0 to 50%), preferably 48% or less, more preferably 45% or less, further preferably 40% or less, and particularly preferably 30% or less. By making the total light transmittance low, the position of the optical surface protection film with a separator relative to the surface of the optical member can be easily adjusted, and the position adjustment property and workability are excellent, which is preferable.
< substrate >
As the substrate, paper and plastic film are suitably used. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include: a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, and the like, and particularly, a polyethylene terephthalate (PET) film, a polyethylene naphthalate film, a polybutylene terephthalate film, and the like, which are polyester films, are preferably used.
As a method for producing the separator, a method for producing the separator with a haze of 90% or more and a total light transmittance of 50% or less may be used without particular limitation, and the separator may be produced by, for example, providing a cavity in a substrate constituting the separator, adding a coloring material, roughening the surface of the substrate, or the like. Specifically, the method described in Japanese patent application laid-open No. 9-12759 can be mentioned.
The thickness of the substrate is usually 5 to 200 μm, preferably about 10 to 100 μm. When the amount is within the above range, the workability of bonding to the adhesive layer, the releasability of the separator from the adhesive layer, and the workability are excellent, and therefore, the range is preferable.
The surface of the substrate may be subjected to various surface treatments such as corona discharge treatment and various surface treatments such as embossing, as required. Further, various additives such as fillers (inorganic fillers, organic fillers, and the like), antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, and the like), and the like may be blended as necessary.
Examples of commercially available products of the substrate include: DIAFOIL W100, DIAFOIL W400 (Miror #50-EA3S (Toyoli corporation), CQ952(KOLON corporation), and the like.
< Release layer >
The release layer has adhesiveness to the base material and releasability from the pressure-sensitive adhesive layer, and may be formed from a release agent composition. The release agent composition is not particularly limited, and for example, an organic silicon compound such as dimethylsiloxane or diphenylsiloxane, a long-chain alkyl compound such as a silicone RESIN, a fluororesin or an ASHIO RESIN, or the like can be used.
The release agent composition may contain other known additives, and for example, powders such as antistatic agents, colorants, pigments, surfactants, plasticizers, tackifiers, low molecular weight polymers, surface lubricants, leveling agents, antioxidants, anticorrosive agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, and particulates may be added as appropriate depending on the application.
< preparation of separator >
The separator is formed on the substrate by using the mold release composition.
The method of forming the release layer on the base material is not limited, and for example, the release layer is formed on the base material by applying a solution of the release agent composition to the base material, drying to remove the polymerization solvent, or the like. Then, the mold release layer may be cured for adjustment of the composition transfer of the mold release layer. In the case of preparing a release layer by applying a release agent composition to a substrate, one or more solvents other than the polymerization solvent may be newly added to the release agent composition so as to be uniformly applied to the substrate.
As the method for forming the release layer, a known method used for producing the release layer can be used. Specifically, examples thereof include: a roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, an air knife coating method, an extrusion coating method by a die coater or the like, and the like.
The thickness of the release layer is typically 1 to 200nm, preferably 5 to 100nm, and more preferably 10 to 50 nm. If the thickness of the release layer is too small, the separator becomes difficult to be peeled, and therefore, the work of bonding the optical surface protection film may become difficult. On the other hand, if the thickness is too large, the staining property of the adhesive layer of the optical surface protective film may be affected.
Examples of commercially available products of the separator include: crisper K7211 to 50 μm, Crisper K7211 to 38 μm (manufactured by Toyo Kagaku Co., Ltd.), PET50(K2411) PAT 18 LK, PET50(K2411) PAT 19K (manufactured by Lindera Kagaku Co., Ltd.), and the like.
< bonding of optical surface protection film to separator (production of optical surface protection film with separator) >
The optical surface-protecting film with a separator of the present invention is in a form in which a pressure-sensitive adhesive layer of the optical surface-protecting film and a release layer of the separator are bonded to each other. The bonding is performed by a known method, and for example, a method of bonding an optical surface protection film to a separator by using a laminator (MRK-600, manufactured by MCK Co., Ltd.) is exemplified.
< optical Member >
In the present invention, the optical member may be protected by attaching the optical surface protection film in which the separator is peeled from the surface of the pressure-sensitive adhesive layer of the optical surface protection film with a separator to the optical member. The separator is excellent in cushioning properties and therefore is less likely to cause indentation, and the optical surface protection film is excellent in appearance quality (appearance), and therefore can be used for surface protection applications (surface protection films) in processing, transportation, shipment, and the like, and is therefore useful for protecting the surface of the optical member (polarizing plate and the like).
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the embodiments shown in these examples. In the following description, "part" and "%" are based on weight unless otherwise specified. Further, the compounding amounts (addition amounts) in the table are given.
The properties described below were measured or evaluated as follows.
< measurement of haze >
The haze (haze value) was measured by using a haze meter (HM-150, manufactured by village color technology research) according to the method specified in JIS K7136 "method for determining haze value of plastic-transparent material".
< measurement of Total light transmittance >
The total light transmittance was measured by using a haze meter (HM-150, manufactured by murakamura color technology research) according to the method specified in JIS K7361 "test method for total light transmittance of plastic-transparent materials".
< measurement of glass transition temperature (Tg) of (meth) acrylic Polymer >
The glass transition temperature (Tg) (° c) was determined from the following formula using the following literature values as the glass transition temperature Tgn (° c) of a homopolymer formed from each monomer.
Formula (II): 1/(Tg +273) ═ Σ [ Wn/(Tgn +273) ]
(wherein Tg (. degree.C.) represents the glass transition temperature of the copolymer, Wn (-) represents the weight fraction of each monomer, Tgn (. degree.C.) represents the glass transition temperature of a homopolymer formed from each monomer, and n represents the type of each monomer.)
Literature values:
2-ethylhexyl acrylate (2 EHA): -70 deg.C
Butyl Acrylate (BA): -55 deg.C
2-hydroxyethyl acrylate (HEA): -15 deg.C
Acrylic Acid (AA): 106 deg.C
As a literature value, reference is made to "synthesis and design of acrylic resins and development of new uses" ("アクリル colophony synthesis and/or assembly 3533 と new uses open/child issue", which was issued by a central business development center (central issue センター).
< measurement of weight average molecular weight (Mw) of (meth) acrylic Polymer >
The weight average molecular weight (Mw) of the (meth) acrylic polymer used was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh corporation. The measurement conditions were as follows.
Sample concentration: 0.2 wt% (THF solution)
Sample injection amount: 10 μ l
Eluent: THF (tetrahydrofuran)
Flow rate: 0.6ml/min
Measuring temperature: 40 deg.C
A chromatographic column:
a sample chromatographic column; TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)
A reference chromatography column; TSKgel SuperH-RC (1 root)
A detector: differential Refractometer (RI)
The weight average molecular weight is determined as a polystyrene equivalent. In addition, when the number average molecular weight (Mn) is measured, the measurement is also performed in the same manner as the weight average molecular weight (Mw).
< automatic bonding Enable >
The surface protective film was cut into 100mm × 110mm without cutting the separator of the optical surface protective film with a separator. Then, holes having a diameter of 5mm were formed in the separator so as to be in contact with 4 corners of the cut surface protective film, respectively.
A suction plate (hereinafter referred to as a suction plate 1) on one side of a precision single chip bonder (SE 650naa, manufactured by clip products) was provided with holes opened by the above method so that the separator side faces upwardA glass sheet having a thickness of 100mm × 110mm is provided on the other suction plate (hereinafter referred to as suction plate 2) of the optical surface protection film with a separator. The adsorption plate 1 is rotated to overlap the adsorption plate 2, and the position of the adsorption plate 2 is adjusted by a CCD camera attached to a precision single-chip laminator so that the hole of the optical surface protection film with a spacer does not overlap the glass. After the position adjustment (see FIG. 2), the suction plate 1 was once lifted from the suction plate 2, the separator was peeled off, and the suction plate 1 was moved onto the suction plate 2 again with a roller pressure of 8kgf/cm2The optical surface-protecting film was bonded to the glass surface at a roll speed of 5 mm/sec.
The automatic bonding (evaluation) was performed by marking a case where the optical surface protection film could be automatically and accurately positioned and bonded as o and a case where the optical surface protection film could not be automatically and accurately positioned and bonded as x.
< preparation of (meth) acrylic Polymer (A) >
100 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 2-hydroxyethyl acrylate (HEA), 0.2 part by weight of 2, 2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator, and 205 parts by weight of ethyl acetate were charged into a four-necked flask equipped with a stirrer blade, a thermometer, a nitrogen gas inlet tube, and a polymerization reaction was carried out for about 4 hours while keeping the liquid temperature in the flask at about 63 ℃ with slow stirring to obtain a (meth) acrylic polymer (A) solution (about 35% by weight). The weight average molecular weight (Mw) of the (meth) acrylic polymer (A) was 65 ten thousand, and the glass transition temperature (Tg) was-68 ℃.
< preparation of (meth) acrylic Polymer (B) >
Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 95 parts by weight of Butyl Acrylate (BA), 5 parts by weight of Acrylic Acid (AA), 0.1 part by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator and 234 parts by weight of ethyl acetate were charged, and while stirring slowly, nitrogen gas was introduced to maintain the liquid temperature in the flask at about 65 ℃ for 6 hours to conduct polymerization reaction, thereby obtaining a (meth) acrylic polymer (B) solution (30% by weight). The weight average molecular weight (Mw) of the (meth) acrylic polymer (B) was 110 ten thousand, and the glass transition temperature (Tg) was-47 ℃.
[ preparation of acrylic adhesive (1) solution ]
The (meth) acrylic polymer (A) solution (35 wt%) was diluted with ethyl acetate to 29 wt%, and to 500 parts by weight of the solution (100 parts by weight of solid content), 4 parts by weight (4 parts by weight of solid content) of isocyanurate (CORONATE HX: C/HX, manufactured by Nippon polyurethane Co., Ltd.) of hexamethylene diisocyanate, which is a 3-functional isocyanate compound, and 1.5 parts by weight (0.015 part by weight of solid content) of dibutyltin dilaurate (Sn "in Table 2, 1 wt% ethyl acetate solution) as a crosslinking catalyst were added, and the mixture was stirred and kept at about 25 ℃ for about 1 minute to obtain an acrylic adhesive (1) solution.
[ preparation of acrylic adhesive (2) solution ]
The (meth) acrylic polymer (A) solution (35 wt%) was diluted to 29 wt% with ethyl acetate, to 500 parts by weight of this solution (100 parts by weight of solid content) was added an isocyanate-based crosslinking agent (isocyanurate of hexamethylene diisocyanate (trade name "CORONATE HX": C/HX, manufactured by Nippon polyurethane Co., Ltd.) 5 parts by weight (solid content: 5 parts by weight), dibutyltin dilaurate (1 wt% ethyl acetate solution) as a crosslinking catalyst 3 parts by weight (solid content: 0.03 parts by weight), and an organopolysiloxane-free polyoxyalkylene chain-containing compound (Aquaron HS-10, manufactured by first Industrial pharmaceutical Co., Ltd.) as an additive 0.3 parts by weight (solid content: 0.3 parts by weight) were mixed and stirred to prepare an acrylic pressure-sensitive adhesive (2) solution.
[ preparation of acrylic adhesive (3) solution ]
The (meth) acrylic polymer (B) solution (30 wt%) was diluted with ethyl acetate to 29 wt%, and to 500 parts by weight of the solution (100 parts by weight of solid content) was added 6 parts by weight of an epoxy crosslinking agent (1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, epoxy equivalent: 110, number of functional groups: 4, trade name "TETRAD-C": T/C, manufactured by Mitsubishi gas chemical Co., Ltd.) (6 parts by weight of solid content), followed by mixing and stirring to obtain an acrylic pressure-sensitive adhesive (3) solution.
[ preparation of urethane adhesive (4) solution ]
85 parts by weight of Preminol S3011 (manufactured by Asahi glass company, Mn: 10000) as a polyol belonging to a polyol having 3 hydroxyl groups, 13 parts by weight of SANNIX GP3000 (manufactured by Sanyo chemical Co., Ltd., Mn: 3000) as a polyol having 3 hydroxyl groups, 18 parts by weight of SANNIX GP1000 (manufactured by Sanyo chemical Co., Ltd., Mn: 1000) as a polyol having 3 hydroxyl groups, 18 parts by weight of isocyanurate compound of hexamethylene diisocyanate (CORONHX: HXC/ATE, manufactured by Nippon polyurethane Co., Ltd.) as a crosslinking agent, iron (III) acetylacetonate (tris (acetylacetone) iron, Fe "in Table 3, manufactured by Tokyo chemical Co., Ltd.) as a catalyst, 0.04 part by weight of isopropyl myristate (EXCEL IPM, 30 parts by Kao corporation) as a wettability improver, The urethane adhesive (4) solution was obtained by using 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant and 210 parts by weight of ethyl acetate as a diluting solvent.
[ preparation of Silicone adhesive (5) solution ]
A silicone adhesive (5) solution was obtained by mixing 100 parts by weight of "X-40-3229" (60% by weight of solid content, manufactured by shin-Etsu chemical Co., Ltd.) as a silicone adhesive, 0.5 part by weight of "CAT-PL-50T" (manufactured by shin-Etsu chemical Co., Ltd.) as a platinum catalyst, and 100 parts by weight of toluene as a solvent, based on 100 parts by weight of the solid content.
[ separators I, II and VII ]
As shown in table 5, commercially available substrates with a release layer, in which a release layer was provided on a substrate (PET film), were used as separators.
[ production of separator III ]
100 parts by weight of a silicone release agent (KS-847H, manufactured by shin-Etsu chemical Co., Ltd.) and 3.3 parts by weight of a silicone curing catalyst (CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.) were added, and the mixture was diluted to 0.3 parts by weight with a solvent prepared from toluene (produced by shin-Etsu chemical Co., Ltd.), hexane (produced by Takayashi chemical Co., Ltd., n-hexane) and methyl ethyl ketone (produced by shin-Etsu chemical Co., Ltd., MEK) at a weight ratio of 1:2:1 to obtain a release agent composition. The release agent composition was applied to a PET film (DIAFOIL W100, manufactured by Mitsubishi resin corporation) having a thickness of 50 μm as a substrate, and dried at 130 ℃ for 1 minute to obtain a separator III. The thickness of the release layer after drying was 20 nm.
[ production of separators IV to VI and VIII ]
As shown in table 5, a PET film having the trade name shown in table 5 was used instead of the PET film used for the separator III, and the same method as that for the separator III was used except that the PET film was used.
< example 1>
[ production of antistatic-treated film ]
An antistatic agent solution was prepared by diluting 10 parts by weight of an antistatic agent (manufactured by solvax inc., MICRO-solvent RMd-142, having tin oxide and polyester resin as main components) with a mixed solvent formed of 30 parts by weight of water and 70 parts by weight of methanol.
The obtained antistatic agent solution was coated on a polyethylene terephthalate (PET) film (thickness: 38 μm) as a base film using a Meyer bar, and the solvent was removed by drying at 130 ℃ for 1 minute to form an antistatic layer (thickness: 0.2 μm) to prepare an antistatic-treated film.
[ production of optical surface protective film with separator ]
The acrylic pressure-sensitive adhesive (1) solution was applied to the surface of the antistatic-treated film opposite to the antistatic-treated surface, and the film was heated at 130 ℃ for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 15 μm. Next, a silicone-treated surface of a polyethylene terephthalate film (trade name: Crisper K7211 to 38 μm, haze: 99.3%, total light transmittance: 13.6%, thickness: 50 μm) as a separator having a silicone treatment on one surface thereof was bonded to the surface of the pressure-sensitive adhesive layer to obtain an optical surface-protecting film with a separator.
< examples 2 and 3>
An optical surface-protecting film with a separator was produced in the same manner as in example 1, except that an acrylic pressure-sensitive adhesive (2) solution or an acrylic pressure-sensitive adhesive (3) solution was used instead of the acrylic pressure-sensitive adhesive (1) solution used in example 1, as shown in Table 2.
< examples 4 and 5>
As shown in tables 3 and 4, optical surface protection films with separators, in which the thickness of the pressure-sensitive adhesive layer obtained was adjusted by heating and the like, were obtained in the same manner as in example 1 except that a urethane-based pressure-sensitive adhesive (4) solution or a silicone-based pressure-sensitive adhesive (5) solution was used instead of the acrylic pressure-sensitive adhesive (1) solution used in example 1.
< examples 6 to 10, comparative examples 1 and 2>
As shown in Table 6, an optical surface protective film with a separator was produced in the same manner as in example 1 except that separators II to VIII were used in place of the separator I used in example 1.
The contents of the above compounding, various measurements and evaluations were made on the surface protective films with separators of examples and comparative examples, and the results are shown in tables 1 to 6. The blending amounts in the tables represent effective ingredients.
[ Table 1]
Figure GDA0002267445650000271
[ Table 2]
Figure GDA0002267445650000272
[ Table 3]
Figure GDA0002267445650000281
[ Table 4]
Figure GDA0002267445650000282
[ Table 5]
Figure GDA0002267445650000291
Note) that all the substrates constituting the separators in table 5 were PET films.
[ Table 6]
Figure GDA0002267445650000301
As can be seen from table 6, in all the embodiments, automatic bonding can be performed at an accurate position. In comparative examples 1 and 2, it was confirmed that since the haze and total light transmittance of the separator did not fall within the desired ranges, the optical surface protective film with the separator could not be automatically adjusted in position with respect to the surface of the optical member, and after the separator was peeled off, the optical surface protective film could not be attached to the surface of the optical member at an accurate position.
Industrial applicability
The optical surface protection film with a separator disclosed herein is suitable as a surface protection film for protecting an optical member used as a component of a liquid crystal display panel, a Plasma Display Panel (PDP), an organic Electroluminescence (EL) display, or the like, at the time of manufacturing the optical member, at the time of transportation, or the like. In particular, the film is useful as an optical surface protective film to be applied to optical members such as a polarizing plate (polarizing film), a wavelength plate, a retardation plate, an optical compensation film, a brightness enhancement film, a light diffusion sheet, and a reflection sheet for a liquid crystal display panel.
Description of the reference numerals
1: insulator
2: surface protective film for optical use
3: optical surface protective film with separator
10: optical member
11: base material
12: release layer
21: adhesive layer
22: base film

Claims (3)

1. An optical surface protective film with a separator, comprising: a base film, an adhesive layer provided on at least one surface of the base film, and a separator provided on the surface of the adhesive layer opposite to the surface thereof in contact with the base film,
the separator has a release layer and a substrate,
it is characterized in that the preparation method is characterized in that,
the separator has a haze of 90% or more and a total light transmittance of 50% or less.
2. The separator-equipped optical surface protective film according to claim 1, wherein the base film is a polyester film.
3. The separator-equipped optical surface-protecting film according to claim 1 or 2, wherein the adhesive layer is formed from an adhesive composition containing at least 1 selected from the group consisting of an acrylic adhesive, a urethane adhesive and a silicone adhesive.
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