CN107107597B - Spacer-equipped surface protection film for optical use - Google Patents

Spacer-equipped surface protection film for optical use Download PDF

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Publication number
CN107107597B
CN107107597B CN201680005154.7A CN201680005154A CN107107597B CN 107107597 B CN107107597 B CN 107107597B CN 201680005154 A CN201680005154 A CN 201680005154A CN 107107597 B CN107107597 B CN 107107597B
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meth
spacer
protective film
adhesive layer
surface protective
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CN107107597A (en
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三井数马
野中崇弘
林圭治
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from PCT/JP2016/052501 external-priority patent/WO2016121875A1/en
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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
    • C09J7/40—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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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

A spacer-equipped optical surface protection film comprising a polyester film on one surface of an adhesive layer and a spacer on the surface of the adhesive layer opposite to the polyester film, wherein the Si-Kalpha linear intensity of the adhesive layer surface after peeling the spacer under fluorescent X-ray is 2.5kcps or less, and the peeling force of the spacer to the optical surface protection film is 0.5N/50mm or less at a stretching speed of 0.3 m/min. The spacer-equipped surface protective film for optical use can prevent a phenomenon that another layer such as an interlayer filler (layer) provided on the surface of an adherend is easily peeled off after the surface protective film is peeled off from the adherend.

Description

Spacer-equipped surface protection film for optical use
Technical Field
The present invention relates to an optical surface protective film with a spacer.
The spacer-equipped surface protective film for optical use of the present invention is useful as a surface protective film for optical use for the purpose of protecting the surface of an optical member used for liquid crystal displays and the like, such as glass, polarizing plates, wave plates, retardation plates, optical compensation films, reflection sheets, brightness enhancement films, and transparent conductive films.
Background
Conventionally, in optical components, electronic components, and the like, a surface protective film is generally bonded to an exposed surface of the component in order to prevent damage to the surface during processing, assembly, inspection, transportation, and the like. The surface protective film is composed of a base film and an adhesive layer, and a spacer (also referred to as a release film or a release liner) is bonded to the adhesive surface for the purpose of protecting the adhesive layer before bonding (use) as necessary (patent document 1). The spacer-attached surface protection film is bonded to an optical member as an adherend after peeling off the spacer.
After the bonded surface protective film is peeled from the optical member at a stage not necessary, a layer having another function (another layer) may be provided on the surface of the peeled optical member (patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-224811
Patent document 2: japanese laid-open patent publication 2014-208756
Disclosure of Invention
Problems to be solved by the invention
However, depending on the state of the surface of the optical member (adherend) after the surface protective film is peeled off, there are the following problems: the other layer is peeled off from the optical member due to deterioration in wettability and adhesiveness to the other layer, and the product is poor. In particular, when a spacer-equipped surface protection film is used, the following problems arise: another layer (e.g., interlayer filler (layer)) provided on an adherend (e.g., a glass surface constituting an optical member) after the optical surface protective film is peeled off is easily peeled off. Therefore, there is a demand for development of a spacer-equipped surface protective film for optical use that can ensure a state in which another layer is not easily peeled off when another layer such as an interlayer filler (layer) is provided on an adherend such as a glass surface after peeling off the surface protective film.
The purpose of the present invention is to provide a surface protective film with a spacer for optical use, which can protect an optical member as an adherend from being soiled or damaged, and can prevent a phenomenon in which another layer such as an interlayer filler (layer) provided on the surface of the adherend is easily peeled off after the surface protective film is peeled off from the adherend.
The present inventors have conducted intensive studies in view of the above circumstances, and have studied that in a surface protective film for optical use with a spacer, when a pressure-sensitive adhesive layer after peeling the spacer is peeled off after being bonded to an adherend such as glass, a pressure-sensitive adhesive layer component remains on the adherend, the surface of the adherend is contaminated, and the releasability of another layer such as an interlayer filler (layer) provided on the adherend later may be affected. Therefore, it has been found that the use of an optical surface protective film with a spacer having specific parameters can reduce the effect of contamination on the surface of an adherend after peeling the optical surface protective film, compared with the conventional one, and therefore can provide an optical surface protective film with a spacer that can prevent peeling of other layers such as an interlayer filler (layer).
Means for solving the problems
That is, the present invention relates to a spacer-equipped optical surface protection film comprising a polyester film on one surface of a pressure-sensitive adhesive layer and a spacer on the surface of the pressure-sensitive adhesive layer opposite to the polyester film, wherein the Si-K α linear intensity of the pressure-sensitive adhesive layer surface after peeling the spacer under fluorescent X-ray is 2.5kcps or less, and the peeling force of the spacer to the optical surface protection film is 0.5N/50mm or less at a stretching speed of 0.3 m/min.
In the spacer-equipped optical surface protective film of the present invention, it is preferable that: the spacer has a release layer and a base, and the release layer is formed from a release agent composition containing a long-chain alkyl material and/or an aliphatic carboxylic acid ester.
In the spacer-equipped optical surface protective film of the present invention, it is preferable that: the adhesive layer is formed from an adhesive composition containing a (meth) acrylic polymer (A) and an aliphatic polyisocyanate-based crosslinking agent (B), wherein the (meth) acrylic polymer (A) contains at least a (meth) acrylic monomer containing an alkyl group having 2 to 14 carbon atoms and a (meth) acrylic monomer containing a hydroxyl group as monomer components, has a glass transition temperature of-50 ℃ or lower, and contains 2 to 20 parts by weight of the (meth) acrylic monomer containing a hydroxyl group per 100 parts by weight of the (meth) acrylic monomer containing an alkyl group having 2 to 14 carbon atoms.
In the spacer-equipped optical surface protective film of the present invention, it is preferable that: the aliphatic polyisocyanate crosslinking agent (B) is contained in an amount of1 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A).
In the spacer-equipped optical surface protective film of the present invention, it is preferable that: the adhesive composition further contains a catalyst (C) containing iron or tin as an active center.
In the spacer-equipped optical surface protective film of the present invention, it is preferable that: the catalyst (C) containing iron or tin as an active center is contained in an amount of 0.002 to 0.5 part by weight based on 100 parts by weight of the (meth) acrylic polymer (A).
Effects of the invention
The spacer-equipped surface protective film for optical use according to the present invention is useful because it is excellent in the releasability of the surface protective film for optical use from the spacer, excellent in the releasability of the surface protective film for optical use after the spacer is peeled from the adherend, and less affected by the contamination of the surface of the adherend by the pressure-sensitive adhesive layer when the surface protective film for optical use is peeled, and therefore, it is possible to prevent the peeling of other layers such as an interlayer filler (layer) provided on the adherend after the peeling from the adherend.
Drawings
Fig. 1 is a schematic cross-sectional view showing one configuration example of a spacer-equipped optical surface protective film according to the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
< integral Structure of spacer-equipped surface protective film for optical use >
The optical surface protective film of the present invention is an optical surface protective film that protects the surface of an optical member (for example, an optical member used for a liquid crystal display or the like such as glass, a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film, a transparent conductive film or the like) during processing and transportation, and is generally in the form of what is called an optical adhesive sheet, an optical adhesive tape (label), an optical adhesive film or the like. The pressure-sensitive adhesive layer in the optical surface protective film is typically formed continuously, but is not limited to this form, and may be formed in a regular or random pattern such as dots or stripes. The optical surface protective film may be in the form of a roll or a sheet.
Fig. 1 schematically shows a typical configuration example of the spacer-equipped optical surface protective film according to the present invention. The spacer-equipped optical surface protection film 3 is formed by laminating a spacer 1 and an optical surface protection film 2. The spacer 1 includes a substrate 11 and a release layer 12, the optical surface protective film 2 includes a polyester film 22 and an adhesive layer 21 provided on one surface thereof, and the release layer 12 and the adhesive layer 21 are laminated. The spacer-equipped surface protective film 3 for optical use is used by attaching the pressure-sensitive adhesive layer 21 to an optical member (a surface of an optical member to be protected, for example, a glass used for a liquid crystal display or the like, a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film, a transparent conductive film or the like) as an adherend after peeling the spacer 1, and is peeled from the optical member at a stage not necessary. The spacer-equipped surface protective film 3 for optical use includes: the polyester film 22 had a form of the adhesive layer 2 on both surfaces thereof, and an antistatic layer on the surface of the polyester film 22 opposite to the surface to which the adhesive layer 2 was applied.
< surface protective film for optical use >
The optical surface protective film of the present invention comprises a polyester film and an adhesive layer.
< polyester film >
Examples of the polyester film of the present invention include: a polyester film containing, as a main resin component, a polymer material (polyester resin) having a main skeleton based on an ester bond, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate. The polyester film is excellent in optical characteristics and dimensional stability, but has a property of being easily charged when used as it is.
Various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (such as a pigment and a dye) may be added to the resin material constituting the polyester film as needed. The first surface of the polyester film may be subjected to 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. Such a surface treatment may be, for example, a treatment for improving the adhesion between the polyester film and the pressure-sensitive adhesive layer (the anchoring property of the pressure-sensitive adhesive layer). It is preferable to use a surface treatment in which a polar group such as a hydroxyl group (-OH group) is introduced into the surface of the polyester film. Further, a pressure-sensitive adhesive layer and an antistatic layer may be provided by subjecting the second surface of the polyester film to the same surface treatment as described above.
The optical surface protective film of the present invention can be provided with an antistatic function by providing the antistatic layer on the surface of the polyester film opposite to the surface provided with the adhesive layer. In addition, a polyester film subjected to antistatic treatment in advance may be used. The use of the polyester film is preferable because electrification can be suppressed when the separator is peeled off or when the pressure-sensitive adhesive layer is peeled off from the optical member as an adherend. 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 containing an antistatic agent and a resin component, a conductive polymer, and a conductive resin containing a conductive substance; a method of evaporating or plating a conductive material; and, a method of mixing an antistatic agent or the like; and so on.
The thickness of the polyester film is usually about 5 to 200 μm, preferably about 10 to 100 μm. When the thickness of the polyester film is within the above range, the adhesion workability to an optical member as an adherend and the peeling workability from the optical member are excellent, and therefore, the polyester film is preferable.
< adhesive layer >
The adhesive layer of the present invention is formed from an adhesive composition that is substantially free of silicone material. The "substantially no silicone material" means that the surface of the pressure-sensitive adhesive layer has an Si-Kalpha linear intensity of 2.5kcps or less under fluorescent X-rays. The pressure-sensitive adhesive composition may be used without particular limitation as long as it has pressure-sensitive adhesiveness, and for example, an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a synthetic rubber pressure-sensitive adhesive composition, a natural rubber pressure-sensitive adhesive composition, and the like may be used, and among them, an acrylic pressure-sensitive adhesive composition may be preferably used.
(meth) acrylic polymer (A) >, and a process for producing the same
The acrylic pressure-sensitive adhesive composition contains a (meth) acrylic polymer (A). The (meth) acrylic polymer means an acrylic polymer and/or a methacrylic polymer.
< C2-14 alkyl group-containing (meth) acrylic monomer >
The (meth) acrylic polymer (A) is not particularly limited as long as it is a (meth) acrylic polymer having adhesiveness, and a (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms is preferably used as a main component of the monomer component. The (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms may be used in an amount of1 or 2 or more as a main component. The main component means the highest blending ratio.
Specific examples of the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms include: 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, suitable monomers include: (meth) acrylic monomers containing an alkyl group having 6 to 14 carbon atoms, such as 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. By using the (meth) acrylic monomer having an alkyl group having 6 to 14 carbon atoms, the pressure-sensitive adhesive layer can be easily formed with low adhesion to an adherend and excellent removability.
The (meth) acrylic polymer (a) preferably contains the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms in an amount of 50 to 99 wt%, more preferably 60 to 98 wt%, even more preferably 70 to 97 wt%, and most preferably 80 to 96 wt%, based on the total amount of monomer components constituting the (meth) acrylic polymer (a). When the content is within this range, the adhesive composition has appropriate wettability and the adhesive layer has excellent cohesive force, which is preferable.
< hydroxyl group-containing (meth) acrylic monomer >
The (meth) acrylic polymer (a) preferably contains a hydroxyl group-containing (meth) acrylic monomer as a monomer component. By including the hydroxyl group-containing (meth) acrylic monomer, the hydroxyl group can be easily controlled to crosslink, and further, the balance between the improvement of wettability by flow and the cohesive force and shear force of the pressure-sensitive adhesive layer can be easily controlled. In addition, when an antistatic agent is added to the pressure-sensitive adhesive layer, unlike a carboxyl group, a sulfonate group, or the like which generally functions as a crosslinking site, a hydroxyl group and an ionic compound or the like which is an antistatic agent have a moderate interaction, and thus, the antistatic agent can be suitably used in view of antistatic property.
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 may be used alone or in combination of 2 or more.
When the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms and the hydroxyl group-containing (meth) acrylic monomer are used in the (meth) acrylic polymer (a), the hydroxyl group-containing (meth) acrylic monomer is preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight, and still more preferably 4 to 12 parts by weight, based on 100 parts by weight of the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms. Within this range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force and shear force of the pressure-sensitive adhesive layer can be easily controlled, and this is preferable.
< carboxyl group-containing (meth) acrylic monomer >
The (meth) acrylic polymer (a) preferably contains a carboxyl group-containing (meth) acrylic monomer as a monomer component. By including the carboxyl group-containing (meth) acrylic monomer, the carboxyl group can increase the shear force, and the increase in adhesive strength with time can be prevented, thereby forming an adhesive layer having excellent removability, adhesion strength increase prevention property, and workability. In particular, by increasing the shear force of the pressure-sensitive adhesive layer, curling of the adherend can be suppressed by bonding the pressure-sensitive adhesive layer to the adherend, and occurrence of sliding or misalignment between the pressure-sensitive adhesive layer and the adherend (interface) can be suppressed.
Examples of the carboxyl group-containing (meth) acrylic monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, 2- (meth) acryloyloxyethylphthalate, 2- (meth) acryloyloxyethylsuccinate, 2- (meth) acryloyloxyethylmaleate, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalate and the like. The carboxyl group-containing (meth) acrylic monomer may be used alone or in combination of 2 or more.
When the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms and the (meth) acrylic monomer having a carboxyl group are used in the (meth) acrylic polymer (a), the amount of the (meth) acrylic monomer having a carboxyl group is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.8 part by weight, even more preferably 0.01 to 0.5 part by weight, and most preferably 0.02 to 0.2 part by weight, based on 100 parts by weight of the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms. Within this range, the pressure-sensitive adhesive layer is preferably excellent in removability, adhesion force increase prevention property, and workability, because the pressure-sensitive adhesive layer can be inhibited from increasing in adhesive force with time, and also excellent in cohesive force and shear force.
< other polymerizable monomer >
In the (meth) acrylic polymer (a), other polymerizable monomers may be used as the monomer component without particular limitation as long as the characteristics of the present invention are not impaired. In particular, the other polymerizable monomer can be used to adjust the glass transition temperature and the peelability so that the Tg of the (meth) acrylic polymer (A) is not more than-50 ℃ and not less than-100 ℃ for the reason that the balance of the adhesive properties can be easily obtained.
The other polymerizable monomers mentioned above can be suitably used, for example: components for improving cohesive force and heat resistance, such as a cyano group-containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer; and a component having a functional group which improves the adhesive (bonding) force and functions as a crosslinking base point, 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. These polymerizable monomers may be used alone, or 2 or more kinds may be used in combination.
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.
Examples of the aromatic vinyl monomer include: styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, other substituted styrenes, and the like.
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 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.
The other polymerizable monomer is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total amount of the monomer components constituting the (meth) acrylic polymer (A). When an ionic compound such as an antistatic agent is used, good interaction with the compound and good removability can be appropriately adjusted by using the other polymerizable monomer within the above range.
The weight average molecular weight (Mw) of the (meth) acrylic polymer (a) is 10 to 500 ten thousand, preferably 20 to 400 ten thousand, and more preferably 30 to 300 ten thousand. When the weight average molecular weight is less than 10 ten thousand, the cohesive force of the adhesive composition is reduced, and the adhesive residue tends to be generated. On the other hand, when the weight average molecular weight (Mw) is more than 500 ten thousand, the fluidity of the polymer decreases, and the adherend (for example, a polarizing plate as an optical member) is insufficiently wetted, and a bulge (フクレ) tends to occur between the adherend and the pressure-sensitive adhesive layer. The weight average molecular weight (Mw) is a weight average molecular weight measured by GPC (gel permeation chromatography).
The glass transition temperature (Tg) of the (meth) acrylic polymer (A) is preferably-50 ℃ or lower, more preferably-55 ℃ or lower, and still more preferably-60 ℃ or lower. The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably-100 ℃ or higher. When the glass transition temperature is higher than-50 ℃, the polymer is not easily flowable, and for example, wetting of an adherend (for example, a polarizing plate or the like as an optical member) becomes insufficient, and a bulge tends to be generated between the adherend and the pressure-sensitive adhesive layer. In particular, by setting the glass transition temperature to-61 ℃ or lower, a pressure-sensitive adhesive composition having excellent wettability and light peelability to an adherend can be easily obtained. The glass transition temperature of the (meth) acrylic polymer (a) can be adjusted to fall within the above range by appropriately changing the monomer components and the composition ratio used.
The polymerization method of the (meth) acrylic polymer (a) is not particularly limited, and polymerization can be carried out by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., and solution polymerization is a more preferable mode from the viewpoint of workability and characteristics such as low staining property to an adherend. The polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
The adhesive composition preferably contains a crosslinking agent. The crosslinking agent may be an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like, and particularly the use of an isocyanate compound is preferable. These compounds may be used alone or in combination of 2 or more.
< aliphatic polyisocyanate-based crosslinking agent (B) >)
Among the isocyanate compounds, the adhesive composition preferably contains an aliphatic polyisocyanate-based crosslinking agent (B). For example, when the (meth) acrylic polymer (a) is contained in the pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer having more excellent heat resistance can be obtained by appropriately adjusting the constituent unit and the constituent ratio of the (meth) acrylic polymer (a), the selection and the addition ratio of the aliphatic polyisocyanate-based crosslinking agent (B), and the like, and crosslinking the resulting composition.
Examples of the aliphatic polyisocyanate-based crosslinking agent (B) include: aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, Hexamethylene Diisocyanate (HDI), and dimer acid diisocyanate; aliphatic isocyanates such as cyclopentane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and the like; modified polyisocyanates obtained by modifying the above isocyanate compounds with allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazinetrione bonds or the like. Examples of commercially available products include: trade names TAKENATE 300S, TAKENATE 500, TAKENATE D165N, TAKENATE D178N (manufactured by Takara Shuzo Co., Ltd.), Sumidle T80, Sumidle L, Desmodur N3400 (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, CORONATE L, CORONATE HL, CORONATE HX (manufactured by Nippon polyurethane industries Co., Ltd.), and the like. The aliphatic polyisocyanate-based crosslinking agent (B) may be used alone, or 2 or more kinds may be mixed and used, or a 2-functional isocyanate compound and a 3-functional isocyanate compound may be used in combination. By using the crosslinking agent in combination, it is possible to achieve both of the adhesion and the resistance to repulsion (resistance to light reflection) (adhesion to a curved surface), and a surface protective film having more excellent adhesion reliability can be obtained.
The content of the aliphatic polyisocyanate-based crosslinking agent (B) is, for example, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 10 parts by weight, and most preferably 3 to 6 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (a). When the content is less than 1 part by mass, crosslinking formation by the crosslinking agent becomes insufficient, and the cohesive force of the obtained pressure-sensitive adhesive layer decreases, so that sufficient heat resistance may not be obtained, and adhesive residue tends to occur. On the other hand, when the content is more than 30 parts by weight, the cohesive force of the polymer is large, the fluidity is lowered, and the wetting with an adherend (for example, optical members such as glass, polarizing plate, wave plate, retardation plate, optical compensation film, reflective sheet, brightness enhancement film, and transparent conductive film used in a liquid crystal display or the like) becomes insufficient, and the swelling tends to occur between the adherend and the pressure-sensitive adhesive layer. In addition, when the amount of the crosslinking agent is large, the peeling electrification characteristics tend to be lowered.
< catalyst (C) >
The pressure-sensitive adhesive composition may further contain a catalyst (C) for promoting the crosslinking reaction more effectively. As the catalyst (C), for example: tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; iron tris (acetylacetonate), iron tris (hexane-2, 4-dione (dionato)), iron tris (heptane-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-dione), iron tris (1-phenylbutane-1, 3-dione), iron tris (hexafluoroacetylacetonate), iron tris (ethylacetoacetate), iron tris (n-propyl acetoacetate), Iron-based catalysts such as 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 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 tris (trimethoxy iron, triethoxy iron, triisopropoxy iron, and iron chloride. The number of the catalyst (C) may be 1 or 2 or more.
The iron-based catalyst may be an iron chelate compound, and may be represented by, for example, the formula Fe (X) (Y) (Z). The iron chelate compound is composed of Fe (X) by a combination of (X) (Y) (Z)3、Fe(X)2(Y)、Fe(X)(Y)2in the iron chelate compound Fe (X) (Y) (Z), each of (X) (Y) (Z) is a ligand for Fe, and when X, Y or Z is a β -diketone, examples of the β -diketone include acetylacetone, hexane-2, 4-dione, heptane-3, 5-dione, 5-methylhexane-2, 4-dione, octane-2, 4-dione, 6-methylheptane-2, 4-dione, 2, 6-dimethylheptane-3, 5-dione, nonane-2, 4-dione, nonane-4, 6-dione, 2, 6, 6-tetramethylheptane-3, 5-dione, tridecane-6, 8-dione, 1-phenylbutane-1, 3-dione, hexafluoroacetylacetone, ascorbic acid, and the like.
When X, Y or Z is a β -ketoester, examples of the β -ketoester include: methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, tert-butyl acetoacetate, methyl propionylacetate, ethyl propionylacetate, n-propyl propionylacetate, isopropyl propionylacetate, n-butyl propionylacetate, sec-butyl propionylacetate, tert-butyl propionylacetate, benzyl acetoacetate, dimethyl malonate, diethyl malonate, etc.
In addition, an iron-based catalyst other than the iron chelate compound, for example, a compound of iron and an alkoxy group, a halogen atom, or an acyloxy group may be used. In the case of a compound of iron and an alkoxy group, the alkoxy group may include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexyl, phenoxy, cyclohexyloxy, benzyloxy, 1-benzylnaphthoxy and the like.
In the case of the compound of iron and a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
In the case of the compound of iron and an acyloxy group, examples of the acyloxy group include: 2-ethylhexanoic acid, octanoic acid, naphthenic acid, resin acids (aliphatic organic acids containing amino acids such as abietic acid, neoabietic acid, d-pimaric acid, iso-d-pimaric acid, podocarpine acid, gluconic acid, fumaric acid, citric acid, aspartic acid, α -ketoglutamic acid, malic acid, succinic acid, glycine, and histidine as a main component, and aromatic fatty acids containing benzoic acid, cinnamic acid, and p-hydroxycinnamic acid as a main component), and the like.
Among the above iron-based catalysts, iron chelate compounds having β -diketone as a ligand are preferable from the viewpoint of reactivity and curability, and tris (acetylacetonato) iron is particularly preferably used.
The content (amount used) of the catalyst (C) is, for example, preferably 0.002 to 0.5 part by mass, more preferably 0.005 to 0.3 part by mass, and still more preferably 0.01 to 0.1 part by mass, based on 100 parts by mass of the (meth) acrylic polymer (A). When the content is within this range, the crosslinking reaction speed is high at the time of forming the adhesive layer, and the pot life (ポットライフ) of the adhesive composition is also increased, which is a preferable embodiment.
Further, the above adhesive composition may contain a compound which causes keto-enol tautomerism as a crosslinking retarder. For example, in an adhesive composition containing the aliphatic polyisocyanate-based crosslinking agent (B) or an adhesive composition which can be used in combination with the aliphatic polyisocyanate-based crosslinking agent (B), a configuration containing the compound which causes keto-enol tautomerism can be preferably employed. This suppresses excessive viscosity increase and gelation of the adhesive composition after the aliphatic polyisocyanate crosslinking agent (B) is added, and the effect of extending the pot life of the adhesive composition can be achieved. This technique is preferably applied to a case where the adhesive composition is in the form of an organic solvent solution or a solvent-free form, for example.
As the above-mentioned compound which causes keto-enol tautomerism, various β -dicarbonyl compounds can be used. Specific examples thereof include: beta-diketones such as acetylacetone, 2, 4-hexanedione, 3, 5-heptanedione, 2-methylhexane-3, 5-dione, 6-methylheptane-2, 4-dione, and 2, 6-dimethylheptane-3, 5-dione; acetoacetic acid esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, and tert-butyl acetoacetate; propionyl acetic acid esters such as propionyl ethyl acetate, propionyl isopropyl acetate, propionyl tert-butyl acetate, and the like; isobutyrylacetic acid esters such as ethyl isobutyrylacetate, isopropyl isobutyrylacetate, and tert-butyl isobutyrylacetate; malonic esters such as methyl malonate and ethyl malonate; and so on. Among these, acetylacetone and acetoacetates are suitable examples. The compound which causes keto-enol tautomerism may be used alone, or 2 or more compounds may be used in combination.
The content of the compound which causes keto-enol tautomerism may be, for example, 0.1 to 20 parts by weight, and is preferably 0.5 to 15 parts by weight (for example, 1 to 10 parts by weight) based on 100 parts by weight of the (meth) acrylic polymer (a). When the amount of the above compound is too small, it may be difficult to exhibit sufficient use effects. On the other hand, if the compound is used in a large amount more than necessary, it remains in the pressure-sensitive adhesive layer and may reduce the cohesive force.
The pressure-sensitive adhesive composition may contain other known additives, and for example, powders such as coloring agents and pigments, surfactants, plasticizers, antistatic agents, 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, particles, and foils may be added as appropriate depending on the intended use.
< production of surface protective film for optical use >
In the case where the optical surface protective film has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on one surface of the polyester film, crosslinking of the pressure-sensitive adhesive composition is generally performed after application of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer containing the crosslinked pressure-sensitive adhesive composition may be transferred to a substrate or the like.
The method for forming the pressure-sensitive adhesive layer on the polyester film is not particularly limited, and the pressure-sensitive adhesive layer can be produced, for example, by: the pressure-sensitive adhesive layer is formed on the film by applying the solution of the pressure-sensitive adhesive composition to the film and drying and removing the polymerization solvent and the like. After that, the curing may be performed for the purpose of adjusting the migration of components in the pressure-sensitive adhesive layer, adjusting the crosslinking reaction, and the like. In addition, when the adhesive composition is applied to a polyester film to prepare an adhesive layer, one or more solvents other than the polymerization solvent may be newly added to the adhesive composition in order to enable uniform application to the film.
In addition, as the method for forming the pressure-sensitive adhesive layer, a known method for producing a pressure-sensitive adhesive layer can be used. Specifically, examples thereof include: roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater or the like, and the like.
The thickness of the adhesive layer is preferably 3 to 100 μm, and more preferably about 5 to 50 μm. When the thickness of the pressure-sensitive adhesive layer is within this range, a proper balance between removability and adhesiveness (adhesiveness) can be easily obtained, which is preferable.
< spacer >
In the optical surface protective film of the present invention, a spacer is bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive layer. The spacer includes a base material and a release layer.
< substrate >
The substrate includes paper and a plastic film, and a plastic film is preferably used because of its excellent surface smoothness. The film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
The thickness of the base material is usually about 5 to 200 μm, preferably about 10 to 100 μm. Within this range, the workability of bonding to the pressure-sensitive adhesive layer and the workability of peeling from the pressure-sensitive adhesive layer 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, if necessary. Further, various additives such as fillers (inorganic fillers, organic fillers, etc.), antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.), and the like may be blended as necessary.
< Release layer >
The release layer is formed from a release agent composition having adhesion to the base material and releasability from the pressure-sensitive adhesive layer, and substantially not containing a silicone material. The above-mentioned "substantially not containing a silicone material" means that a difference [ (b) - (a) ] between the Si — K α linear intensity (a) under fluorescent X-rays of the surface of the release layer of the spacer and the Si — K α linear intensity (b) under fluorescent X-rays of the surface (untreated surface) of the base material having no release layer of the spacer is 0.3kcps or less.
The release agent composition preferably contains a long-chain alkyl material and/or an aliphatic carboxylic acid ester. These compounds are preferable in that the releasability can be effectively obtained even when only a small amount of the release agent composition is blended, and that the coating layer formed from the release layer composition has an appearance free from unevenness, whitening, and the like. These compounds may be used in combination of1 or more than 2.
< long chain alkyl group materials >
The long-chain alkyl material is a compound having a linear or branched alkyl group having 6 or more, preferably 8 or more, and more preferably 12 or more carbon atoms. Examples of the alkyl group include octyl, decyl, lauryl, octadecyl, and docosyl. Examples of the compound having an alkyl group include: various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, long-chain alkyl group-containing quaternary ammonium salts, and the like. In view of heat resistance and contamination, a polymer compound is preferable. Further, from the viewpoint that a suitable water repellency ( water repellency) can be effectively obtained with a small content, a polymer compound having a long-chain alkyl group in the side chain is more preferable.
Examples of the polymer compound having a long-chain alkyl group in a side chain include: a (meth) acrylic polymer obtained by polymerizing a monomer component including a (meth) acrylic monomer having an alkyl group having 6 or more carbon atoms; a polymer obtained by reacting a polymer having a reactive group with a compound having an alkyl group which is reactive with the reactive group, and the like. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Examples of the compound having such a reactive group include: polyvinyl alcohol, butyral resin, ethylene-vinyl alcohol resin, polyethyleneimine, polyvinylamine, polyester resin containing a reactive group, poly (meth) acrylic resin containing a reactive group, and the like. Among these, in view of mold release performance and easy handling, preferred are (meth) acrylic polymers, polyvinyl alcohol, butyral resins, and vinyl alcohol resins.
< C6 or higher alkyl group-containing (meth) acrylic polymer >
The (meth) acrylic polymer obtained by polymerizing a monomer component including a (meth) acrylic monomer having an alkyl group with 6 or more carbon atoms preferably contains the (meth) acrylic monomer having an alkyl group with 6 or more carbon atoms in an amount of 10 to 80 wt%, more preferably 20 to 70 wt%, even more preferably 30 to 70 wt%, and most preferably 30 to 60 wt%, based on the total amount of the monomer components constituting the (meth) acrylic polymer. When the content is within this range, the resulting release layer is excellent in light releasability from the pressure-sensitive adhesive layer.
Other polymerizable monomers than the (meth) acrylic monomer having an alkyl group having 6 or more carbon atoms can be suitably used, for example: hydroxyl group-containing (meth) acrylic monomers, (meth) acrylic monomers containing carboxyl groups, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, and the like. These polymerizable monomers may be used alone, or 2 or more kinds may be used in combination.
Among them, from the viewpoint of excellent light peelability to the pressure-sensitive adhesive layer and excellent adhesion to the base material, a carboxyl group-containing (meth) acrylic monomer and a cyano group-containing monomer are preferably used. Examples of the carboxyl group-containing (meth) acrylic monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, 2- (meth) acryloyloxyethylphthalate, 2- (meth) acryloyloxyethylsuccinate, 2- (meth) acryloyloxyethylmaleate, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalate and the like. Examples thereof include acrylonitrile and methacrylonitrile. Examples of the cyano group-containing monomer include: acrylonitrile, methacrylonitrile.
< Polymer obtained by reacting Polymer having reactive group with Compound having alkyl group reactive with the reactive group >
In addition, examples of the above-mentioned compound having an alkyl group which is reactive with a reactive group include: long chain alkyl group-containing isocyanates such as octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate; acyl chlorides containing long-chain alkyl groups such as octanoyl chloride, decanoyl chloride, lauroyl chloride, octadecanoyl chloride and behenoyl chloride; long chain alkyl group-containing amines, long chain alkyl group-containing alcohols, and the like. Among these, in view of mold release performance and easy handling, long chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanate is particularly preferable.
The reactive group-reactive compound is preferably reacted at 100 to 1000 parts by weight, more preferably 200 to 800 parts by weight, and still more preferably 300 to 700 parts by weight, based on 100 parts by weight of the reactive group-reactive polymer. In this range, it is preferable to obtain a light peelability to the pressure-sensitive adhesive layer and to suppress contamination of the pressure-sensitive adhesive layer of the optical surface protective film.
< aliphatic carboxylic acid ester >
The aliphatic carboxylic acid ester can be obtained by reacting an aliphatic carboxylic acid with an alcohol. The aliphatic carboxylic acid component is preferably a C6-36 mono-or dicarboxylic acid, and more preferably a C6-36 aliphatic saturated monocarboxylic acid. Specific examples of such aliphatic carboxylic acids include: palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid (テトラリアコンタン acid), montanic acid, glutaric acid, adipic acid, azelaic acid, and the like.
On the other hand, examples of the alcohol include saturated or unsaturated monohydric alcohol, saturated or unsaturated polyhydric alcohol, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes alicyclic alcohol. Specific examples of these alcohols include: octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2-dihydroxyperfluoropropanol, neopentyl glycol, ditrimethylolpropane, dipentaerythritol, and the like. These aliphatic carboxylic acid esters may contain aliphatic carboxylic acids and/or alcohols as impurities, or may be a mixture of a plurality of compounds.
Specific examples of the aliphatic carboxylic acid ester include: beeswax (a mixture containing melissa palmitate as a main component), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate.
The carboxylic acid ester is contained in the mold release composition preferably in an amount of 70 to 99% by weight, more preferably 80 to 99% by weight, and still more preferably 90 to 99% by weight. When the content is within this range, the pressure-sensitive adhesive layer is preferably excellent in light peelability.
The release agent composition may contain other known additives, and for example, an antistatic agent, a colorant, powder such as a pigment, a surfactant, a plasticizer, a thickener, a low molecular weight polymer, a surface lubricant, a leveling agent, an antioxidant, an anticorrosive agent, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, a silane coupling agent, an inorganic or organic filler, a metal powder, a particulate form, and the like may be appropriately added depending on the use.
< production of spacer >
The spacer is formed on the base material by using the mold release composition.
The method for forming the release layer on the base material is not particularly limited, and for example, the release layer can be formed on the base material by applying a solution of the above release agent composition to the base material and drying and removing the polymerization solvent or the like. After that, the mold layer may be cured for the purpose of, for example, adjusting the migration of the components of the mold layer. In the case of producing 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.
In addition, a known method used for producing a release layer can be used for the method of forming the release layer. Specifically, examples thereof include: roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using 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 is difficult to peel off, and therefore, the work of bonding the optical surface protective film may become difficult. On the other hand, if the thickness is too large, the staining property of the pressure-sensitive adhesive layer of the optical surface protective film may be affected.
< bonding of surface protective film and spacer for optical use >)
The spacer-equipped optical surface protective film of the present invention is in a form in which the pressure-sensitive adhesive layer of the optical surface protective film and the release layer of the spacer are bonded to each other. The bonding can be performed by a known manufacturing method.
< measurement of Si-Kalpha line intensity under fluorescent X-ray >
In the spacer-attached optical surface protective film of the present invention, the silicon atomic weight of the surface of the pressure-sensitive adhesive layer can be measured from the Si — K α line intensity under fluorescent X-rays of the surface of the pressure-sensitive adhesive layer from which the spacer attached to the optical surface protective film has been peeled. The Si-Kalpha linear intensity of the surface of the adhesive layer under the fluorescent X-ray is less than or equal to 2.5kcps, preferably less than or equal to 2.4, more preferably less than or equal to 2.2, and most preferably less than or equal to 2.0. When the amount of the organic silicone compound is within this range, the optical surface protective film after the separator is peeled off is bonded to an adherend (e.g., a glass plate), and then the adherend is peeled off, whereby the influence of the contamination of the surface of the adherend by the pressure-sensitive adhesive layer can be reduced (e.g., the transfer of an organic silicone compound such as polydimethylsiloxane contained in the release layer of the separator for improving the peelability to the surface of the pressure-sensitive adhesive layer due to the bonding of the separator and the optical surface protective film and the transfer of the transferred organic silicone compound to the adherend can be suppressed). As a result, peeling of other layers such as an interlayer filler (layer) provided on an adherend can be prevented.
< measurement of the difference in peeling force of adhesive tape >
The effect of the above-described contamination on the surface of the adherend can be measured from the difference in the peeling force of the pressure-sensitive adhesive tape. The difference in the peeling force of the adhesive tape can be represented by formula (1): the difference in the release force (N/50mm) of the adhesive tape is F0F (N/50 mm).
Here, F is the following peel force, namely: the optical surface protective film after the separator was peeled off was bonded to a glass plate as an adherend, the glass plate was heated at 70 ℃ for 48 hours, the optical surface protective film was left at room temperature for 1 hour, and then the optical surface protective film was peeled off, and a single-sided pressure-sensitive adhesive tape manufactured by Nidoku K.K. "No. 31B" (19 mm wide) was bonded to the surface of the glass plate to which the optical surface protective film was bonded using a 2kg roll, and the tape was peeled off at a peeling angle of 180 ° and a stretching speed of 0.3 m/min under conditions of 23 ℃ and 50% RH for 20 minutes, and the peeling force (N/19mm) of the tape was converted into a peeling force (N/50mm) obtained as a measurement value under a condition of 50mm wide.
In addition, the，F0Is the following peel force: a single-sided pressure-sensitive adhesive tape of type No.31B manufactured by Nindon electric K.K., was directly bonded to the surface of a glass plate using a 2kg roll without bonding an optical surface protective film to the glass plate, and was peeled at a peeling angle of 180 ℃ and a stretching speed of 0.3 m/min for 20 minutes at 23 ℃ and 50% RH, and the peeling force (N/19mm) of the pressure-sensitive adhesive tape at this time was converted into a peeling force (N/50mm) obtained by measuring the tape width at 50 mm.
The difference in the peeling force of the pressure-sensitive adhesive tape is an index of the adhesiveness to another layer (for example, an interlayer filler (layer)) provided on the optical member after the optical surface protective film is peeled, and thus the degree of the contamination of the surface of the adherend can be evaluated.
The difference in the peeling force between the pressure-sensitive adhesive tapes is preferably 4.0N/50mm or less, more preferably 3.6N/50mm or less, still more preferably 3.2N/mm or less, and most preferably 2.8N/mm or less. When the content is in this range, the pressure-sensitive adhesive layer after the optical protective film is peeled has little effect on the surface of the adherend, and peeling of other layers such as an interlayer filler (layer) provided on the adherend can be prevented.
< measurement of peeling force of spacer against surface protective film for optical use >
The spacer-equipped optical surface protection film of the present invention was bonded to a spacer, left at 23 ℃ and 50% RH for 20 minutes, and then peeled off at a peeling angle of 180 ° and a peeling speed of 0.3 m/min, thereby obtaining the peeling force of the spacer to the optical surface protection film. The peeling force of the spacer to the optical surface protective film is 0.5N/50mm or less, preferably 0.4N/50mm or less, more preferably 0.3N/50mm or less, still more preferably 0.2N/50mm or less, and most preferably 0.1N/50mm or less. Further, it is preferably 0.03N/50mm or more, more preferably 0.05N/50mm or more, and further preferably 0.08N/50mm or more. When the content is within this range, the separator has excellent releasability from the pressure-sensitive adhesive layer and excellent workability in bonding.
< measurement of glass peeling force of surface protective film for optical use >
The spacer-equipped optical surface protection film of the present invention was bonded to the surface of a glass plate with a 2kg roll, and then peeled under the conditions of a peeling angle of 180 ° and a drawing speed of 0.3 m/min after 20 minutes at 23 ℃ and 50% RH, thereby measuring the peeling force of the optical surface protection film from the glass. The optical surface protective film has a peeling force to glass of preferably 0.08N/25mm or less, preferably 0.07N/25mm or less, more preferably 0.06N/25mm or less, still more preferably 0.05N/25mm or less, and most preferably 0.04N/25mm or less. Further, it is preferably 0.01N/25mm or more, more preferably 0.02N/25mm or more, and further preferably 0.03N/25mm or more. When the content is within this range, the pressure-sensitive adhesive layer has excellent releasability from an adherend such as glass.
< determination of elemental ratio of silicon atom by X-ray photoelectron spectroscopy (ESCA) >)
In the spacer-equipped optical surface protective film of the present invention, the element ratio (atomic%) of silicon atoms (Si) on the outermost surface of the pressure-sensitive adhesive layer can be calculated by peeling the spacer bonded to the optical surface protective film and measuring the surface of the pressure-sensitive adhesive layer by X-ray photoelectron spectroscopy. The elemental ratio (atomic%) of silicon atoms (Si) on the outermost surface of the pressure-sensitive adhesive layer is preferably 0.5 or less, more preferably 0.3 or less, and most preferably 0.2 or less. When the amount of the organic silicone compound is within this range, the optical surface protective film after peeling the separator is bonded to an adherend (e.g., a glass plate), and then the adherend is peeled off, whereby the influence of the contamination of the surface of the adherend by the pressure-sensitive adhesive layer can be reduced (e.g., the transfer of an organic silicone compound such as polydimethylsiloxane contained in the release layer of the separator to improve the peelability to the surface of the pressure-sensitive adhesive layer due to the bonding of the separator and the optical surface protective film and the transfer of the organic silicone compound to the adherend can be suppressed). As a result, peeling of other layers such as an interlayer filler (layer) provided on an adherend can be prevented.
The other layers provided on the adherend after peeling off the optical surface protective film of the present invention include, for example: interlayer filler (layer). The interlayer filler (layer) is, for example, a substance for filling a space between the cover glass and the liquid crystal panel to improve the visibility, and specifically includes: SVR7000 series, SVR1120, SVR1150, SVR1320, SVR1241H (product of Dexerials), WORLD ROCK700 series, WORLD ROCK801, A-350 series, WORLDROCK HRJ-40, HRJ-203, HRJ-300, HRJ-302 (product of Co-ordinated chemical industries, Ltd.), and the like.
Hereinafter, examples and the like which specifically show the configuration and effects of the present invention will be described, but the present invention is not limited thereto. The evaluation items in the examples and the like were measured as follows.
< example 1 >
Production of (meth) acrylic Polymer (A1)
Into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a cooler, 100 parts by weight of 2-ethylhexyl acrylate (2EHA, manufactured by east asia synthesis, 2-ethylhexyl acrylate), 4 parts by weight of 2-hydroxyethyl acrylate (HEA, manufactured by east asia synthesis, ACRYCS HEA), 0.2 parts by weight of 2, 2' -azobisisobutyronitrile (wako pure chemical industries, AIBN) as a polymerization initiator, and 205 parts by weight of ethyl acetate (sho and electrician, manufactured by wayokoku corporation, ethyl acetate) were charged, nitrogen gas was introduced while gradually stirring, and a polymerization reaction was carried out for about 4 hours while maintaining the liquid temperature in the flask at about 63 ℃. The weight average molecular weight of the (meth) acrylic polymer (A1) was 65 ten thousand, and the Tg was-68.3 ℃.
< preparation of adhesive composition >
The (meth) acrylic polymer (a1) solution (about 35 wt%) was diluted with ethyl acetate to 29 wt%, 4 parts by weight of isocyanurate of hexamethylene diisocyanate (CORONATE HX, manufactured by japan polyurethane industries), 0.015 part by weight of dioctyltin laurate (manufactured by Tokyo Fine Chemicals, EMBILIZER OL-1) as a tin catalyst, and 0.69 part by weight of acetylacetone as a compound which causes keto-enol tautomerism were added to 100 parts by weight (solid content) of the (meth) acrylic polymer in the solution, and the mixture was stirred and mixed at about 25 ℃ for about 1 minute to prepare an adhesive composition (1).
< production of spacer A >
100 parts by weight of a resin obtained by drying a butyral resin (S-lec KW-10, manufactured by waterlogging Chemical industries) was dissolved in 900 parts by weight of xylene (キシロール, manufactured by Sun Chemical industries), and 480 parts by weight of octadecyl isocyanate (R-NCO, manufactured by Ohara Paragium Chemical Co., Ltd.) was added thereto. The solution was diluted with toluene (manufactured by shin-Etsu chemical Co., Ltd.) so that the solid content became 0.3 wt%, to obtain a mold release composition. The release agent composition was applied to a 38 μm thick PET film (made of Mitsubishi resin, Diafil T100C38) and dried at 130 ℃ for 1 minute to prepare a spacer A. The thickness of the release layer after drying was 20 nm.
< production of spacer-equipped surface protective film for optical use >
The pressure-sensitive adhesive composition (1) was applied to one surface of a PET substrate (made of Mitsubishi resin, Diafil T100C38, thickness 38 μm) and heated at 130 ℃ for 60 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm, thereby producing an optical surface protective film. Next, the release layer of the spacer a was bonded to the surface of the pressure-sensitive adhesive layer by a hand press roll to produce a spacer-attached surface protective film for optical use. In the case of bonding (use) to an adherend, the spacer is removed and used.
< production of spacer B >
100 parts by weight of acrylonitrile (manufactured by Showa Denko K.K., Acrylonitrile), 62.5 parts by weight of stearyl methacrylate (manufactured by Mitsubishi gas chemical Co., Ltd., SMA), 18 parts by weight of methacrylic acid (manufactured by Mitsubishi Yangyo Co., Ltd., methacrylic acid), 1.8 parts by weight of 1-dodecylmercaptan (manufactured by Wako pure chemical Co., Ltd., 1-dodecylmercaptan), and 0.55 part by weight of benzoyl peroxide (manufactured by Nikko Co., Ltd., Nyper BW) were charged into a reaction vessel equipped with a cooler, diluted to 24 parts by weight with toluene (manufactured by Wako pure chemical Co., Ltd.), and reacted at 70 ℃ for 7 hours under a nitrogen gas flow. The obtained liquid was diluted to 0.3 wt% with toluene to obtain a mold release composition, and then a spacer B was produced in the same manner as the spacer a.
< spacer C >
Toyo spun Toyo polyester film TN101 (thickness 38 μm) was used. The release layer constituting the spacer C is formed from a release agent composition containing pentaerythritol fatty acid ester.
< production of spacer D >
200 parts by weight of xylene (キシロール, manufactured by Ohara Paragium Chemical Co., Ltd.) and 600 parts by weight of octadecyl isocyanate (R-NCO) were charged into a reaction vessel equipped with a cooler, and heated while stirring, and 100 parts by weight of polyvinyl alcohol (KURAYAYPOVAL 205, manufactured by KURARARAY Co., Ltd.) was added little by little from the time when the reflux of xylene was started, and the addition was carried out in small amounts every 10 minutes for 2 hours. After the addition of polyvinyl alcohol was completed, the reaction was further refluxed for 2 hours to complete the reaction. After the reaction mixture was cooled to about 80 ℃ and added to methanol, the reaction product precipitated as a white precipitate, and the operation of filtering the precipitate several times, adding 140 parts by weight of xylene, heating to completely dissolve the precipitate, adding methanol to precipitate the precipitate was repeated, the precipitate was washed with methanol, and the dried and pulverized powder was diluted with water to 0.3% by weight. Using the obtained solution, a spacer D was produced in the same manner as the spacer a.
< spacer E >
Filmbyna 50E-0010 NSD (thickness 50 μm), manufactured by Tenssen industries, was used. The release layer constituting the spacer E was formed from a release agent composition containing pentaerythritol fatty acid ester.
< spacer F >
100 parts by weight of a silicone release agent (KS-847H, manufactured by shin-Etsu chemical industries, Ltd.) and 3.3 parts by weight of a silicone curing catalyst (CAT-PL-50T, manufactured by shin-Etsu chemical industries, were added thereto, and the mixture was prepared by mixing toluene (produced by shin-Etsu Petroleum Chemicals, Ltd.), hexane (produced by shin-Etsu Petroleum Chemicals, n-hexane) and methyl ethyl ketone (produced by shin-Etsu chemical, MEK) in the ratio of 1: 2: the solvent was diluted to 0.3% by weight at a weight ratio of1 to obtain a mold release composition. Using the obtained release agent composition, a spacer F was produced in the same manner as the spacer a.
< examples 2 to 8, comparative examples 1 to 3, blank 1 >)
Other than changing the monomer components constituting the (meth) acrylic polymer and the treatment of the spacer as shown in tables 1 and 2, a surface protective film for optical use with a spacer of examples 2 to 8 and comparative examples 1 to 3 was produced in the same manner as in example 1. As blank 1, a surface protective film for optical use was produced without using a spacer. In addition, tris (acetylacetonato) iron (product name "ナーセム -iron-ii" manufactured by japan chemical industries) was used as the iron catalyst.
< measurement & evaluation >
Specific amounts and measurement and evaluation methods are described below, and the results are shown in tables 1 and 2.
[ measurement of weight average molecular weight (Mw) < (meth) acrylic Polymer (A) ]
The weight average molecular weight of the prepared polymer was measured by GPC (gel permeation chromatography). The conditions are shown below.
The device comprises the following steps: HLC-8220 GPC, manufactured by Tosoh corporation
Sample column: TSK guard column Super HZ-H (1 root) manufactured by Tosoh corporation and TSK gel Super HZM-H (2 root)
A reference column; TSK gel Super H-RC (1 root)
Flow rate: 0.6ml/min
Injection amount: 10 μ l
Column temperature: 40 deg.C
Eluent: THF (tetrahydrofuran)
Concentration of injected sample: 0.2% by weight
A detector: differential refractometer
The weight average molecular weight is calculated by polystyrene conversion.
[ measurement of glass transition temperature (Tg) < (meth) acrylic Polymer (A) ]
The glass transition temperature (Tg) (° c) was determined by the following formula using the following literature values based on the glass transition temperature Tgn (° c) of the homopolymer of 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 based on each monomer, and n represents the type of each monomer.)
2-ethylhexyl acrylate (2 EHA): -70 deg.C
Hydroxyethyl acrylate (HEA): -15 deg.C
4-hydroxybutyl acrylate (HBA): -32 deg.C
Acrylic Acid (AA): 106 deg.C
The literature refers to "synthesis and design of acrylic resin and development of new use (the colophony アクリル colophony resin synthesis/marquis (r) \\ 35336g (new use of the invention)' (published by central business development center).
< measurement of Si-Kalpha Linear Strength >
The silicon atomic weight of the surface of the pressure-sensitive adhesive layer was measured under the following conditions from the Si — K α line intensity under fluorescent X-ray of the surface of the pressure-sensitive adhesive layer after the spacer was peeled from the obtained optical surface protective film with a spacer.
The device comprises the following steps: XRF ZSX100e manufactured by Rigaku
An X-ray source: vertical Rh pipe
Analysis area:
Figure BDA0001343264350000261
analyzing elements: si
Spectroscopic crystallization: RX4
Output power: 50kv, 70mA
To the sample
Figure BDA0001343264350000262
The intensity of the fluorescent X-ray of Si dispersed by the spectroscopic crystal (RX 4) was measured by irradiating an excitation X-ray (a line source is a vertical Rh tube, and an output power is 50kv and 70 mA).
In addition, the surface of the adhesive layer of the surface protective film for optical use (blank 1) without using a spacerAs a result, with respect to the above silicon atom amount, silicon atoms of the polyester film and the base material (for example, Silica (SiO) as a filler in the PET film) were detected even when no silicone material was used for the pressure-sensitive adhesive layer and the release layer2) etc.) and thus the Si-K α linear strength was not 0kcps, and was 1.9kcps in the adhesive layer of the optical surface protective film (blank 1) not using a spacer.
The Si-Kalpha linear strength of the surface of the pressure-sensitive adhesive layer after the separator is peeled is preferably 2.5kcps or less. When the amount is in this range, the effect of staining the surface of the glass by the pressure-sensitive adhesive layer after the optical surface protective film after the separator is peeled off from the glass plate is small (for example, it is possible to suppress transfer of an organic silicone compound such as polydimethylsiloxane contained in the release layer of the separator for improving the peelability to the surface of the pressure-sensitive adhesive layer by adhesion of the separator and the optical surface protective film, and transfer of the transferred organic silicone compound to the adherend), and therefore, it is possible to prevent peeling of other layers such as an interlayer filler (layer) from the adherend.
< measurement of the difference in peeling force of adhesive tape >
The spacer was peeled off from the obtained optical surface protective film with spacer, and the resultant was bonded to a glass plate (made OF Sonlang Nitro, a blue plate edge polished product (cyan plate edge polished product) OF1 "), and heated in an oven at 70 ℃ for 48 hours. After being taken out of the oven and left at room temperature for 1 hour, the optical surface protective film was peeled off, and an acrylic pressure-sensitive adhesive tape (No. 31B, width 19mm) was bonded to the surface to which the optical surface protective film was bonded by using a 2kg roll, and left at 23 ℃ for about 20 minutes in an environment with a relative humidity of 50%. The sheet was peeled at an angle of 180 ℃ at a speed of 0.3 m/min, and the peel force was measured and converted into a value measured under a condition of a width of 50mm, which was taken as the value of F in the following formula (1).
No.31B was directly bonded to a glass plate without bonding an optical surface protective film, and the peel strength was measured in the same manner and converted to a value measured under a width of 50mm, as F in the following formula (1)0The value of (c). In this case, the peel force of No.31B is18.7N/50mm。
Then, the difference in the peeling force between these pressure-sensitive adhesive tapes was calculated by the following formula (1).
Formula (1): the difference in the release force (N/50mm) of the adhesive tape is F0－F(N/50mm)
The difference in the release force of the adhesive tape is preferably 4.0N/50mm or less. As the value becomes smaller, the influence of the surface contamination of the glass by the pressure-sensitive adhesive layer after the optical protective film is peeled is small, and peeling of other layers such as an interlayer filler (layer) provided on the glass surface can be prevented.
< measurement of peeling force of spacer against surface protective film for optical use >
The obtained spacer-attached optical surface protective film was cut into a width of 50mm, and the surface (polyester film) opposite to the surface to which the adhesive layer was attached was fixed to a SUS plate (SUS304 BA). After leaving in an environment of 23 ℃ and a relative humidity of 50% for about 20 minutes, the spacer was peeled at an angle of 180 ℃ at a speed of 0.3 m/min, and the peeling force (N/50mm) of the spacer against the surface protective film for optical use was measured.
The peeling force of the spacer to the optical surface protective film is preferably 0.5N/50mm or less. When the content is within this range, the separator has excellent releasability from the pressure-sensitive adhesive layer and excellent workability in bonding.
< evaluation of Release Property of spacer >
For the evaluation of the peeling property of the spacer, the peeling force of the spacer against the optical surface protective film was set to be 0.5N/50mm or less as good (. largecircle.), and more than 0.5N/50mm as bad (. largecircle.).
< measurement of glass peeling force of surface protective film for optical use >
The obtained optical surface protective film with spacer was cut into a width OF 25mm, the spacer was peeled off, and the resultant was bonded to a glass plate (made OF Sonlang Nitro, a blue plate edge polished product (cyan plate edge polished product), OF1) with a 2kg roller and left to stand at 23 ℃ under a relative humidity OF 50% for about 20 minutes. The optical surface protective film was peeled at an angle of 180 ℃ at a speed of 0.3 m/min, and the peeling force (N/25mm) of the optical surface protective film from the glass was measured.
The optical surface protective film preferably has a peeling force to glass of 0.08N/25mm or less. When the content is within this range, the optical protective film has a pressure-sensitive adhesive layer having excellent releasability from an adherend such as glass.
< determination of elemental ratio of silicon atom by X-ray photoelectron spectroscopy (ESCA) >)
From the measurement by X-ray photoelectron spectroscopy of the surface of the pressure-sensitive adhesive layer after the spacer was peeled from the obtained optical surface protective film with a spacer, the elemental ratio of silicon atoms (Si) at the outermost surface of the pressure-sensitive adhesive layer was calculated under the following conditions.
The device comprises the following steps: PHI Quantera SXM manufactured by ULVAC PHI
An X-ray source: monochromatic AlK alpha
XRay Setting：
Figure BDA0001343264350000281
[15kV，25W]
Photoelectron extraction angle: at 45 deg. to the sample surface.
The obtained spacer-attached surface protective film for optical use was appropriately cut out, and subjected to measurement by X-ray photoelectron spectroscopy, and the element ratio (atomic%) was calculated for silicon atoms.
The element ratio is preferably 0.5 atomic% or less with respect to the silicon atom. Within this range, the effect of staining the surface of the glass by the pressure-sensitive adhesive layer after the optical surface protective film after the separator is peeled off from the glass plate is small (for example, it is possible to suppress transfer of an organic silicone compound such as polydimethylsiloxane contained in the release layer of the separator for improving the peelability to the surface of the pressure-sensitive adhesive layer by adhesion of the separator and the optical surface protective film, and transfer of the transferred organic silicone compound to the adherend), and therefore, for example, it is possible to prevent peeling of other layers such as an interlayer filler (layer) from the adherend.
< measurement of the difference between the Si-Kalpha line intensities of the surface of the release layer of the spacer and the surface of the substrate of the spacer under fluorescent X-ray >
Using the above-described conditions for measuring the Si — ka line intensity, the Si — ka line intensity (a) under fluorescent X-rays of the surface of the release layer of the spacer and the Si — ka line intensity (b) under fluorescent X-rays of the surface (untreated surface) of the base material having no release layer of the spacer were measured, and the difference [ (b) - (a) ] was obtained. As a result, the Si — K α linear strength (a) of the spacer C was 3.78kcps, and the Si — K α linear strength (b) of the spacer C was 3.98kcps, so that the difference [ (b) - (a) ] was 0.20 kcps. Further, since the Si — K α linear strength (a) of the spacer E is 6.52kcps and the Si — K α linear strength (b) of the spacer E is 6.73kcps, the difference [ (b) - (a) ] is 0.21 kcps. Further, since the above-mentioned Si — K α linear strength (a) of the spacer F is 75.5kcps and the above-mentioned Si — K α linear strength (b) of the spacer F is 7.36kcps, the difference [ (b) - (a) ] is 68.14 kcps.
[ TABLE 1 ]
Figure BDA0001343264350000301
[ TABLE 2 ]
Figure BDA0001343264350000311
From the results of table 2, it was confirmed that in all the examples, the Si — K α linear strength was 2.5kcps or less, and therefore, the contamination resistance was excellent, and the peeling force of the spacer to the optical surface protective film was 0.5N/50mm or less, and therefore, the workability in the bonding was excellent. On the other hand, in comparative examples 1 and 3, the Si-Ka linear strength was more than 2.5kcps, and in comparative example 2, the peeling force of the spacer from the pressure-sensitive adhesive layer was more than 0.5N/50mm, and it was confirmed that these performances were inferior to those of comparative examples 1 to 3.
From the results of table 2, it was confirmed that in all examples, the difference in the peeling force between the pressure-sensitive adhesive tapes was 4.0N/50mm or less, and therefore the effect of the surface of the glass being stained with the pressure-sensitive adhesive layer when the optical protective film was peeled off was small, and therefore, peeling of other layers such as an interlayer filler (layer) could be prevented, and the peeling force of the surface protective film to the glass was 0.08N/25mm or less, and therefore, the peeling property to the glass was excellent. In addition, the separator has good peelability. In addition, the elemental ratio of silicon atoms (Si) on the outermost surface of the pressure-sensitive adhesive layer was 0.5 atomic% or less, and therefore excellent stain resistance was confirmed. On the other hand, in comparative examples 1 and 3, the difference in the release force between the pressure-sensitive adhesive tapes was larger than 4.0N/50mm, the elemental ratio of silicon atoms on the outermost surface of the pressure-sensitive adhesive layer was 2.0 atomic% or more, and in comparative example 2, the release force of the optical surface protective film to glass was larger than 0.08N/25mm, and the separator release property was poor, and it was confirmed that these performances were poor in comparative examples 1 to 3 as compared with examples.
Description of the symbols
1: spacer member
2: optical surface protective film
3: spacer-equipped surface protection film for optical use
11: base material
12: release layer
21: adhesive layer
22: polyester film

Claims (5)

1. An optical surface protection film with a spacer, which has a polyester film on one surface of a pressure-sensitive adhesive layer and a spacer on the surface of the pressure-sensitive adhesive layer opposite to the polyester film,
the spacer has a release layer and a substrate,
the release layer is formed from a release agent composition containing a long-chain alkyl material and/or an aliphatic carboxylic acid ester,
the surface of the adhesive layer after the separator is peeled has an Si-Kalpha linear intensity of 2.5kcps or less under fluorescent X-ray,
the separator has a peeling force to the optical surface protective film of 0.3N/50mm or less at a stretching speed of 0.3 m/min.
2. The spacer-equipped surface protective film for optical use according to claim 1, wherein the adhesive layer is formed from an adhesive composition comprising a (meth) acrylic polymer (A) and an aliphatic polyisocyanate-based crosslinking agent (B),
the (meth) acrylic polymer (A) is a copolymer of a (meth) acrylic polymer,
comprises at least a (meth) acrylic monomer having an alkyl group of 2 to 14 carbon atoms and a (meth) acrylic monomer having a hydroxyl group as monomer components, and has a glass transition temperature of-50 ℃ or lower,
the hydroxyl group-containing (meth) acrylic monomer is contained in an amount of 2 to 20 parts by weight per 100 parts by weight of the (meth) acrylic monomer having an alkyl group having 2 to 14 carbon atoms.
3. The spacer-equipped optical surface protective film according to claim 2, wherein the aliphatic polyisocyanate-based crosslinking agent (B) is contained in an amount of1 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A).
4. The spacer-equipped optical surface protective film according to claim 2, wherein the adhesive composition further contains a catalyst (C) having iron or tin as an active center.
5. The spacer-equipped optical surface protective film according to claim 4, wherein the catalyst (C) containing iron or tin as an active center is contained in an amount of 0.002 to 0.5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A).
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