JP7253391B2 - Laminated film for reinforcement - Google Patents

Description

The present invention relates to a reinforcing laminated film.

In order to impart rigidity and impact resistance to optical members, electronic members, etc., a reinforcing film (reinforcing base material provided with an adhesive layer) is pasted in advance on the exposed surface side of the optical member or electronic member. In some cases, it is also reinforced (Patent Document 1). Such a reinforcing film usually has a pressure-sensitive adhesive layer for lamination, and a separator is usually placed on the surface of the pressure-sensitive adhesive layer until use in order to protect the surface of the pressure-sensitive adhesive layer. is provided.

Furthermore, in order to prevent the surface of the reinforcing film from being damaged during processing, assembly, inspection, transportation, etc., processing, assembly, and inspection are performed with a surface protection film attached to the exposed surface of the reinforcing film in advance. , transportation, etc. Such a surface protection film is peeled off from the reinforcing film when the surface protection is no longer required (Patent Document 2).

Such a reinforcing laminated film having a surface protective film and a separator is normally stacked in the same direction during storage. However, when the reinforcing laminated films stacked in the same direction are picked up one by one, electrostatic attraction occurs between the reinforcing laminated films, causing blocking. There is a problem that it is not possible to smoothly pick up sheets one by one.

Japanese Patent No. 6366199 JP 2016-17109 A

An object of the present invention is to provide a reinforcing laminated film having a surface protective film and a separator, which can be smoothly picked up one by one from a stacked state.

The reinforcing laminated film of the present invention is
A reinforcing laminated film having a separator, an adhesive layer (1), a reinforcing substrate, and a surface protective film in this order,
The separator comprises a release layer (B1), a substrate layer (B2) and an antistatic layer (B3) in this order,
The surface protective film comprises an adhesive layer (C1), a base layer (C2) and an antistatic layer (C3) in this order,
The release layer (B1) and the adhesive layer (1) are directly laminated,
The reinforcing base material and the pressure-sensitive adhesive layer (C1) are directly laminated,
Two reinforcing laminated films, one reinforcing laminated film (A1) on the antistatic layer (B3) side and the other reinforcing laminated film (A2) on the antistatic layer (C3) side The antistatic layer (B3) of the reinforcing laminated film (A1) is laminated so that it overlaps and is picked up at a peeling angle of 150 degrees and a peeling speed of 10 m / min at a temperature of 23 ° C. and a humidity of 50% RH. The charged voltage on the side surface is 10 kV or less.

In one embodiment, the antistatic layer (B3) has a surface resistance value of 1.0×10 ⁴ Ω to 1.0×10 ⁹ Ω at a temperature of 23° C. and a humidity of 50% RH.

In one embodiment, the antistatic layer (C3) has a surface resistance value of 1.0×10 ⁴ Ω to 1.0×10 ⁹ Ω at a temperature of 23° C. and a humidity of 50% RH.

In one embodiment, the antistatic layer (B3) contains a conductive polymer.

In one embodiment, the antistatic layer (C3) contains a conductive polymer.

In one embodiment, the reinforcing substrate is a plastic film.

In one embodiment, the adhesive layer (1) is composed of at least one selected from the group consisting of acrylic adhesives, urethane adhesives, rubber adhesives, and silicone adhesives.

In one embodiment, the pressure-sensitive adhesive layer (C1) is composed of at least one selected from the group consisting of acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone pressure-sensitive adhesives.

In one embodiment, the acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition has (a component) an alkyl ester moiety having an alkyl group having 4 to 12 carbon atoms. Formed by polymerization from a composition (A) containing a (meth)acrylic acid alkyl ester, (component b) at least one selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid and (component c) at least one selected from the group consisting of polyfunctional isocyanate cross-linking agents and epoxy cross-linking agents.

In one embodiment, the pressure-sensitive adhesive layer (1) exposed by peeling the separator at a temperature of 23° C., a humidity of 50% RH, a peeling angle of 150° C., and a peeling speed of 10 m/min. The initial adhesive force to a glass plate is 1.0 N/25 mm or more at 50% RH, a peeling angle of 180°C, and a peeling speed of 300 mm/min.

According to the present invention, it is possible to provide a reinforcing laminated film having a surface protection film and a separator, which can be smoothly picked up one by one from a stacked state.

1 is a schematic cross-sectional view of one embodiment of a reinforcing laminated film of the present invention; FIG. FIG. 2 is a schematic explanatory diagram of a method of picking up one sheet from two stacked reinforcing laminated films and measuring the charged voltage.

In the present specification, the expression "weight" may be read as "mass" which is commonly used as an SI unit indicating weight.

When the expression "(meth) acrylic" is used in this specification, it means "acrylic and/or methacrylic", and when the expression "(meth) acrylate" is used, "acrylate and/or methacrylate ", and the expression "(meth)allyl" means "allyl and/or methallyl", and the expression "(meth)acrolein" means "acrolein and/or methacrolein". means rain.

≪≪Laminate film for reinforcement≫≫
The reinforcing laminated film of the present invention has a separator, an adhesive layer (1), a reinforcing substrate, and a surface protective film in this order. As long as the reinforcing laminated film of the present invention has a separator, an adhesive layer (1), a reinforcing base material, and a surface protective film in this order, any appropriate other may have a layer of

In the reinforcing laminated film of the present invention, the separator includes a release layer (B1), a base layer (B2) and an antistatic layer (B3) in this order.

In the reinforcing laminated film of the present invention, the surface protective film comprises an adhesive layer (C1), a substrate layer (C2) and an antistatic layer (C3) in this order.

In the reinforcing laminated film of the present invention, the release layer (B1) and the adhesive layer (1) are directly laminated.

In the reinforcing laminated film of the present invention, the reinforcing substrate and the adhesive layer (C1) are directly laminated.

The overall thickness of the reinforcing laminated film of the present invention is preferably 80 μm to 600 μm, more preferably 90 μm to 500 μm, still more preferably 95 μm to 400 μm, from the viewpoint that the effects of the present invention can be more expressed. , particularly preferably 100 μm to 300 μm.

FIG. 1 is a schematic cross-sectional view of one embodiment of the reinforcing laminated film of the present invention. In FIG. 1, the reinforcing laminated film 1000 of the present invention has a separator 100, an adhesive layer (1) 200, a reinforcing substrate 300, and a surface protection film 400 in this order, and the separator 100 is a release layer (B1 ) 110, a substrate layer (B2) 120, and an antistatic layer (B3) 130 in this order, and the surface protection film 400 includes an adhesive layer (C1) 410, a substrate layer (C2) 420, and an antistatic layer ( C3) 430, in that order.

Taking FIG. 1 as an example, in one embodiment of the method of using the reinforcing laminated film 1000 of the present invention, first, the separator 100 is peeled off to expose the pressure-sensitive adhesive layer (1) 200, and an optical member, an electronic member, or the like to reinforce the optical member or the electronic member. The surface protective film 400 is adhered to prevent the surface of the reinforcing base material 300 from being scratched when the product in this state is processed, assembled, inspected, transported, etc., eliminating the need for surface protection. It is separated from the reinforcing base material 300 at the time

In the reinforcing laminated film of the present invention, by appropriately designing the charging characteristics of the separator and the charging characteristics of the surface protective film, the reinforcing laminated films stacked in the same direction are picked up one by one. At this time, the generation of electrostatic attraction between the reinforcing laminated films can be suppressed, the occurrence of blocking can be suppressed, and the sheets can be picked up smoothly one by one.

As the above design, in the reinforcing laminated film of the present invention, preferably, two reinforcing laminated films are provided, one reinforcing laminated film (A1) on the antistatic layer (B3) side and the other reinforcing laminated film (A2) is laminated so that the antistatic layer (C3) side overlaps, and the reinforcing lamination when picking up at a peeling angle of 150 degrees and a peeling speed of 10 m / min at a temperature of 23 ° C. and a humidity of 50% RH The charged voltage of the surface of the film (A1) on the antistatic layer (B3) side is 10 kV or less. Specifically, as shown in FIG. 2, the reinforcing laminated film (A1) and the reinforcing laminated film (A2) are placed in the same direction with the separator side facing up, and the antistatic layer (A1) of the reinforcing laminated film (A1) is Laminate so that the B3) side and the antistatic layer (C3) side of the reinforcing laminated film (A2) overlap, and at a temperature of 23 ° C. and a humidity of 50% RH, a peeling angle of 150 degrees and a peeling speed of 10 m / min for reinforcement. The laminated film (A2) is picked up, and the charged voltage on the surface of the reinforcing laminated film (A1) on the antistatic layer (B3) side is measured. The details of the method for measuring the charged voltage will be described later. Note that FIG. 2 is only a schematic illustration, and when picking up the reinforcing laminated film (A2) from the reinforcing laminated film (A1) at a peeling angle of 150 degrees and a peeling speed of 10 m / min, the reinforcing laminated film The film (A2) is picked up by being peeled from the edge so as to be turned over.

The charged voltage is preferably 9.0 kV or less, more preferably 8.5 kV or less, even more preferably 8.0 kV or less, and particularly preferably 7.0 kV or less, from the viewpoint that the effects of the present invention can be more expressed. .5 kV or less. The lower limit of the charged voltage is preferably 0 kV or higher.

The reinforcing laminated film of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired. For example, a pressure-sensitive adhesive layer (1) is formed on a reinforcing base material, a separator is laminated on the formed pressure-sensitive adhesive layer (1), and on the other hand, the pressure-sensitive adhesive layer (1) on the side of the reinforcing base material opposite to the pressure-sensitive adhesive layer (1) is It can be produced by laminating a surface protection film on the surface.

≪Separator≫
The separator includes a release layer (B1), a substrate layer (B2) and an antistatic layer (B3) in this order. If the separator includes the release layer (B1), the base layer (B2), and the antistatic layer (B3) in this order, it has any appropriate other layers within a range that does not impair the effects of the present invention. may be

The release layer (B1) of the separator is laminated directly on the adhesive layer (1). When using the reinforcing laminated film of the present invention, preferably, the separator is first peeled off to expose the pressure-sensitive adhesive layer (1), and the adhesive layer (1) is then laminated to the exposed surface side of an optical member or an electronic member. or reinforce the electronic component.

The thickness of the separator is preferably 1 μm to 100 μm, more preferably 5 μm to 90 μm, still more preferably 10 μm to 80 μm, and particularly preferably 20 μm to 75 μm, from the viewpoint of making the effects of the present invention more manifest. is.

<Release layer (B1)>
The release layer (B1) is provided to enhance releasability from the pressure-sensitive adhesive layer (1). Any suitable material can be adopted as the material for forming the release layer (B1) as long as the effects of the present invention are not impaired. Examples of such forming materials include silicone-based release agents, fluorine-based release agents, long-chain alkyl-based release agents, fatty acid amide-based release agents, and the like. Among these, silicone release agents are preferred. The release layer (B1) can be formed as a coating layer.

As the thickness of the release layer (B1), any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. Such a thickness is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, still more preferably 10 nm to 1000 nm, and particularly preferably 10 nm to 500 nm.

The release layer (B1) may consist of only one layer, or may consist of two or more layers.

Examples of silicone-based release layers include addition-reactive silicone resins. Specific examples of the addition reaction type silicone resin include, for example, KS-774, KS-775, KS-778, KS-779H, KS-847H, and KS-847T manufactured by Shin-Etsu Chemical; TPR- 6700, TPR-6710, TPR-6721; SD7220, SD7226 manufactured by Dow Corning Toray; The ^coating amount (after drying) of the silicone release layer is preferably 0.01 g/m ² to 2 g/m 2 , more preferably 0.01 g/m ² to 1 g/m ² , still more preferably 0.01 g/m ² to 0.5 g/m ² .

The release layer (B1) is formed, for example, by applying the above-described forming material on any appropriate layer by a conventionally known coating method such as reverse gravure coating, bar coating, and die coating. It can be cured by heat treatment at about 200°C. Moreover, you may combine heat processing and active-energy-ray irradiation, such as ultraviolet irradiation, as needed.

<Base material layer (B2)>
As the substrate layer (B2), a substrate layer formed from any appropriate material can be employed as long as the effects of the present invention are not impaired. Examples of such materials include plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, laminates thereof (especially laminates containing plastic films), and the like.

Examples of plastic films include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyethylene (PE), polypropylene (PP), polymethyl Plastic film composed of olefin-based resins whose monomer components are α-olefins such as pentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA); composed of polyvinyl chloride (PVC) plastic film made of vinyl acetate resin; plastic film made of polycarbonate (PC); plastic film made of polyphenylene sulfide (PPS); polyamide (nylon), wholly aromatic polyamide (aramid ) plastic film composed of amide-based resin such as; plastic film composed of polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); olefin-based resin such as polyethylene (PE) and polypropylene (PP) Plastic films composed of resin; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. a plastic film composed of a fluororesin; and the like.

Examples of nonwoven fabrics include nonwoven fabrics made of heat-resistant natural fibers such as nonwoven fabrics containing manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics and ester resin nonwoven fabrics; and the like.

The base material layer (B2) may consist of only one layer, or may consist of two or more layers.

The thickness of the substrate layer (B2) is preferably from 4 μm to 500 μm, more preferably from 10 μm to 400 μm, even more preferably from 15 μm to 350 μm, and particularly preferably from the viewpoint that the effects of the present invention can be exhibited more effectively. It is preferably 20 μm to 300 μm.

The substrate layer (B2) may be surface-treated. Examples of surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.

The base material layer (B2) may contain any appropriate other additive within a range that does not impair the effects of the present invention.

<Antistatic layer (B3)>
As the thickness of the antistatic layer (B3), any appropriate thickness can be adopted depending on the purpose within a range that does not impair the effects of the present invention. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, even more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.

The antistatic layer (B3) may consist of only one layer, or two or more layers.

As the antistatic layer (B3), any appropriate antistatic layer can be employed as long as it is a layer capable of exhibiting an antistatic effect within a range that does not impair the effects of the present invention. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer. Specifically, for example, it is an antistatic layer formed by coating the substrate layer (B2) with a conductive coating liquid containing a conductive polymer. Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.

As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effects of the present invention are not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of π-conjugated conductive polymers include linear conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, polymethacrylic carboxylic acid, and the like.

The surface resistance value of the antistatic layer (B3) is preferably 1.0×10 ⁴ Ω to 1.0×10 ⁹ Ω, more preferably 1.0×10 Ω at a temperature of 23° C. and a humidity of 50% RH. ⁴ Ω to 5.0×10 ⁸ Ω, more preferably 5.0×10 ⁴ Ω to 1.0×10 ⁸ Ω, particularly preferably 1.0×10 ⁵ Ω to 5.0×10 ⁷ Ω. If the surface resistance value of the antistatic layer (B3) is within the above range, the effects of the present invention can be exhibited more effectively.

<<Adhesive layer (1)>>
Any appropriate pressure-sensitive adhesive layer can be adopted as the pressure-sensitive adhesive layer (1) as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive layer (1) may consist of only one layer, or may consist of two or more layers.

The thickness of the pressure-sensitive adhesive layer (1) is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, still more preferably 3 μm to 80 μm, in order to further express the effects of the present invention. Especially preferred is 5 μm to 50 μm, most preferred is 10 μm to 30 μm.

When using the reinforcing laminated film of the present invention, the pressure-sensitive adhesive layer (1) is preferably applied by peeling off the separator to expose the pressure-sensitive adhesive layer (1) and attaching it to the exposed surface side of an optical member or an electronic member. Together, the optical member and the electronic member are reinforced. That is, it is not assumed that the pressure-sensitive adhesive layer (1) is attached to the exposed surface side of an optical member, an electronic member, or the like, and then peeled off like a surface protective film. For this reason, the pressure-sensitive adhesive layer (1) is preferably designed to have a certain level or more of pressure-sensitive adhesive strength. Specifically, the adhesive layer (1) exposed by peeling off the separator at a temperature of 23° C., a humidity of 50% RH, a peeling angle of 150° C., and a peeling speed of 10 m/min was exposed at a temperature of 23° C., a humidity of 50% RH, The initial adhesive force to a glass plate at a peel angle of 180° C. and a peel speed of 300 mm/min is preferably 1.0 N/25 mm or more, more preferably 2.0 N/25 mm or more, and still more preferably 3.0 N/ It is 25 mm or more, particularly preferably 4.0 N/25 mm or more, and most preferably 4.5 N/25 mm or more. Realistically, the upper limit of the initial adhesive strength is preferably 5.0 N/25 mm or less.

The pressure-sensitive adhesive layer (1) preferably comprises at least one selected from the group consisting of acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone pressure-sensitive adhesives.

The adhesive layer (1) can be formed by any appropriate method. As such a method, for example, at least one selected from the group consisting of an adhesive composition (acrylic adhesive composition, urethane adhesive composition, rubber adhesive composition, silicone adhesive composition ) is applied onto any suitable substrate, heated and dried as necessary, and cured as necessary to form a pressure-sensitive adhesive layer on the substrate. Examples of such coating methods include gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, roll brush coater, and the like. method.

<Acrylic adhesive>
An acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.

The acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a cross-linking agent so that the effects of the present invention can be exhibited more effectively.

Acrylic polymers can be referred to as so-called base polymers in the field of acrylic pressure-sensitive adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.

The content of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 50% to 100% by weight, more preferably 60% to 100% by weight, and still more preferably 70% by weight in terms of solid content. % to 100% by weight, particularly preferably 80% to 100% by weight, most preferably 90% to 100% by weight.

As the acrylic polymer, any appropriate acrylic polymer can be adopted as long as the effects of the present invention are not impaired.

The weight-average molecular weight of the acrylic polymer is preferably from 100,000 to 3,000,000, more preferably from 150,000 to 2,000,000, from the viewpoint that the effects of the present invention can be exhibited more, More preferably 200,000 to 1,500,000, and particularly preferably 250,000 to 1,000,000.

The acrylic polymer is preferably (component a) an alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (b Component) An acrylic polymer formed by polymerization from a composition (A) containing at least one member selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid. (Component a) and (Component b) may each independently be one kind or two or more kinds.

Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. s-butyl acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate etc. Among these, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and acrylic are more preferred, in that the effects of the present invention can be more expressed. acid 2-ethylhexyl.

At least one (component b) selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid includes, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid esters having an OH group such as hydroxybutyl (meth)acrylate, and (meth)acrylic acid. Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred, from the viewpoint that the effects of the present invention can be exhibited more.

Composition (A) may contain copolymerizable monomers other than components (a) and (b). The number of copolymerizable monomers may be one, or two or more. Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). ) and other carboxyl group-containing monomers (excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide and other amide group-containing monomers; aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, t-butyl (meth)acrylate amino group-containing monomers such as aminoethyl; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, Heterocycle-containing vinyl-based monomers such as (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine and vinyloxazole; sulfonic acids such as sodium vinylsulfonate Group-containing monomers; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (Meth)acrylic acid esters having alicyclic hydrocarbon groups such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; aromatics such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and benzyl (meth)acrylate (Meth)acrylic acid esters having a hydrocarbon group; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as alkyl ether; vinyl chloride; and the like.

Polyfunctional monomers may also be employed as copolymerizable monomers. A polyfunctional monomer refers to a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired. Such ethylenically unsaturated groups include, for example, radically polymerizable functional groups such as vinyl groups, propenyl groups, isopropenyl groups, vinyl ether groups (vinyloxy groups), and allyl ether groups (allyloxy groups). Examples of polyfunctional monomers include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and neopentyl glycol. Di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (Meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Only one such polyfunctional monomer may be used, or two or more thereof may be used.

(Meth)acrylic acid alkoxyalkyl esters may also be employed as copolymerizable monomers. Examples of (meth)acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-(meth)acrylate. methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate and the like. The (meth)acrylic acid alkoxyalkyl ester may be used alone or in combination of two or more.

The content of the (meth)acrylic acid alkyl ester (ingredient a) in which the alkyl group of the alkyl ester portion has 4 to 12 carbon atoms is the monomer constituting the acrylic polymer in that the effect of the present invention can be expressed more. It is preferably 50% by weight or more, more preferably 60% to 100% by weight, still more preferably 70% to 100% by weight, and particularly preferably 80% by weight based on the total amount of components (100% by weight). % to 100% by weight.

The content of at least one (component b) selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid is such that the effects of the present invention can be more expressed, and the acrylic polymer is It is preferably 0.1% by weight or more, more preferably 1.0% to 50% by weight, still more preferably 1.5% to 40% by weight, based on the total amount (100% by weight) of the constituent monomer components. % by weight, particularly preferably 2.0% to 30% by weight.

Composition (A) may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, polymerization initiators, chain transfer agents, solvents and the like. Any appropriate content can be adopted as the content of these other components as long as the effects of the present invention are not impaired.

A thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be used as the polymerization initiator depending on the type of polymerization reaction. Only one polymerization initiator may be used, or two or more polymerization initiators may be used.

A thermal polymerization initiator can preferably be employed when the acrylic polymer is obtained by solution polymerization. Examples of such thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox polymerization initiators, and the like. . Among these thermal polymerization initiators, the azo initiators disclosed in JP-A-2002-69411 are particularly preferred. Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a portion that causes the generation of heat-generated gas (outgas). As the azo polymerization initiator, 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN) ), 2,2′-azobis(2-methylpropionate)dimethyl, 4,4′-azobis-4-cyanovaleric acid, and the like. The amount of the azo polymerization initiator used is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. 0.15 to 3.0 parts by weight, most preferably 0.1 to 3.0 parts by weight, more preferably 0.1 to 3.0 parts by weight. 20 parts by weight to 2.0 parts by weight.

A photopolymerization initiator can be preferably employed when obtaining an acrylic polymer by active energy ray polymerization. Examples of photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators. benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.

Examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. and methyl ether. Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). and dichloroacetophenone. Examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. . Examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. Benzoin-based photopolymerization initiators include, for example, benzoin. Examples of benzyl-based photopolymerization initiators include benzyl. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone, and the like. Examples of ketal-based photopolymerization initiators include benzyl dimethyl ketal. Thioxanthone-based photopolymerization initiators include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

The amount of the photopolymerization initiator used is preferably 0.01 to 3.0 parts by weight, more preferably 0.015 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. parts to 2.0 parts by weight, more preferably 0.02 parts to 1.5 parts by weight, particularly preferably 0.025 parts to 1.0 parts by weight, most preferably 0.03 parts by weight. parts by weight to 0.50 parts by weight.

The acrylic pressure-sensitive adhesive composition may contain a cross-linking agent. By using a cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effects of the present invention can be exhibited more. The number of cross-linking agents may be one, or two or more.

Examples of cross-linking agents include polyfunctional isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide cross-linking agents, metal chelate-based cross-linking agents, and metal salts. cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, and the like. Among these, at least one (component c) selected from the group consisting of polyfunctional isocyanate-based cross-linking agents and epoxy-based cross-linking agents is preferable in that the effects of the present invention can be exhibited more effectively.

Polyfunctional isocyanate-based cross-linking agents include, for example, lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and aromatic polyisocyanates. Polyfunctional isocyanate-based cross-linking agents include, for example, trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd. company, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, trade name "Takenate 110N"), etc. A commercial item is also mentioned.

Examples of epoxy-based cross-linking agents (polyfunctional epoxy compounds) include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylamino methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipate diglycidyl ester, o-phthalate diglycidyl ester, triglycidyl-tris(2- hydroxyethyl)isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule, and the like. Examples of epoxy-based cross-linking agents include commercially available products such as the trade name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Company, Inc.).

Any appropriate content can be adopted as the content of the cross-linking agent in the acrylic pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. Such a content is, for example, preferably 0.1 parts by weight to 5.0 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer in terms of more expressing the effects of the present invention. , more preferably 0.2 parts by weight to 4.5 parts by weight, still more preferably 0.3 parts by weight to 4.0 parts by weight, particularly preferably 0.4 parts by weight to 3.5 parts by weight Department.

The acrylic pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, polymer components other than acrylic polymers, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Antiaging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, Surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

<Urethane adhesive>
A urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition.

The urethane-based pressure-sensitive adhesive composition preferably contains at least one selected from the group consisting of urethane prepolymers and polyols, and a cross-linking agent, in order that the effects of the present invention can be exhibited more effectively.

At least one selected from the group consisting of urethane prepolymers and polyols can be called a so-called base polymer in the field of urethane pressure-sensitive adhesives. Only one type of urethane prepolymer may be used, or two or more types may be used. Only one kind of polyol may be used, or two or more kinds thereof may be used.

[Urethane prepolymer]
The urethane prepolymer is preferably a polyurethane polyol, more preferably polyester polyol (a1) or polyether polyol (a2), each alone or in a mixture of (a1) and (a2) in the presence of a catalyst. It is obtained by reacting with an organic polyisocyanate compound (a3) under or without a catalyst.

Any appropriate polyester polyol can be used as the polyester polyol (a1). Examples of such polyester polyols (a1) include polyester polyols obtained by reacting an acid component and a glycol component. Examples of acid components include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, Examples include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Polyester polyols (a1) also include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone) and polyvalerolactone.

As the molecular weight of the polyester polyol (a1), it is possible to use from low molecular weight to high molecular weight. As for the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably 100 to 100,000 from the viewpoint that the effects of the present invention can be exhibited more effectively. If the number average molecular weight is less than 100, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 100,000, the reactivity may become low, and furthermore, the cohesive strength of the polyurethane polyol itself may become small. The amount of the polyester polyol (a1) to be used is preferably 0 mol % to 90 mol % of the polyols constituting the polyurethane polyol, from the point of view that the effects of the present invention can be exhibited more effectively.

Any appropriate polyether polyol can be used as the polyether polyol (a2). Examples of such polyether polyols (a2) include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and other low-molecular-weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like. Examples include polyether polyols obtained by polymerizing oxirane compounds. Specific examples of such polyether polyols (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As the molecular weight of the polyether polyol (a2), it is possible to use from low molecular weight to high molecular weight. As for the molecular weight of the polyether polyol (a2), the number average molecular weight is preferably 100 to 100,000 from the viewpoint that the effects of the present invention can be exhibited more. If the number average molecular weight is less than 100, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 100,000, the reactivity may become low, and furthermore, the cohesive strength of the polyurethane polyol itself may become small. The amount of the polyether polyol (a2) to be used is preferably 0 mol % to 90 mol % of the polyols constituting the polyurethane polyol, from the point of view that the effects of the present invention can be exhibited more effectively.

Part of the polyether polyol (a2), if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, It can be used in combination with polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 100 to 100,000 and at least 3 or more hydroxyl groups in one molecule. Part or all of the polyol may be used. As the polyether polyol (a2), when a polyether polyol having a number average molecular weight of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used in whole or in part, the effects of the present invention are further exhibited. In addition, the balance between adhesive strength and releasability can be improved. In such a polyether polyol, if the number average molecular weight is less than 100, the reactivity becomes high and there is a possibility that gelation is likely to occur. Moreover, in such a polyether polyol, if the number average molecular weight exceeds 100,000, the reactivity may be lowered, and the cohesive strength of the polyurethane polyol itself may be lowered. The number average molecular weight of such a polyether polyol is more preferably 100 to 10,000 in terms of making the effects of the present invention more manifest.

Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3). Examples of such organic polyisocyanate compounds (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4″-triphenylmethane triisocyanate and the like.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

Examples of araliphatic polyisocyanates include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

Examples of alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 ,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane and the like. be done.

As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a water-reacted biuret compound, a trimer having an isocyanurate ring, and the like can be used in combination.

Any appropriate catalyst can be used as the catalyst that can be used when obtaining the polyurethane polyol. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

Tertiary amine compounds include, for example, triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) and the like.

Examples of organometallic compounds include tin-based compounds and non-tin-based compounds.

Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.

Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate;

When a catalyst is used to obtain a polyurethane polyol, in a system in which two kinds of polyols, a polyester polyol and a polyether polyol, are present, gelation or a reaction solution may occur in a single catalyst system due to the difference in reactivity. The problem of turbidity is likely to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, etc. can be easily controlled, and these problems can be solved. Combinations of such two types of catalysts include, for example, tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably. is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The weight ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation may tend to occur due to the balance of catalytic activity.

When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 0.01 with respect to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3). % to 1.0% by weight.

If a catalyst is used in obtaining the polyurethane polyol, the reaction temperature is preferably below 100°C, more preferably between 85°C and 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become difficult to obtain a polyurethane polyol having a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, the reaction temperature is preferably 100° C. or higher, more preferably 110° C. or higher. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to carry out reaction for 3 hours or more.

Methods for obtaining polyurethane polyol include, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a volumetric flask, and 2) a method of charging a polyester polyol, a polyether polyol, and a catalyst into a flask to produce an organic polyisocyanate. A method of adding the As a method for obtaining a polyurethane polyol, the method 2) is preferable from the viewpoint of controlling the reaction.

Any suitable solvent may be used in obtaining the polyurethane polyol. Examples of such solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene and acetone. Among these solvents, toluene is preferred.

[Polyol]

Polyols preferably include, for example, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols. The polyol is more preferably polyether polyol.

A polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

Polyol components include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 ,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. Examples of acid components include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, acid anhydrides thereof etc.

Examples of polyether polyols include water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.). is used as an initiator, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

Examples of polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

Polycarbonate polyols include, for example, polycarbonate polyols obtained by subjecting the above polyol component and phosgene to a polycondensation reaction; Polycarbonate polyols obtained by subjecting carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate to transesterification condensation; copolymerized polycarbonate polyols obtained by combining two or more of the above polyol components; various polycarbonate polyols and carboxyl groups above. Polycarbonate polyol obtained by esterification reaction with the containing compound; Polycarbonate polyol obtained by etherification reaction of the above various polycarbonate polyols and hydroxyl group-containing compounds; Obtained by transesterifying the above various polycarbonate polyols and ester compounds. Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds; Various polycarbonates above a copolymerized polyether-based polycarbonate polyol obtained by copolymerizing a polyol and an alkylene oxide; and the like.

Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with the above polyol components. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

The number average molecular weight Mn of the polyol is preferably from 300 to 100,000, more preferably from 400 to 75,000, even more preferably from 450 to 50,000, and particularly preferably 500, from the viewpoint that the effects of the present invention can be more expressed. ~30,000.

As the polyol, a polyol (A1) having three OH groups and a number average molecular weight Mn of 300 to 100,000 is preferably contained in order to further develop the effects of the present invention. Only one kind of polyol (A1) may be used, or two or more kinds thereof may be used.

The content of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and still more preferably 50% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 100% by weight.

The number average molecular weight Mn of the polyol (A1) is preferably 1,000 to 100,000, more preferably more than 1,000 and 80,000 or less, still more preferably 1,100 to 70,000, in terms of being able to further express the effects of the present invention. , more preferably 1,200 to 60,000, more preferably 1,300 to 50,000, still more preferably 1,400 to 40,000, still more preferably 1,500 to 35,000, particularly preferably 1,700 to 32,000, most preferably 2000-30000.

The polyol may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 20000 or less. Only one kind of polyol (A2) may be used, or two or more kinds thereof may be used. The number average molecular weight Mn of the polyol (A2) is preferably from 100 to 20,000, more preferably from 150 to 10,000, still more preferably from 200 to 7,500, and particularly Preferably 300-6000, most preferably 300-5000. The polyol (A2) is preferably a polyol having 3 OH groups (triol), a polyol having 4 OH groups (tetraol), or 5 OH groups, in that the effects of the present invention can be further expressed. and polyols (hexaols) having six OH groups.

The total amount of the polyol (tetraol) having 4 OH groups, the polyol (pentaol) having 5 OH groups, and the polyol (hexaol) having 6 OH groups as the polyol (A2) is From the viewpoint that the effect can be expressed more, the content in the polyol is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight. % or less.

The content of the polyol (A2) in the polyol is preferably 95% by weight or less, more preferably 0% by weight to 75% by weight, from the viewpoint that the effects of the present invention can be exhibited more effectively.

As the polyol (A2), the content of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less is preferably 70 wt. %, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less.

[Crosslinking agent]
The urethane pressure-sensitive adhesive composition preferably contains a cross-linking agent so that the effects of the present invention can be exhibited more.

Urethane prepolymers and polyols as base polymers can each be a component of a urethane pressure-sensitive adhesive composition in combination with a cross-linking agent.

As the cross-linking agent to be combined with the urethane prepolymer and the polyol as the base polymer, a polyfunctional isocyanate-based cross-linking agent is preferable in that the effects of the present invention can be further exhibited.

Any appropriate polyfunctional isocyanate-based cross-linking agent that can be used in the urethanization reaction can be employed as the poly-functional isocyanate-based cross-linking agent. Examples of such polyfunctional isocyanate-based cross-linking agents include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; Alicyclic polyisocyanates such as silylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as diisocyanate; Polyfunctional isocyanate-based cross-linking agents include, for example, trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd. company, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, trade name "Takenate 110N"), etc. A commercial item is also mentioned.

[Urethane adhesive composition]
The urethane-based pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, polymer components other than urethane prepolymers and polyols, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.). ), anti-aging agents, inorganic fillers, organic fillers, metal powders, coloring agents (pigments, dyes, etc.), foil products, anti-degradation agents, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

The urethane-based pressure-sensitive adhesive composition preferably contains an anti-degradation agent in that the effects of the present invention can be exhibited more effectively. Only one kind of anti-degradation agent may be used, or two or more kinds thereof may be used.

As the anti-deterioration agent, an antioxidant, an ultraviolet absorber, and a light stabilizer are preferable in that the effects of the present invention can be exhibited more.

Antioxidants include, for example, radical chain inhibitors and peroxide decomposers.

Examples of radical chain inhibitors include phenol antioxidants and amine antioxidants.

Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, polymeric phenolic antioxidants, and the like. Examples of monophenol antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate and the like. Examples of bisphenol antioxidants include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4' -thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane and the like. Examples of polymeric phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane , bis[3,3′-bis-(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3′,5′-di-t-butyl -4′-Hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and the like.

Examples of peroxide decomposers include sulfur-based antioxidants and phosphorus-based antioxidants. Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate. Phosphorus antioxidants include, for example, triphenylphosphite, diphenylisodecylphosphite, and phenyldiisodecylphosphite.

Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. be done.

Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2' -dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl ) methane and the like.

Benzotriazole-based UV absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3'',4'',5'',6'',-tetrahydrophthalimidomethyl )-5′-methylphenyl]benzotriazole, 2,2′methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2- (2'-Hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole and the like.

Examples of salicylic acid-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

Examples of cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

Examples of light stabilizers include hindered amine light stabilizers and ultraviolet stabilizers. Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl -1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like. UV stabilizers include, for example, nickel bis(octylphenyl) sulfide, [2,2′-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert- Butyl-4-hydroxybenzyl-phosphate monoethylate, benzoate-type quenchers, nickel-dibutyldithiocarbamate, and the like.

[Urethane-based polymer formed from urethane-based adhesive composition containing urethane prepolymer and polyfunctional isocyanate-based cross-linking agent]
Only one type of urethane prepolymer may be used, or two or more types may be used. Only one type of polyfunctional isocyanate-based cross-linking agent may be used, or two or more types may be used.

As a method for forming a urethane polymer from a urethane pressure-sensitive adhesive composition containing a urethane prepolymer and a polyfunctional isocyanate cross-linking agent, any method of producing a urethane polymer using a so-called "urethane prepolymer" as a raw material may be used. For example, any appropriate manufacturing method can be adopted.

The number average molecular weight Mn of the urethane prepolymer is preferably from 3,000 to 1,000,000 in order to exhibit the effects of the present invention.

The equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate-based cross-linking agent is preferably 5.0 or less as NCO groups/OH groups, in terms of allowing the effects of the present invention to be exhibited more, More preferably 0.01 to 4.75, still more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, most preferably 0.05 to 4.0 be.

The content of the polyfunctional isocyanate-based cross-linking agent is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the urethane prepolymer, in that the effects of the present invention can be more expressed. parts by weight, more preferably 0.05 to 25 parts by weight, still more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 17.5 parts by weight and most preferably 1 to 15 parts by weight.

[Urethane-based polymer formed from urethane-based adhesive composition containing polyol and polyfunctional isocyanate-based cross-linking agent]
Only one kind of polyol may be used, or two or more kinds thereof may be used. Only one type of polyfunctional isocyanate-based cross-linking agent may be used, or two or more types may be used.

The equivalent ratio of the NCO group to the OH group in the polyol and the polyfunctional isocyanate-based cross-linking agent is preferably 5.0 or less as NCO group/OH group, and more preferably 5.0 or less, from the viewpoint that the effects of the present invention can be further expressed. is 0.1 to 3.0, more preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, most preferably 0.5 to 2.0.

The content of the polyfunctional isocyanate cross-linking agent is preferably 1.0 to 30 parts by weight with respect to 100 parts by weight of the polyol, in that the effects of the present invention can be further expressed. , more preferably 1.5 to 27 parts by weight, still more preferably 2.0 to 25 parts by weight, particularly preferably 2.3 to 23 parts by weight, most preferably is 2.5 to 20 parts by weight.

Specifically, the urethane-based polymer formed from the urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent is preferably a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent. It is formed by curing an object. As a method for forming a urethane-based polymer by curing a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent, the effect of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, etc. Any appropriate method can be adopted as long as it does not impair the

A catalyst is preferably used to cure the urethane pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate cross-linking agent. Examples of such catalysts include organometallic compounds and tertiary amine compounds.

Examples of organometallic compounds include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, and zinc-based compounds. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction speed and pot life of the pressure-sensitive adhesive layer.

Examples of iron-based compounds include iron acetylacetonate, iron 2-ethylhexanoate, ferric Nasem, and the like.

Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.

Titanium compounds include, for example, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride and the like.

Zirconium-based compounds include, for example, zirconium naphthenate and zirconium acetylacetonate.

Examples of lead-based compounds include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.

Examples of cobalt-based compounds include cobalt 2-ethylhexanoate and cobalt benzoate.

Examples of zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate.

Tertiary amine compounds include, for example, triethylamine, triethylenediamine, 1,8-diazabisic-(5,4,0)-undecene-7 and the like.

Only one kind of catalyst may be used, or two or more kinds thereof may be used. Moreover, a catalyst and a cross-linking retarder may be used in combination. The amount of the catalyst is preferably 0.005 parts by weight to 1.00 parts by weight, more preferably 0.01 parts by weight to 100 parts by weight of the polyol, in order to further express the effects of the present invention. It is 0.75 parts by weight, more preferably 0.01 to 0.50 parts by weight, and particularly preferably 0.01 to 0.20 parts by weight.

<Rubber adhesive>
As the rubber-based pressure-sensitive adhesive, any suitable rubber-based pressure-sensitive adhesive such as known rubber-based pressure-sensitive adhesives described in JP-A-2015-074771 can be employed as long as the effects of the present invention are not impaired. . These may be of only one type, or may be of two or more types. The rubber-based pressure-sensitive adhesive may contain any appropriate component within a range that does not impair the effects of the present invention.

<Silicone adhesive>
As the silicone-based pressure-sensitive adhesive, any suitable silicone-based pressure-sensitive adhesive such as known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 can be employed as long as the effects of the present invention are not impaired. . These may be of only one type, or may be of two or more types. The silicone-based pressure-sensitive adhesive may contain any appropriate component within a range that does not impair the effects of the present invention.

≪Reinforcing base material≫
As the reinforcing base material, a reinforcing base material formed of any appropriate material can be adopted as long as the effects of the present invention are not impaired. Examples of such materials include plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, laminates thereof (especially laminates containing plastic films), and the like.

As the reinforcing base material, a plastic film is preferable from the viewpoint that the effects of the present invention can be exhibited more.

Examples of plastic films include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyethylene (PE), polypropylene (PP), polymethyl Plastic film composed of olefin-based resins whose monomer components are α-olefins such as pentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA); composed of polyvinyl chloride (PVC) plastic film made of vinyl acetate resin; plastic film made of polycarbonate (PC); plastic film made of polyphenylene sulfide (PPS); polyamide (nylon), wholly aromatic polyamide (aramid ) plastic film composed of amide-based resin such as; plastic film composed of polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); olefin-based resin such as polyethylene (PE) and polypropylene (PP) Plastic film composed of resin; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. a plastic film composed of a fluororesin; and the like.

As the thickness of the reinforcing base material, any suitable thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. Such a thickness is preferably from 25 μm to 500 μm, more preferably from 25 μm to 400 μm, even more preferably from 25 μm to 300 μm, and particularly preferably from 25 μm to 25 μm, from the viewpoint that the effects of the present invention can be more expressed. 200 μm, most preferably between 25 μm and 150 μm.

The reinforcing base material may consist of only one layer, or may consist of two or more layers.

The reinforcing base material may be surface-treated. Examples of surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, and coating treatment with a primer.

The reinforcing base material may contain any appropriate additive depending on the purpose within a range that does not impair the effects of the present invention.

≪Surface protection film≫
A surface protection film contains an adhesive layer (C1), a base material layer (C2), and an antistatic layer (C3) in this order. If the surface protective film includes the pressure-sensitive adhesive layer (C1), the base layer (C2) and the antistatic layer (C3) in this order, any appropriate other layer may be added as long as the effects of the present invention are not impaired. may have.

The pressure-sensitive adhesive layer (C1) is directly laminated to the reinforcing substrate.

The thickness of the surface protection film is preferably from 5 μm to 500 μm, more preferably from 10 μm to 400 μm, even more preferably from 20 μm to 300 μm, and particularly preferably from 30 μm to 30 μm, from the viewpoint that the effects of the present invention can be more expressed. 200 μm, most preferably between 40 μm and 100 μm.

A surface protection film can be manufactured by arbitrary appropriate methods. As such a manufacturing method, for example,
(1) A solution or hot melt of the material for forming the pressure-sensitive adhesive layer (C1) is applied to the surface of the substrate layer (C2) provided with the antistatic layer (C3) opposite to the antistatic layer (C3). how to,
(2) The pressure-sensitive adhesive layer (C1) formed by applying a solution or hot melt of the forming material of the pressure-sensitive adhesive layer (C1) on the separator, and the base layer (C2) provided with the antistatic layer (C3) on the surface opposite to the antistatic layer (C3) of
(3) A method of extruding the material for forming the pressure-sensitive adhesive layer (C1) onto the surface opposite to the antistatic layer (C3) of the base layer (C2) provided with the antistatic layer (C3) to form and apply the method;
(4) A method of extruding the substrate layer (C1), the substrate layer (C2) and the antistatic layer (C3) in multiple layers,
(5) A method of laminating the pressure-sensitive adhesive layer (C1) as a single layer on the surface of the substrate layer (C2) provided with the antistatic layer (C3) opposite to the antistatic layer (C3), or laminating the pressure-sensitive adhesive together with the laminate layer A method for two-layer lamination of layer (C1),
(6) A method of two-layer or multi-layer lamination of an adhesive layer (C1), a material for forming a base layer (C2) such as a film or a laminate layer, and an antistatic layer (C3),
It can be performed according to any appropriate manufacturing method such as.

Examples of coating methods that can be used include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method.

<Adhesive layer (C1)>
Any appropriate pressure-sensitive adhesive layer can be adopted for the pressure-sensitive adhesive layer (C1) as long as the effects of the present invention are not impaired. The pressure-sensitive adhesive layer (C1) may consist of only one layer, or may consist of two or more layers.

The thickness of the pressure-sensitive adhesive layer (C1) is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, still more preferably 3 μm to 80 μm, from the viewpoint that the effects of the present invention can be further expressed, Especially preferred is 5 μm to 50 μm, most preferred is 10 μm to 30 μm.

The adhesive layer (C1) is preferably composed of at least one selected from the group consisting of acrylic adhesives, urethane adhesives, rubber adhesives, and silicone adhesives.

The pressure-sensitive adhesive layer (C1) can be formed by any appropriate method. As such a method, for example, at least one selected from the group consisting of an adhesive composition (acrylic adhesive composition, urethane adhesive composition, rubber adhesive composition, silicone adhesive composition ) is applied onto any suitable substrate, heated and dried as necessary, and cured as necessary to form a pressure-sensitive adhesive layer on the substrate. Examples of such coating methods include gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, roll brush coater, and the like. method.

A detailed description of each of the acrylic pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, and silicone-based pressure-sensitive adhesive can be found in the acrylic pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, and rubber pressure-sensitive adhesive in the description of the pressure-sensitive adhesive layer (1) above. The detailed descriptions of each of the silicone-based pressure-sensitive adhesive and the silicone-based pressure-sensitive adhesive can be used as they are.

<Base material layer (C2)>
The base material layer (C2) may consist of only one layer, or may consist of two or more layers. The base layer (C2) may be drawn.

The thickness of the substrate layer (C2) is preferably from 4 μm to 450 μm, more preferably from 8 μm to 350 μm, still more preferably from 12 μm to 250 μm, and particularly preferably from the viewpoint that the effects of the present invention can be further expressed. is between 16 μm and 150 μm, most preferably between 20 μm and 100 μm.

As the substrate layer (C2), a substrate layer formed from any appropriate material can be employed as long as the effects of the present invention are not impaired. Examples of such materials include plastic films, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, laminates thereof (especially laminates containing plastic films), and the like.

The substrate layer (C2) is preferably a plastic film in that the effects of the present invention can be exhibited more.

Examples of plastic films include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyethylene (PE), polypropylene (PP), polymethyl Plastic film composed of olefin-based resins whose monomer components are α-olefins such as pentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA); composed of polyvinyl chloride (PVC) plastic film made of vinyl acetate resin; plastic film made of polycarbonate (PC); plastic film made of polyphenylene sulfide (PPS); polyamide (nylon), wholly aromatic polyamide (aramid ) plastic film composed of amide-based resin such as; plastic film composed of polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); olefin-based resin such as polyethylene (PE) and polypropylene (PP) Plastic film composed of resin; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. a plastic film composed of a fluororesin; and the like.

The base material layer (C2) may contain any suitable additive depending on the purpose within a range that does not impair the effects of the present invention.

<Antistatic layer (C3)>
As the thickness of the antistatic layer (C3), any suitable thickness can be adopted depending on the purpose within a range that does not impair the effects of the present invention. Such a thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, even more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.

The antistatic layer (C3) may consist of only one layer, or two or more layers.

As the antistatic layer (C3), any appropriate antistatic layer can be employed as long as it is a layer capable of exhibiting an antistatic effect within a range that does not impair the effects of the present invention. Such an antistatic layer is preferably an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the substrate layer (C2). Specific coating methods include a roll coating method, a bar coating method, a gravure coating method, and the like.

As the conductive polymer, any appropriate conductive polymer can be adopted as long as the effects of the present invention are not impaired. Examples of such a conductive polymer include a conductive polymer obtained by doping a π-conjugated conductive polymer with a polyanion. Examples of π-conjugated conductive polymers include linear conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyethyl acrylate sulfonic acid, polymethacrylic carboxylic acid, and the like.

The surface resistance value of the antistatic layer (C3) is preferably 1.0×10 ⁴ Ω to 1.0×10 ⁹ Ω, more preferably 1.0×10 Ω at a temperature of 23° C. and a humidity of 50% RH. ⁴ Ω to 5.0×10 ⁸ Ω, more preferably 5.0×10 ⁴ Ω to 1.0×10 ⁸ Ω, particularly preferably 1.0×10 ⁵ Ω to 5.0×10 ⁷ Ω. If the surface resistance value of the antistatic layer (C3) is within the above range, the effects of the present invention can be exhibited more effectively.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods used in Examples and the like are as follows. "Parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

<Measurement of weight average molecular weight>
A weight average molecular weight was measured by a gel permeation chromatography (GPC) method. Specifically, as a GPC measuring device, using a product name "HLC-8120GPC" (manufactured by Tosoh Corporation), measurement was performed under the following conditions, and the values were calculated in terms of standard polystyrene.
(Molecular weight measurement conditions)
・ Sample concentration: 0.2% by weight (tetrahydrofuran solution)
・Sample injection volume: 10 μL
・ Column: Product name “TSKguardcolumn SuperHZ-H (1 piece) + TSKgel SuperHZM-H (2 pieces)” (manufactured by Tosoh Corporation)
・ Reference column: Product name “TSKgel SuperH-RC (1 piece)” (manufactured by Tosoh Corporation)
- Eluent: tetrahydrofuran (THF)
・Flow rate: 0.6mL/min
・Detector: Differential refractometer (RI)
・Column temperature (measurement temperature): 40°C

<Measurement of surface resistance>
The surface resistance value of the object to be measured was measured with MODEL152-1 (152P-2P probe) manufactured by TREK. The measurement was performed at a voltage of 10 V, a time of 10 seconds, a temperature of 23° C., and a humidity of 50% RH.

<Measurement of electrified voltage at pick-up>
Two reinforcing laminated films (a reinforcing laminated film (A1) and a reinforcing laminated film (A2)) were prepared by cutting the reinforcing laminated film to a width of 70 mm and a length of 130 mm. As shown in FIG. 2, the reinforcing laminated film (A1) and the reinforcing laminated film (A2) are placed in the same direction so that the separator side faces upward, and the antistatic layer (B3) side of the reinforcing laminated film (A1) and the reinforcing laminated film (A1) are reinforced. Laminated so that the antistatic layer (C3) side of the laminated film (A2) for reinforcement overlaps, at a temperature of 23 ° C. and a humidity of 50% RH, at a peeling angle of 150 degrees and a peeling speed of 10 m / min. was picked up, and the charged voltage on the surface of the antistatic layer (B3) side of the reinforcing laminated film (A1) at this time was fixed at a position 30 mm away with an electrostatic potential measuring instrument (STATIRON DZ4, Shishido Electrostatic Co., Ltd.). Measured at The measurement was performed at a temperature of 23° C. and a humidity of 50% RH.

<Measurement of initial adhesive strength of adhesive layer (1) to glass plate>
The reinforcing laminated film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation.
In an environment of 23° C. and 50% RH, the adhesive layer surface of the evaluation sample was attached to a glass plate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Microslide Glass S) by one reciprocation of a 2.0 kg roller. . After curing for 30 minutes in an environment of 23 ° C. × 50% RH, using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), peel at a peel angle of 180 degrees and a tensile speed of 300 mm / min. Adhesion was measured.

<Evaluation of pick-up property>
In the reinforcing laminated film having the surface protective film and the separator, it was evaluated whether or not the reinforcing laminated films stacked in the same direction could be smoothly picked up one by one.
◯: When picking up reinforcing laminated films stacked in the same direction one by one, they could be picked up smoothly one by one.
x: When the reinforcing laminated films stacked in the same direction were picked up one by one, blocking occurred and the films could not be picked up smoothly one by one.

[Production Example 1]: Production of acrylic pressure-sensitive adhesive composition (1) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 95 weight Part, acrylic acid (manufactured by Toagosei Co., Ltd.): 5 parts by weight, 2,2'-azobisisobutyronitrile as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight Nitrogen gas is introduced while gently stirring, the liquid temperature in the flask is maintained at around 63° C., and the polymerization reaction is carried out for 10 hours to obtain a solution of an acrylic polymer having a weight average molecular weight of 700,000 (40% by weight). was prepared.
Next, 0.1 part by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a cross-linking agent in terms of solid content is added to 100 parts by weight of the solid content of the resulting acrylic polymer solution. The mixture was diluted with ethyl acetate so that the solid content was 25% by weight, and stirred with a disper to obtain an acrylic pressure-sensitive adhesive composition (1).

[Production Example 2]: Production of acrylic pressure-sensitive adhesive composition (2) 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler: 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts by weight, 2,2'-azobisisobutyronitrile as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, Ethyl acetate: 156 parts by weight was charged, nitrogen gas was introduced while gently stirring, the liquid temperature in the flask was maintained at around 65°C, and a polymerization reaction was carried out for 6 hours to obtain an acrylic polymer solution with a weight average molecular weight of 550,000. (40% by weight) was prepared.
Next, in the solution of the obtained acrylic polymer, 4 parts by weight of the solid content of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a cross-linking agent per 100 parts by weight of the solid content, and Envirizer OL- as a cross-linking catalyst. 1 (manufactured by Tokyo Fine Chemical Co., Ltd.) was added 0.03 parts by weight in terms of solid content, diluted with ethyl acetate so that the total solid content was 25% by weight, stirred with a disper, and the acrylic pressure-sensitive adhesive composition ( 2) was obtained.

[Production Example 3]: Production of urethane-based pressure-sensitive adhesive composition (3) Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyfunctional polyol was added to 100 parts by weight in terms of solid content, and Coronate HX (Japan Polyurethane Industry Co., Ltd.) is 18 parts by weight in terms of solid content, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a crosslinking catalyst is 0.04 parts by weight in terms of solid content, and Irganox 1010 (manufactured by BASF) is used as a deterioration inhibitor. 0.5 part by weight in terms of solid content was added, diluted with ethyl acetate so that the total solid content was 35% by weight, and stirred with a disper to obtain a urethane pressure-sensitive adhesive composition (3).

[Production Example 4]: Production of [antistatic layer X] / [base layer] laminate As a conductive coating agent, S-948 (manufactured by Chukyo Yushi Co., Ltd.): 100 parts by weight, P-795 (manufactured by Chukyo Yushi Co., Ltd.) ): 10 wt. The resulting conductive coating liquid (a) was applied to a polyester resin substrate "Lumirror S10" (thickness: 38 µm, manufactured by Toray Industries, Inc.) with a wire bar so that the thickness after drying was 40 nm, and the drying temperature was 130°C. , and dried under the conditions of a drying time of 3 minutes to produce a laminate of [antistatic layer X]/[base layer].

[Production Example 5]: Production of [antistatic layer Y] / [base layer] laminate As a conductive coating agent, Bondip PA-100 (manufactured by Konishi Co., Ltd.) main agent: 50 parts by weight, curing agent: 50 parts by weight A part thereof was diluted to 5% by weight with an isopropyl alcohol aqueous solution to obtain a conductive coating liquid (b). The resulting conductive coating liquid (b) was applied to a polyester resin substrate "Lumirror S10" (thickness: 38 µm, manufactured by Toray Industries, Inc.) with a wire bar so that the thickness after drying was 500 nm, and the drying temperature was 130°C. , and dried under the conditions of a drying time of 3 minutes to produce a laminate of [antistatic layer Y]/[base layer].

[Production Example 6]: Production of separator (1) Silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 100 parts by weight, catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT PL-50T): 1.0 weight A part thereof was diluted with toluene to 1.0% by weight to obtain a silicone release agent treatment liquid. The resulting silicone mold release agent treatment liquid was applied to the surface of the base layer of the laminate of [antistatic layer X]/[base layer] obtained in Production Example 4 to a thickness of 100 nm after drying with a wire bar. and dried under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and a separator (1 ) was manufactured.

[Production Example 7]: Production of separator (2) Silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 100 parts by weight, catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT PL-50T): 1.0 weight A part thereof was diluted with toluene to 1.0% by weight to obtain a silicone release agent treatment liquid. The resulting silicone release agent treatment liquid was applied to the surface of the base layer of the laminate of [antistatic layer Y]/[base layer] obtained in Production Example 5, and dried with a wire bar to a thickness of 100 nm. and dried under the conditions of a drying temperature of 130 ° C. and a drying time of 3 minutes, and a separator (2 ) was manufactured.

[Production Example 8]: Production of separator (3) Silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 100 parts by weight, catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT PL-50T): 1.0 weight A part thereof was diluted with toluene to 1.0% by weight to obtain a silicone release agent treatment liquid. The resulting silicone release agent treatment liquid was applied to the surface of a polyester resin substrate "Lumirror S10" (thickness: 38 µm, manufactured by Toray Industries, Inc.) with a wire bar so that the thickness after drying was 100 nm. It was cured and dried under the conditions of 130° C. and a drying time of 3 minutes to produce a separator (3) consisting of a laminate of [releasing layer]/[base layer].

[Production Example 9]: Production of surface protective film (A) The acrylic pressure-sensitive adhesive composition (2) obtained in Production Example 2 was combined with [antistatic layer X] / [base layer ] was applied to the surface of the base material layer of the laminate of No. 1 with a fountain roll so that the thickness after drying was 23 μm, and the composition was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was produced on the substrate layer. Next, the release layer side of the separator (3) obtained in Production Example 8 was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protection film (A).

[Production Example 10]: Production of surface protective film (B) The urethane-based pressure-sensitive adhesive composition (3) obtained in Production Example 3 was combined with the [antistatic layer X] obtained in Production Example 4 / [base layer ] was applied to the surface of the substrate layer of the laminate of No. 1 with a fountain roll so that the thickness after drying was 12 μm, and the composition was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was produced on the substrate layer. Next, the release layer side of the separator (3) obtained in Production Example 8 was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (B).

[Production Example 11]: Production of surface protective film (C) The acrylic pressure-sensitive adhesive composition (2) obtained in Production Example 2 was combined with [antistatic layer Y] obtained in Production Example 5 / [base layer ] was applied to the surface of the base material layer of the laminate of No. 1 with a fountain roll so that the thickness after drying was 23 μm, and the composition was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was produced on the substrate layer. Next, the release layer side of the separator (3) obtained in Production Example 8 was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protection film (C).

[Production Example 12]: Production of surface protective film (D) The urethane-based pressure-sensitive adhesive composition (3) obtained in Production Example 3 was combined with [antistatic layer Y] obtained in Production Example 5 / [base layer ] was applied to the surface of the substrate layer of the laminate of No. 1 with a fountain roll so that the thickness after drying was 12 μm, and the composition was cured and dried under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was produced on the substrate layer. Then, the release layer side of the separator (3) obtained in Production Example 8 was attached to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (D).

[Example 1]
The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 1 was applied to "Lumirror S10" (manufactured by Toray Industries, Inc.) having a thickness of 75 μm as a reinforcing base material made of polyester resin, and dried with a fountain roll to a thickness of 25 μm. and dried by curing under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was formed on the reinforcing substrate.
Next, the release layer side of the separator (1) obtained in Production Example 6 is attached to the surface of the adhesive layer, [reinforcing base material] / [adhesive layer] / [release layer] / [base] A laminate of material layer]/[antistatic layer X] was obtained.
Next, on the surface of the reinforcing base material of the obtained laminate, the separator (3) is peeled off from the surface protective film (A) obtained in Production Example 9 to expose the adhesive layer, and the adhesive layer side pasted together.
As described above, [antistatic layer X] / [base material layer] / [adhesive layer] / [reinforcing base material] / [adhesive layer] / [release layer] / [base layer] / A reinforcing laminate film (1) having the structure of [antistatic layer X] was obtained.
Table 1 shows the results.

[Examples 2 and 3]
The same procedure as in Example 1 was repeated except that the thickness of the pressure-sensitive adhesive layer formed by applying the acrylic pressure-sensitive adhesive composition (1) on the reinforcing substrate was changed as shown in Table 1. Films (2) to (3) were obtained.
Table 1 shows the results.

[Examples 4 to 6]
Except that the thickness of "Lumirror S10" (manufactured by Toray Industries, Inc.) as a reinforcing base material was changed as shown in Table 1, the same procedures as in Examples 1 to 3 were performed, and reinforcing laminated films (4) to ( 6) was obtained.
Table 1 shows the results.

[Example 7]
The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 1 was applied to "Lumirror S10" (manufactured by Toray Industries, Inc.) having a thickness of 75 μm as a reinforcing base material made of polyester resin, and dried with a fountain roll to a thickness of 25 μm. and dried by curing under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, an adhesive layer was formed on the reinforcing substrate.
Next, the release layer side of the separator (1) obtained in Production Example 6 is attached to the surface of the adhesive layer, [reinforcing base material] / [adhesive layer] / [release layer] / [base] A laminate of material layer]/[antistatic layer X] was obtained.
Next, on the surface of the reinforcing base material of the obtained laminate, the separator (3) is peeled off from the surface protective film (B) obtained in Production Example 10 to expose the adhesive layer, and the adhesive layer side pasted together.
As described above, [antistatic layer X] / [base material layer] / [adhesive layer] / [reinforcing base material] / [adhesive layer] / [release layer] / [base layer] / A reinforcing laminate film (7) having the structure of [antistatic layer X] was obtained.
Table 1 shows the results.

[Example 8]
A reinforcing laminated film (8) was obtained in the same manner as in Example 7, except that the thickness of "Lumirror S10" (manufactured by Toray Industries, Inc.) as a reinforcing substrate was changed as shown in Table 1.
Table 1 shows the results.

[Comparative Example 1]
In the same manner as in Example 1 except that the separator (3) obtained in Production Example 8 was used instead of the separator (1) obtained in Production Example 6, [antistatic layer X] / [base material layer]/[adhesive layer]/[reinforcing base material]/[adhesive layer]/[releasing layer]/[base material layer] to obtain a reinforcing laminated film (C1).
Table 1 shows the results.

[Comparative Example 2]
[Antistatic layer X] /[base material layer]/[adhesive layer]/[reinforcement base material]/[adhesive layer]/[releasing layer]/[base material layer]. rice field.
Table 1 shows the results.

[Comparative Example 3]
In the same manner as in Example 1 except that the separator (2) obtained in Production Example 7 was used instead of the separator (1) obtained in Production Example 6, [antistatic layer X] / [base material layer] / [adhesive layer] / [reinforcing base material] / [adhesive layer] / [releasing layer] / [base layer] / [antistatic layer Y] Reinforcing laminated film (C3 ).
Table 1 shows the results.

[Comparative Example 4]
[Antistatic layer X] /[base material layer]/[adhesive layer]/[reinforcing base material]/[adhesive layer]/[releasing layer]/[base material layer]/[antistatic layer Y] for reinforcement A laminated film (C4) was obtained.
Table 1 shows the results.

[Comparative Example 5]
[Antistatic layer Y] /[base material layer]/[adhesive layer]/[reinforcing base material]/[adhesive layer]/[releasing layer]/[base material layer]/[antistatic layer Y] for reinforcement A laminated film (C5) was obtained.
Table 1 shows the results.

[Comparative Example 6]
[Antistatic layer Y] /[base material layer]/[adhesive layer]/[reinforcing base material]/[adhesive layer]/[releasing layer]/[base material layer]/[antistatic layer Y] for reinforcement A laminated film (C6) was obtained.
Table 1 shows the results.

INDUSTRIAL APPLICABILITY The reinforcing laminated film of the present invention can be smoothly picked up one by one from a stacked state, so that it can be suitably used for manufacturing optical members, electronic members, and the like.

Laminated film for reinforcement 1000
Separator 100
Adhesive layer (1) 200
Reinforcing base material 300
Surface protection film 400
Release layer (B1) 110
Base layer (B2) 120
Antistatic layer (B3) 130
Adhesive layer (C1) 410
Base layer (C2) 420
Antistatic layer (C3) 430

Claims (3)

A reinforcing laminated film having a separator, an adhesive layer (1), a reinforcing substrate, and a surface protective film in this order,
The separator comprises a release layer (B1), a substrate layer (B2) and an antistatic layer (B3) in this order,
The surface protective film comprises an adhesive layer (C1), a base layer (C2) and an antistatic layer (C3) in this order,
The release layer (B1) and the adhesive layer (1) are directly laminated,
The reinforcing base material and the pressure-sensitive adhesive layer (C1) are directly laminated,
The antistatic layer (B3) contains a conductive polymer and has a surface resistance value of 1.0×10 4 Ω ^to 1.0×10 ⁹ Ω at a temperature of 23° C. and a humidity of 50% RH,
The base layer (B2) is a plastic film made of a polyester-based resin,
The material for forming the release layer (B1) is a silicone-based release agent,
The adhesive layer (1) is composed of an acrylic adhesive,
The reinforcing base material is a plastic film made of a polyester-based resin,
The pressure-sensitive adhesive layer (C1) is composed of at least one selected from the group consisting of acrylic pressure-sensitive adhesives and urethane-based pressure-sensitive adhesives,
The substrate layer (C2) is a plastic film composed of a polyester-based resin,
The antistatic layer (C3) contains a conductive polymer and has a surface resistance value of 1.0×10 4 Ω to 1.0×10 9 Ω ^at a ^temperature of 23° C. and a humidity of 50% RH,
Two reinforcing laminated films, one reinforcing laminated film (A1) on the antistatic layer (B3) side and the other reinforcing laminated film (A2) on the antistatic layer (C3) side The antistatic layer (B3) of the reinforcing laminated film (A1) is laminated so that it overlaps and is picked up at a peeling angle of 150 degrees and a peeling speed of 10 m / min at a temperature of 23 ° C. and a humidity of 50% RH. The charged voltage on the surface of the side is 10 kV or less,
Laminated film for reinforcement. The acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition is an alkyl (meth)acrylate in which the alkyl group of the (a component) alkyl ester moiety has 4 to 12 carbon atoms. an acrylic polymer formed by polymerization from a composition (A) containing an ester, (component b) at least one selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid; 2. The reinforcing laminate film according to claim 1 , further comprising (component c) at least one selected from the group consisting of polyfunctional isocyanate-based cross-linking agents and epoxy-based cross-linking agents. The pressure-sensitive adhesive layer (1) exposed by peeling the separator at a temperature of 23° C., a humidity of 50% RH, a peeling angle of 150 degrees, and a peeling speed of 10 m/min was exposed at a temperature of 23° C., a humidity of 50% RH, and a peeling angle of 180. 3. The reinforcing laminated film according to claim 1, which has an initial adhesive strength of 1.0 N/25 mm or more to a glass plate at a peel rate of 300 mm/min.

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