CN114729242A

CN114729242A - Reinforcing film

Info

Publication number: CN114729242A
Application number: CN202080081669.1A
Authority: CN
Inventors: 小川圭太; 佐佐木翔悟
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2019-11-26
Filing date: 2020-07-27
Publication date: 2022-07-08
Also published as: WO2021106272A1; KR20220103727A; TW202120643A; JPWO2021106272A1

Abstract

The invention provides a reinforcing film which can be stuck to an optical member or an electronic member, and which suppresses a change in retardation and does not deteriorate detectability when the optical member or the electronic member is detected through the reinforcing film. In addition, there is provided: an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, there is provided: a reinforcing film with a surface-protecting film, which is provided with a surface-protecting film, and a method for using the reinforcing film with a surface-protecting film. Based on thisThe reinforcing film according to the embodiment of the invention is a reinforcing film comprising a base layer A1 and a pressure-sensitive adhesive layer A2, and the reinforcing film has an in-plane retardation (R) at a wavelength of 590nm after being stored at 60 ℃ and 90% RH for 1 week₀) The absolute value of the rate of change of (b) is 20.0% or less.

Description

Reinforcing film

Technical Field

The present invention relates to a reinforcing film.

Background

In order to impart rigidity and impact resistance to optical members, electronic members, and the like represented by organic EL panels, LCD panels, touch panels, and the like, a reinforcing film may be laminated on an exposed surface side of the optical members, the electronic members, and the like and reinforced in advance (patent document 1).

Further, in order to prevent surface scratches during processing, assembly, inspection, conveyance, and the like, a surface protective film may be attached to an exposed surface of the reinforcing film in advance. Such a surface protection film is peeled from the reinforcing film when surface protection is no longer necessary (patent document 2).

Such a reinforcing film may be bonded to an optical member or an electronic member, and the optical member or the electronic member may be detected through the reinforcing film.

However, when the reinforcing film is attached to an optical member or an electronic member and stored under a severe environment for a long period of time, the phase difference of the reinforcing film changes, and the detectability may be deteriorated due to occurrence of rainbow unevenness or the like.

As described above, in the reinforcing film which is attached to the optical member or the electronic member and detects the optical member or the electronic member through the reinforcing film, it is important to suppress a change in retardation of the reinforcing film in order to improve the film, that is, in the case where the film is attached to the optical member or the electronic member and stored in a severe environment for a long period of time.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 6366199

Patent document 2: japanese patent laid-open publication No. 2016-

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a reinforcing film that can be attached to an optical member or an electronic member, and that suppresses a change in retardation and does not reduce detectability when the optical member or the electronic member is detected through the reinforcing film. Further, an object is to provide an optical member with a reinforcing film or an electronic member with a reinforcing film, which is provided with such a reinforcing film. Further, the object is: provided are a reinforcing film with a surface protection film, which is provided with a surface protection film on the reinforcing film, and a method for using the reinforcing film with the surface protection film.

Means for solving the problems

The reinforcing film according to the embodiment of the present invention is as follows:

a reinforcing film comprising a substrate layer A1 and an adhesive layer A2,

an in-plane retardation (R) at a wavelength of 590nm after storing the film for reinforcement at 60 ℃ and 90% RH for 1 week₀) The absolute value of the rate of change of (b) is 20.0% or less.

In one embodiment, the haze change rate of the reinforcing film after 1 week of storage at 60 ℃ and 90% RH is 10.0% or less.

In one embodiment, the reinforcing film has a total light transmittance of 80% or more.

In one embodiment, in the reinforcing film according to an embodiment of the present invention, the adhesive strength to the PET film at a peel angle of 180 degrees and a peel speed of 300 mm/min after the pressure-sensitive adhesive layer a2 is stuck to the PET film and left at 23 ℃ for 30 minutes is 0.30N/25mm or more.

In one embodiment, the reinforcing film according to the embodiment of the present invention is attached to an adherend, which is an optical member or an electronic member.

An optical member with a reinforcing film or an electronic member with a reinforcing film according to an embodiment of the present invention includes the reinforcing film according to an embodiment of the present invention.

The reinforcing film with a surface protective film according to the embodiment of the present invention includes a surface protective film on the substrate layer a1 side of the reinforcing film according to the embodiment of the present invention.

The method of using the reinforcing film with a surface protective film of the present invention is as follows: the pressure-sensitive adhesive layer a2 of the reinforcing film with a surface protective film according to the embodiment of the present invention is adhered to an adherend with the pressure-sensitive adhesive layer a2 exposed, and then the surface protective film is peeled off.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a reinforcing film that can be stuck to an optical member or an electronic member, and that suppresses a change in retardation and does not deteriorate detectability when the optical member or the electronic member is detected through the reinforcing film. In addition, there may be provided: an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Further, a reinforcing film with a surface protection film, which is provided with such a reinforcing film, and a method for using such a reinforcing film with a surface protection film can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view of one embodiment of a reinforcing film in an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view of another embodiment of a reinforcing film in an embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view of one embodiment of a surface protection film.

Fig. 4 is a schematic cross-sectional view of another embodiment of a surface protection film.

FIG. 5 is a schematic cross-sectional view of one embodiment of a reinforcing film with a surface protective film of the present invention.

Detailed Description

The term "mass" as used herein is to be interpreted as "weight" which is conventionally used as a general weight unit, and the term "weight" as used herein is to be interpreted as "mass" which is conventionally used as an SI-based unit representing weight.

In the present specification, the expression "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and the expression "(meth) acrylate" means "acrylate and/or methacrylate", the expression "(meth) allyl", the expression "allyl and/or methallyl", and the expression "(meth) acrolein", the expression "acrolein and/or methacrolein".

[ 1] reinforcing film

The reinforcing film of the present invention comprises a base material layer a1 and an adhesive layer a 2. The reinforcing film of the present invention may have the base layer a1 and the pressure-sensitive adhesive layer a2, and may have any other suitable layer as long as the effects of the present invention are not impaired. Typically, the reinforcing film of the present invention is composed of a base layer a1 and a pressure-sensitive adhesive layer a 2.

For protection, a release sheet described later may be provided on the surface of the pressure-sensitive adhesive layer a 2.

In order to impart various functions, a functional layer A3 described later may be provided on the surface of the base layer a 1.

The thickness of the reinforcing film may be any suitable thickness according to the purpose within a range not impairing the effects of the present invention. The thickness is preferably 5 to 800. mu.m, more preferably 10 to 650. mu.m, still more preferably 20 to 550. mu.m, and particularly preferably 25 to 450 μm.

One embodiment of the reinforcing film is composed of a base layer a1(10) and a pressure-sensitive adhesive layer a2(20), as shown in fig. 1.

The film for reinforcement of the present invention has an in-plane retardation (R) at a wavelength of 590nm after storage for 1 week at 60 ℃ and 90% RH₀) The absolute value of the rate of change of (b) is 20.0% or less, preferablyIs 15.0% or less, more preferably 12.0% or less, still more preferably 10.0% or less, and particularly preferably 9.5% or less. In-plane retardation (R) at a wavelength of 590nm₀) If the absolute value of the change rate of (b) is within the above range, a reinforcing film can be provided which does not deteriorate the detectability when an optical member or an electronic member is detected through the reinforcing film.

The reinforcing film of the present invention has a haze change rate of preferably 10.0% or less, more preferably 7.0% or less, further preferably 6.0% or less, further preferably 5.0% or less, particularly preferably 4.0% or less, and most preferably 3.5% or less after being stored in an environment of 60 ℃ and 90% RH for 1 week. The above haze change ratio can be within the above range: a reinforcing film which is not further deteriorated in detectability when an optical member or an electronic member is detected through the reinforcing film.

The total light transmittance of the reinforcing film of the present invention is preferably 80% or more, more preferably 83% or more, further preferably 85% or more, and particularly preferably 88% or more. The total light transmittance of the reinforcing film is within the above range, and can provide: a reinforcing film which is not further deteriorated in detectability when an optical member or an electronic member is detected through the reinforcing film.

<1-1. base Material layer A1>

As the base layer a1, a base material formed of any suitable material may be used according to the purpose within the range not impairing the effects of the present invention. Examples of such a material include a resin sheet, a nonwoven fabric, paper, a metal foil, a woven fabric, a rubber sheet, a foamed sheet, and a laminate thereof (particularly, a laminate including a resin sheet).

Examples of the resin constituting the resin sheet include acrylic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) and polymethyl methacrylate (PMMA), polycarbonates, triacetyl cellulose (TAC), polysulfones, polyarylates, Polyethylene (PE), polypropylene (PP), ethylene-propylene copolymers, ethylene-vinyl acetate copolymers (EVA), polyamides (nylon), wholly aromatic polyamides (aramid), Polyimides (PI), polyvinyl chloride (PVC), polyvinyl acetate, Polyphenylene Sulfide (PPs), fluorine resins, polyether ether ketone (PEEK), and cyclic olefin polymers.

Examples of the nonwoven fabric include nonwoven fabrics based on 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 a1 may have only 1 layer, or may have 2 or more layers.

The thickness of the base layer a1 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 4 to 500. mu.m, more preferably 10 to 400. mu.m, still more preferably 15 to 350. mu.m, and particularly preferably 20 to 300. mu.m.

The total light transmittance of the base material layer a1 is preferably 90% or more, more preferably 91% or more, further preferably 92% or more, and particularly preferably 93% or more. As long as the total light transmittance of the base material layer a1 is within the above range, it can provide: a reinforcing film which is not further deteriorated in detectability when an optical member or an electronic member is detected through the reinforcing film.

The base material layer a1 may also contain an antistatic agent. As the base layer a1 containing an antistatic agent, for example, a resin sheet kneaded with an antistatic agent can be used. Such a resin sheet may be formed from a composition for forming base layer a1 containing a resin and an antistatic agent.

The base material layer a1 itself may also function as an antistatic agent. For example, when a metal foil is used as the material of the base layer a1, the base layer a1 itself can function as an antistatic agent.

The base material layer a1 may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.

Examples of the organic coating material include those described in plastic hard coat material II (CMC published, (2004)). As such an organic coating material, a urethane-based polymer is preferably used, and a polyacrylic urethane, a polyester urethane, or a precursor thereof is more preferably used. The reason is that the base material layer a1 can be easily coated and applied, and a variety of materials can be selected in the industry, and can be obtained at low cost. Examples of such urethane polymers include polymers formed from a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound). The organic coating material may contain a chain extender such as polyamine, an antioxidant, an oxidation stabilizer, and the like as optional additives.

The base material layer a1 may contain any other suitable additive according to the purpose, as long as the effects of the present invention are not impaired.

<1-2. adhesive layer A2>

The thickness of the adhesive layer a2 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 1 to 300. mu.m, more preferably 2 to 250. mu.m, still more preferably 4 to 200. mu.m, and particularly preferably 5 to 150. mu.m.

The pressure-sensitive adhesive layer a2 may be 1 layer only, or may be 2 or more layers.

Adhesive layer a2 may also contain conductive components. The number of the conductive components may be 1 or 2 or more.

The adhesive strength to the PET film at a peel angle of 180 degrees and a peel speed of 300 mm/min after the pressure-sensitive adhesive layer A2 is stuck to the PET film and left to stand at 23 ℃ for 30 minutes is preferably 0.30N/25mm or more, more preferably 1N/25mm to 40N/25mm, still more preferably 5N/25mm to 35N/25mm, and particularly preferably 10N/25mm to 30N/25 mm.

The adhesive strength to the PET film at a peel angle of 180 degrees and a peel speed of 300 mm/min after the adhesive layer A2 is stuck to the PET film and left to stand at 60 ℃ for 60 minutes is preferably 10N/25mm or more, more preferably 10N/25mm to 40N/25mm, still more preferably 15N/25mm to 35N/25mm, and particularly preferably 20N/25mm to 30N/25 mm.

Adhesive layer a2 was formed from adhesive composition a 2. The pressure-sensitive adhesive layer a2 can be formed by any suitable method as long as the pressure-sensitive adhesive composition a2 can be formed into a layer. For example, the following methods can be mentioned: the pressure-sensitive adhesive layer a2 is prepared by a method in which the pressure-sensitive adhesive composition a2 is applied to an arbitrary suitable substrate, and if necessary, the substrate is subjected to heating or the like, irradiation with active energy rays (ultraviolet rays or the like), drying or the like, and if necessary, cured to form a pressure-sensitive adhesive layer on the substrate. Examples of the method of such coating include gravure roll coater, reverse roll coater, roll-licking coater, feed roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, and roll coater.

From the viewpoint of being able to further exhibit the effect of the present invention, the adhesive composition a2 preferably contains a polymer component.

The polymer component is preferably at least 1 selected from the group consisting of acrylic polymers, urethane polymers, and silicone polymers. The following description will be given by taking an acrylic polymer as a representative example.

The acrylic polymer may be referred to as a so-called base polymer in the field of acrylic adhesives. The number of the acrylic polymer may be only 1, or may be 2 or more.

The content of the acrylic polymer in the pressure-sensitive adhesive composition a2 is preferably 60 to 99.999 wt%, more preferably 65 to 99.99 wt%, even more preferably 70 to 99.9 wt%, particularly preferably 75 to 99.9 wt%, and most preferably 80 to 99.9 wt%, in terms of solid content.

As the acrylic polymer, any suitable acrylic polymer may be used within a range not impairing the effects of the present invention.

From the viewpoint of further exhibiting the effects of the present invention, the weight average molecular weight of the acrylic polymer is preferably 30 to 250 ten thousand, more preferably 35 to 200 ten thousand, still more preferably 40 to 180 ten thousand, and particularly preferably 50 to 150 ten thousand.

The acrylic polymer is preferably an acrylic polymer obtained by polymerizing a composition (a) containing (a) an alkyl (meth) acrylate having an alkyl group of an alkyl ester moiety and having 4 to 12 carbon atoms and (b) at least 1 selected from the group consisting of a (meth) acrylate having an OH group and a (meth) acrylic acid, from the viewpoint of further exhibiting the effects of the present invention.

The (a) component and the (b) component may be used independently of each other in only 1 kind, or in 2 or more kinds.

Examples of the alkyl (meth) acrylate (component a) having an alkyl group of an alkyl ester portion having 4 to 12 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, from the viewpoint of further exhibiting the effects of the present invention.

Examples of the at least 1 (b component) selected from the group consisting of a (meth) acrylate having an OH group and (meth) acrylic acid include (meth) acrylates having an OH group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and (meth) acrylic acid. Among these, hydroxyethyl (meth) acrylate and (meth) acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, from the viewpoint of further exhibiting the effects of the present invention.

The composition (a) may contain a copolymerizable monomer other than the components (a) and (b). The number of the copolymerizable monomer may be only 1, or may be 2 or more. Examples of such copolymerizable monomers include alkyl (meth) acrylates having an alkyl group of 1 to 3 carbon atoms in the alkyl ester moiety, such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate; carboxyl group-containing monomers (excluding (meth) acrylic acid) such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride); amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide; amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; heterocyclic vinyl monomers such as N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine and vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; alicyclic hydrocarbon group-containing (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; aromatic hydrocarbon group-containing (meth) acrylates such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.

As the copolymerizable monomer, a polyfunctional monomer may be used. The polyfunctional monomer means a monomer having 2 or more ethylenically unsaturated groups in 1 molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group may be used within a range not impairing the effects of the present invention. Examples of such an ethylenically unsaturated group include a radical polymerizable functional group such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Such polyfunctional monomers may be 1 type or 2 or more types.

As the copolymerizable monomer, alkoxyalkyl (meth) acrylate may also be used. Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The number of the alkoxyalkyl (meth) acrylates may be only 1, or may be 2 or more.

The content of the alkyl (meth) acrylate (component a) having an alkyl group of an alkyl ester moiety having 4 to 12 carbon atoms is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, even more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight to 96% by weight, based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer, from the viewpoint of further exhibiting the effects of the present invention.

The content of at least 1 (b component) selected from the group consisting of (meth) acrylates having OH groups and (meth) acrylic acids is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, even more preferably 2% by weight to 20% by weight, and particularly preferably 3% by weight to 15% by weight, relative to the total amount (100% by weight) of the monomer components constituting the acrylic polymer, from the viewpoint of further enabling the effects of the present invention to be exhibited.

The composition (a) may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent. The content of these other components may be any suitable content within a range not impairing the effect of the present invention.

The polymerization initiator may be a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like, depending on the kind of polymerization reaction. The number of polymerization initiators may be only 1, or may be 2 or more.

The thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization. Examples of such a thermal polymerization initiator include azo polymerization initiators, peroxide polymerization initiators (e.g., dibenzoyl peroxide, t-butyl peroxymaleate, etc.), redox polymerization initiators, and the like. Among these thermal polymerization initiators, the azo-based initiators disclosed in Japanese patent application laid-open No. 2002-69411 are particularly preferable. Such an azo polymerization initiator is preferable because a portion of a decomposition product as a polymerization initiator which causes generation of a gas (outgas) by heating is less likely to remain in the acrylic polymer. Examples of the azo polymerization initiator include 2,2 '-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2' -azobis-2-methylbutyronitrile (hereinafter, sometimes referred to as AMBN), dimethyl 2,2 '-azobis (2-methylpropionate), and 4, 4' -azobis-4-cyanovaleric acid.

The photopolymerization initiator is preferably used when an acrylic polymer is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include benzoin ether type photopolymerization initiators, acetophenone type photopolymerization initiators, α -ketol type photopolymerization initiators, aromatic sulfonyl chloride type photopolymerization initiators, photoactive oxime type photopolymerization initiators, benzoin type photopolymerization initiators, benzil type photopolymerization initiators, benzophenone type photopolymerization initiators, ketal type photopolymerization initiators, and thioxanthone type photopolymerization initiators.

Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethane-1-one, and methyl anisole. Examples of the acetophenone photopolymerization initiator include 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone and 4- (tert-butyl) dichloroacetophenone. Examples of the α -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl ] -2-methylpropan-1-one. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the optically active oxime-based photopolymerization initiator include 1-phenyl-1, 1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzil-based photopolymerization initiator include benzil and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, and α -hydroxycyclohexyl phenyl ketone. Examples of the ketal-based photopolymerization initiator include benzildimethylketal. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone, and dodecylthioxanthone.

Adhesive composition a2 may also contain a crosslinking agent. By using the crosslinking agent, the cohesive force of the acrylic adhesive can be improved, and the effects of the present invention can be further exhibited. The number of the crosslinking agents may be only 1, or may be 2 or more.

Examples of the crosslinking agent include a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, and a peroxide crosslinking agent, and further include a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and an amine crosslinking agent. Of these, at least 1 (component c) selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferable from the viewpoint of further exhibiting the effects of the present invention.

Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1, 2-ethylenediisocyanate, 1, 4-butylidenediisocyanate and 1, 6-hexamethylenediisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (product name "Coronate L" manufactured by Nippon Polyurethane Industry co., Ltd.), trimethylolpropane/hexamethylene diisocyanate adduct (product name "Coronate HL" manufactured by Nippon Polyurethane Industry co., Ltd.), product name "Coronate HX" (product name "TAKENATE co., Ltd."), trimethylolpropane/xylylene diisocyanate adduct (product name "TAKENATE 110N" manufactured by mitsui chemical co., Ltd.), and the like.

Examples of the epoxy-based crosslinking agent (polyfunctional epoxy compound) include N, N, N ', N' -tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, Resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having 2 or more epoxy groups in the molecule. Examples of the epoxy-based crosslinking agent include commercially available products such as "TETRAD C" (manufactured by Mitsubishi gas chemical Co., Ltd.).

As for the content of the crosslinking agent in the adhesive composition a2, any suitable content may be employed within a range not impairing the effects of the present invention. Such a content is, for example, preferably 0.005 to 20 parts by weight, more preferably 0.05 to 18 parts by weight, still more preferably 0.01 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight, based on the solid content (100 parts by weight) of the acrylic polymer, from the viewpoint of further exhibiting the effects of the present invention.

The adhesive composition a2 may contain any other suitable component within a range not impairing the effects of the present invention. Examples of such other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, adhesion-imparting resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, and the like), antioxidants, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, and the like), foils, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, anticorrosive agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The pressure-sensitive adhesive composition a2 preferably does not contain an oligomer (X) obtained from a monomer composition containing, as a main component, an acrylic monomer having a tricyclic or higher cyclic structure. In this case, the content ratio of the acrylic monomer having a tricyclic or higher cyclic structure is preferably 50 parts by weight or more, more preferably 60 parts by weight to 99 parts by weight, even more preferably 70 parts by weight to 98 parts by weight, and particularly preferably 80 parts by weight to 96 parts by weight, based on 100 parts by weight of the total monomer components contained in the monomer composition used for obtaining the oligomer (X). The adhesive composition a2 can be provided by not including an oligomer (X) obtained from a monomer composition containing, as a main component, an acrylic monomer having a tricyclic or higher cyclic structure: a reinforcing film which is not further deteriorated in detectability when an optical member or an electronic member is detected through the reinforcing film.

Examples of the acrylic monomer having a tricyclic or higher cyclic structure include dicyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentyl methacrylate, dicyclopentyloxyethyl acrylate, tricyclopentylmethacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, and 2-ethyl-2-adamantyl acrylate.

The number of the acrylic monomers having a tricyclic or higher cyclic structure may be 1 or 2 or more.

The monomer composition used for obtaining the oligomer (X) may contain other monomers in addition to the acrylic monomer having a tricyclic or higher cyclic structure. Such other monomers may be only 1 type, or may be 2 or more types.

Examples of the other monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate and methyl (meth) acrylate glycidyl ester; vinyl ester monomers such as vinyl acetate and vinyl propionate; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; olefin monomers such as ethylene, propylene, isoprene, and butadiene; vinyl ether monomers such as vinyl ether; and so on.

Examples of the other monomer include polyfunctional monomers such as hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di (meth) acrylate, and hexyl di (meth) acrylate.

Examples of the other monomer include a nitrogen atom-containing monomer (for example, aminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate, (N-substituted) amide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hydroxy (meth) acrylamide, (cyanoacrylate monomers such as acrylonitrile and methacrylonitrile, and isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate).

Adhesive composition a2 may also contain an oligomer (Y) other than oligomer (X). However, the content of the oligomer (Y) is preferably small in order to further exhibit the effect of the present invention.

From the viewpoint of further exhibiting the effects of the present invention, the content of the oligomer (Y) in the adhesive composition a2 is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, further preferably 30 parts by weight or less, and particularly preferably 25 parts by weight or less, based on 100 parts by weight of the acrylic polymer contained in the adhesive composition a 2.

The oligomer (Y) is preferably an oligomer obtained from a monomer composition containing an acrylic monomer having a cyclic structure of not more than two rings as a main component and containing 1 to 10 parts by weight of a carboxyl group-containing monomer per 100 parts by weight of the total amount of the monomer components.

The cyclic structure of the bicyclic or bicyclic ring may be an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferable. Examples of the aromatic ring include an aromatic hydrocarbon ring (e.g., a benzene ring, a condensed carbocyclic ring in naphthalene, etc.), various aromatic heterocyclic rings, and the like. Examples of the nonaromatic ring include nonaromatic alicyclic rings (e.g., cycloalkane rings such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane rings; cycloalkene rings such as cyclohexene rings), nonaromatic bridged rings (e.g., bicyclic hydrocarbon rings in pinane, pinene, camphane, norbornane, and norbornene), and the like.

Examples of the acrylic monomer having a cyclic structure of not more than two rings include ethylenically unsaturated monomers having a cyclic structure in the molecule, such as cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, aryl (meth) acrylates such as phenyl (meth) acrylate, aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, arylalkyl (meth) acrylates such as benzyl (meth) acrylate, and styrene monomers such as styrene and α -methylstyrene.

The acrylic monomer having a cyclic structure of not more than two rings is preferably a (meth) acrylate having a non-aromatic ring such as cyclohexyl methacrylate or isobornyl (meth) acrylate, and more preferably cyclohexyl methacrylate from the viewpoint of transparency.

The number of the acrylic monomers having a cyclic structure of not more than two rings may be only 1, or may be 2 or more.

The content ratio of the acrylic monomer having a cyclic structure of not more than two rings is preferably 50 to 99 parts by weight, more preferably 70 to 99 parts by weight, still more preferably 80 to 98 parts by weight, particularly preferably 90 to 97 parts by weight, and most preferably 92 to 96 parts by weight, based on 100 parts by weight of all monomer components contained in the monomer composition used for obtaining the oligomer (Y).

The oligomer (Y) may contain a carboxyl group-containing monomer as a monomer component. Examples of such a carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, as in the case of a carboxyl group-containing monomer that can constitute an acrylic polymer. Further, examples of the carboxyl group-containing monomer include acid anhydrides of these carboxyl group-containing monomers (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride).

The content ratio of the carboxyl group-containing monomer is preferably 1 to 10 parts by weight, more preferably 2 to 9 parts by weight, much more preferably 3 to 8 parts by weight, and particularly preferably 4 to 7 parts by weight, based on 100 parts by weight of the total monomer components contained in the monomer composition used for obtaining the oligomer (Y).

The monomer composition used for obtaining the oligomer (Y) may contain other monomers in addition to the acrylic monomer having a cyclic structure of a bicyclo ring or less. Such other monomers may be only 1 type, or may be 2 or more types.

Examples of the other monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate and methyl (meth) acrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; olefin monomers such as ethylene, propylene, isoprene, and butadiene; vinyl ether monomers such as vinyl ether; and the like.

Examples of the other monomer include a nitrogen atom-containing monomer (for example, aminoalkyl acrylate monomers such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate, (N-substituted) amide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hydroxy (meth) acrylamide, (cyanoacrylate monomers such as acrylonitrile and methacrylonitrile, and isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate). However, such a nitrogen atom-containing monomer is not preferably used when it is not necessary to use, because it may cause yellowing of the adhesive upon heating.

The oligomer (X) and the oligomer (Y) can be produced by any suitable polymerization method within a range not impairing the effects of the present invention. Examples of the method for polymerizing the acrylic polymer include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method by ultraviolet irradiation, and the like, and the solution polymerization method is preferable in view of transparency, water resistance, cost, and the like.

Any suitable polymerization initiator, chain transfer agent, and the like that can be used in the polymerization can be used within a range that does not impair the effects of the present invention.

The amount of the polymerization initiator to be used may be any suitable amount within a range not impairing the effects of the present invention. Such an amount is preferably 0.1 to 15% by weight based on the total amount of the monomer components.

The amount of the chain transfer agent may be any suitable amount within a range not impairing the effects of the present invention. Such an amount is preferably 0.01 to 15 wt% based on the total amount of the monomer components.

In the solution polymerization method, various general solvents can be used. Examples of such solvents include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-pentane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and the like. The number of the solvents may be only 1, or may be 2 or more.

The weight average molecular weights of the oligomers (X) and (Y) are preferably 3000 to 6000, more preferably 3300 to 5500, and still more preferably 3500 to 5000.

The weight average molecular weights of the oligomers (X) and (Y) can be controlled by the monomer concentration, the monomer dropping rate, and the like, in addition to the types of the polymerization initiator and the chain transfer agent, the amount thereof, and the temperature and time at the time of polymerization.

When the pressure-sensitive adhesive composition a2 contains an acrylic polymer and an oligomer, the ratio of the oligomer to the acrylic polymer is preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight, based on 100 parts by weight of the acrylic polymer. When the adhesive composition a2 contains an acrylic polymer and an oligomer, the effect of the present invention can be further exhibited if the ratio of the acrylic polymer to the oligomer is within the above range.

The pressure-sensitive adhesive composition a2 may contain, as required, known additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, an antioxidant, an adhesion-imparting agent, a plasticizer, a softening agent, a filler, a colorant (such as a pigment and a dye), a surfactant, and an antistatic agent.

<1-3. Release sheet >

For protection, a release sheet may be provided on the surface of the pressure-sensitive adhesive layer a 2. The release sheet may have 1 layer or 2 or more layers.

The thickness of the release sheet is preferably 5 to 300. mu.m, more preferably 10 to 200. mu.m, still more preferably 10 to 150. mu.m, particularly preferably 10 to 130 μm, and most preferably 20 to 120 μm, from the viewpoint of further exhibiting the effects of the present invention.

The release sheet comprises a resin base film.

Examples of the resin base film include plastic films made of polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); plastic films made of olefin resins containing α -olefins as monomer components, such as Polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymers, and ethylene-vinyl acetate copolymers (EVA); a plastic film composed of polyvinyl chloride (PVC); a plastic film made of a vinyl acetate resin; a plastic film composed of Polycarbonate (PC); a plastic film made of polyphenylene sulfide (PPS); plastic films made of amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film made of a polyimide resin; a plastic film composed of polyether ether ketone (PEEK); plastic films made of olefin resins such as Polyethylene (PE) and polypropylene (PP); plastic films made of fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and chlorofluoroethylene-vinylidene fluoride copolymers; and the like.

The resin base film may have only 1 layer or 2 or more layers. The resin substrate film may be stretched.

The resin base film may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.

The resin base film may contain any suitable additive within a range not impairing the effects of the present invention.

The release sheet may have a release layer in order to improve releasability from the pressure-sensitive adhesive layer a 2. When the release sheet has a release layer, the release layer side is directly laminated on the adhesive layer a 2.

As the material for forming the release layer, any suitable material may be used as long as the effects of the present invention are not impaired. Examples of such a forming material include silicone release agents, fluorine release agents, long-chain alkyl release agents, and fatty acid amide release agents. Among these, silicone-based release agents are preferable. The release layer may be formed as a coating layer.

The thickness of the release layer may be any suitable thickness according to the purpose within a range not impairing the effects of the present invention. The thickness is preferably 10nm to 2000nm, more preferably 10nm to 1500nm, still more preferably 10nm to 1000nm, and particularly preferably 10nm to 500 nm.

The releasing layer may be 1 layer only, or may be 2 or more layers.

Examples of the silicone-based release layer include addition reaction type silicone resins. Specific examples of the addition reaction type silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T; TPR-6700, TPR-6710 and TPR-6721 made of Toshiba organosilicone; SD7220 and SD7226 manufactured by Dow Toray co, ltd; and the like. The amount of the silicone-based release layer applied (after drying) is preferably 0.01g/m²～2g/m²More preferably 0.01g/m²～1g/m²More preferably 0.01g/m²～0.5g/m²。

The release layer can be formed, for example, as follows: the above-mentioned forming material is applied to any suitable layer by a conventionally known coating method such as reverse gravure coating, bar coating, die coating, etc., and then cured by heat treatment at about 120 to 200 ℃. Further, if necessary, a combination of heat treatment and irradiation with active energy rays such as ultraviolet irradiation may be used.

The release sheet may also have an antistatic layer.

As the thickness of the antistatic layer, any suitable thickness can be adopted within a range not impairing the effects of the present invention. The thickness is preferably 1nm to 1000nm, more preferably 5nm to 900nm, still more preferably 7.5nm to 800nm, and particularly preferably 10nm to 700 nm.

The antistatic layer may be 1 layer only, or may be 2 or more layers.

As the antistatic layer, any suitable antistatic layer may be used as long as it can exert an antistatic effect within a range not impairing the effects of the present invention. The antistatic layer is preferably formed by applying a conductive coating solution containing a conductive polymer to an arbitrary suitable base material layer. Specifically, for example, the antistatic layer is formed by applying a conductive coating liquid containing a conductive polymer onto a resin base film. Specific coating methods include roll coating, bar coating, and gravure coating.

As the conductive polymer, any suitable conductive polymer can be used within a range not impairing the effects of the present invention. Examples of such a conductive polymer include a conductive polymer in which a polyanion is doped in a pi-conjugated conductive polymer. Examples of the n-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrenesulfonic acid, polyisoprenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyethylenesulfonic acid, and polymethacrylic carboxylic acid. The number of the conductive polymers may be only 1, or may be 2 or more.

<1-4. functional layer A3>

The reinforcing film may include a functional layer A3, a base layer a1, and an adhesive layer a2 in this order. That is, as shown in fig. 2, another embodiment of the reinforcing film is composed of a functional layer A3(30), a base layer a1(10), and a pressure-sensitive adhesive layer a2 (20).

The functional layer a3 is an optional layer, and is a layer that can impart various functions to the reinforcing film.

The thickness of the functional layer a3 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 1nm to 1000nm, more preferably 2nm to 800nm, still more preferably 5nm to 400nm, and particularly preferably 10nm to 200 nm.

The functional layer a3 may be only 1 layer, or may be 2 or more layers.

As the functional layer a3, any suitable functional layer may be used within a range not impairing the effects of the present invention. Examples of such a functional layer include an antistatic layer, an anti-reflection layer, an antiglare layer, and a hard coat layer, and the anti-reflection layer can be selected from the viewpoint that the effects of the present invention can be further exhibited.

As the antireflection layer, any suitable antireflection layer may be used within a range not impairing the effects of the present invention. Examples of such an antireflection layer include those described in Japanese patent laid-open publication No. 2019-144577 and the like.

As the functional layer a3, an antistatic layer can also be appropriately selected in order to exhibit an antistatic effect.

When both an anti-reflective layer and an antistatic layer are selected as the functional layer A3, it is preferable to dispose an antistatic layer on the base layer a1 side in order to further exhibit the function of the anti-reflective layer.

As the antistatic layer, any suitable antistatic layer may be used as long as it can exert an antistatic effect within a range not impairing the effects of the present invention. The antistatic layer is preferably formed by applying a conductive coating solution containing a conductive polymer to an arbitrary suitable base material layer. Specifically, for example, the antistatic layer is formed by applying a conductive coating liquid containing a conductive polymer onto base layer a 1. Specific coating methods include roll coating, bar coating, and gravure coating.

As the conductive polymer, any suitable conductive polymer can be used within a range not impairing the effects of the present invention. Examples of such a conductive polymer include a conductive polymer in which a polyanion is doped in a pi-conjugated conductive polymer. Examples of the n-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrenesulfonic acid, polyisoprenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyethylenesulfonic acid, and polymethacrylic carboxylic acid.

<1-5 > use of a reinforcing film, optical member with a reinforcing film, and electronic member with a reinforcing film >

The reinforcing film of the present invention is attached to an adherend, which is any suitable member. Typically, the reinforcing film of the present invention is attached to an adherend, which is an optical member or an electronic member. In this case, the exposed surface side of the pressure-sensitive adhesive layer a2 of the reinforcing film of the present invention is bonded to an adherend, which is an optical member or an electronic member. Thus, the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention can be obtained. That is, the optical member with a reinforcing film or the electronic member with a reinforcing film of the present invention includes the reinforcing film of the present invention.

Surface protective film

The surface protecting film is disposed on the reinforcing film side of the base layer a 1. When the base layer a1 includes the functional layer A3, a surface protective film is disposed on the functional layer A3 side.

The thickness of the surface protective film may be any suitable thickness according to the purpose within a range not impairing the effects of the present invention. The thickness is preferably 4 to 500. mu.m, more preferably 10 to 400. mu.m, still more preferably 15 to 350. mu.m, and particularly preferably 20 to 300. mu.m.

The surface protective film includes a base material layer B1 and an adhesive layer B2. The surface protective film may have any other suitable layer as long as it has the base layer B1 and the adhesive layer B2, within a range not impairing the effects of the present invention.

For protection, a release sheet may be provided on the surface of the adhesive layer B2.

In order to impart various functions, the functional layer B3 may be provided on the surface of the base material layer B1.

The thickness of the surface protecting film may be any suitable thickness according to the purpose within a range not impairing the effects of the present invention. The thickness is preferably 5 to 500. mu.m, more preferably 10 to 450. mu.m, still more preferably 15 to 400. mu.m, and particularly preferably 20 to 300. mu.m.

As shown in fig. 3, one embodiment of the surface protective film is composed of a base material layer B1(40), a pressure-sensitive adhesive layer B2(50), and a release sheet (60).

As shown in fig. 4, one embodiment of the surface protective film is composed of a functional layer B3(70), a base layer B1(40), an adhesive layer B2(50), and a release sheet (60).

<2-1. base Material layer B1>

As the base material layer B1, a base material formed of any suitable material may be used according to the purpose within the range not impairing the effects of the present invention. Examples of such a material include those listed in the items <1-1. base material layer a1 >.

The base material layer B1 may have only 1 layer, or may have 2 or more layers.

The thickness of the base material layer B1 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 4 to 350. mu.m, more preferably 8 to 325. mu.m, still more preferably 12 to 290. mu.m, and particularly preferably 15 to 205. mu.m.

The base material layer B1 may also contain an antistatic agent. As the base layer B1 containing an antistatic agent, for example, a resin sheet kneaded with an antistatic agent can be used. Such a resin sheet may be formed from a composition for forming base layer B1 containing a resin and an antistatic agent.

The base material layer B1 itself may also function as an antistatic agent. For example, when a metal foil is used as the material of the base layer B1, the base layer B1 itself can function as an antistatic agent.

The base material layer B1 may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with an undercoating agent.

Examples of the organic coating material include those listed in the items <1-1. base material layer a1 >.

The base layer B1 may contain any other suitable additive according to the purpose within a range not impairing the effects of the present invention.

<2-2. adhesive layer B2>

The thickness of the adhesive layer B2 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 1 to 150. mu.m, more preferably 2 to 125. mu.m, still more preferably 3 to 110 μm, and particularly preferably 5 to 95 μm.

As the adhesive layer B2, an adhesive layer made of any suitable adhesive can be used as long as the effects of the present invention are not impaired. Examples of such adhesives include adhesives constituting the adhesive layer described in jp 2019-127526 a, and preferably include at least 1 selected from the group consisting of acrylic adhesives, urethane adhesives, and silicone adhesives described in the publication.

<2-3. Release sheet >

For protection, a release sheet may be provided on the surface of the adhesive layer B2. The release sheet may have 1 layer or 2 or more layers.

As the release sheet that the surface protective film may have, the description in the item <1-3. release sheet > may be applied.

<2-4. functional layer B3>

The surface protection film may include a functional layer B3, a base material layer B1, and an adhesive layer B2 in this order.

The functional layer B3 is an optional layer, and is a layer that can impart various functions to the reinforcing film.

The thickness of the functional layer B3 may be any suitable thickness according to the purpose, within a range not impairing the effects of the present invention. The thickness is preferably 1nm to 1000nm, more preferably 2nm to 800nm, still more preferably 5nm to 400nm, and particularly preferably 10nm to 200 nm.

The functional layer B3 may be only 1 layer, or may be 2 or more layers.

For the functional layer B3, the descriptions in the item <1-4. functional layer A3> may be applied.

[ 3 ] reinforcing film with surface protective film ]

The reinforcing film with a surface protective film of the present invention includes a surface protective film on the substrate layer a1 side of the reinforcing film of the present invention. When the reinforcing film of the present invention further includes the functional layer A3 on the base layer a1, a surface protective film is provided on the surface of the functional layer A3.

The reinforcing film with a surface protective film of the present invention has a reinforcing film and a surface protective film. The reinforcing film with a surface protective film of the present invention may have any other suitable layer as long as it has the reinforcing film and the surface protective film, within a range not impairing the effects of the present invention.

In the reinforcing film with a surface protective film of the present invention, the reinforcing film includes a base layer a1 and a pressure-sensitive adhesive layer a2, and the surface protective film includes a base layer B1 and a pressure-sensitive adhesive layer B2.

The thickness of the reinforcing film with a surface protective film of the present invention may be any suitable thickness according to the purpose within the range not impairing the effects of the present invention. The thickness is preferably 9 to 1300 μm, more preferably 20 to 1050 μm, still more preferably 35 to 900 μm, and particularly preferably 45 to 750 μm.

The reinforcing film with a surface protective film of the present invention can be obtained by: the reinforcing film and the surface protection film were directly laminated on a base material layer a1 (in the case where the base material layer a1 further includes the functional layer A3, this functional layer A3) and a pressure-sensitive adhesive layer B2 (in the case where a release sheet is provided on the pressure-sensitive adhesive layer B2, this release sheet is peeled off and the pressure-sensitive adhesive layer B2 is exposed) of the surface protection film, and they were bonded to each other.

As shown in fig. 5, one embodiment of the reinforcing film with a surface protective film of the present invention is as follows: a reinforcing film composed of the base layer a1(10) and the pressure-sensitive adhesive layer a2(20), and a surface protective film composed of the base layer B1(40) and the pressure-sensitive adhesive layer B2(50) were directly laminated to the base layer a1(10) and the pressure-sensitive adhesive layer B2 (50).

(4. usage of reinforcing film)

The reinforcing film of the present invention is typically attached to an adherend, which is an optical member or an electronic member. Specifically, the exposed surface of the pressure-sensitive adhesive layer a2 of the reinforcing film of the present invention is stuck to an adherend, which is an optical member or an electronic member. When a release sheet is provided on the surface of the pressure-sensitive adhesive layer a2, the pressure-sensitive adhesive layer a2 exposed by peeling the release sheet is stuck to an adherend which is an optical member or an electronic member.

The adherend is an optical member or an electronic member, and examples thereof include an LED, a micro LED, a mini LED, and an OLED. Such an adherend is typically an OLED.

The OLED is preferably at least 1 selected from the group consisting of a folding member, a flexible member, and a rollable member, in view of further making full use of the effect exhibited by the reinforcing film of the present invention.

The foldable member is a (foldable) member having a movable bending portion, the flexible member is a bendable member, and the crimpable member is a rollable member.

Method of Using reinforcing film with surface protecting film

The method of using the laminated film with a surface protective film of the present invention is as follows: the pressure-sensitive adhesive layer a2 included in the reinforcing film with a surface protection film of the present invention was exposed, the pressure-sensitive adhesive layer a2 was adhered to an adherend, and then the surface protection film was peeled off. In the reinforcing film with a surface protective film of the present invention, when the release sheet is provided on the surface of the pressure-sensitive adhesive layer a2, first, the release sheet is peeled to expose the pressure-sensitive adhesive layer surface on the pressure-sensitive adhesive layer a2 side, and the pressure-sensitive adhesive layer surface is adhered to an adherend. Subsequently, the surface protective film is peeled off.

In this way, a member in which the reinforcing film is attached to the adherend can be obtained.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The test and evaluation methods in examples and the like are as follows. In the case of "part(s)", unless otherwise specified, "part(s) by weight" means "part(s) by weight", and in the case of "%" means "% by weight" means "wt%" unless otherwise specified.

< measurement of weight average molecular weight >

The weight average molecular weight was measured by Gel Permeation Chromatography (GPC). Specifically, the GPC measurement apparatus used was the product "HLC-8120 GPC" (manufactured by Tosoh corporation), and the measurement was performed under the following conditions, and the calculation was performed based on the standard polystyrene conversion value.

(conditions for measuring molecular weight)

Sample concentration: 0.2 wt% (tetrahydrofuran solution)

Sample injection amount: 10 μ L

Column: the trade name is "TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 parts)" (manufactured by Tosoh Co., Ltd.)

Reference column: the trade name is "TSKgel SuperH-RC (1 root)" (manufactured by Tosoh corporation)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.6 mL/min

The detector: differential Refractometer (RI)

Column temperature (measurement temperature): 40 deg.C

< Absolute value of rate of change of in-plane retardation at wavelength 590nm >

The reinforcing film obtained in examples or comparative examples was peeled off from the release sheet, and the in-plane retardation R from the substrate side was measured at a measurement wavelength of 590nm by a polarization/retardation measurement system (Axometrics, manufactured by Axoscan)₀In-plane retardation R₀1 (nm). Next, the reinforcing films obtained in examples and comparative examples were stored at 60 ℃ and 90% RH for 1 week, then left at 23 ℃ for 30 minutes to return to room temperature, and after peeling off the release sheet, the in-plane retardation R from the substrate side of the remaining reinforcing film was measured in the same manner as described above₀As the in-plane retardation R₀2 (nm). Using the obtained in-plane retardation R₀1(nm) and in-plane retardation R₀2(nm), and the in-plane retardation (R) at a wavelength of 590nm was calculated₀) Is the absolute value of the rate of change of (Δ R)₀(nm)＝|(R₀2-R₀1)/(R₀1)×100|。

< haze Change Rate >

The reinforcing film obtained in examples or comparative examples was peeled off from the release sheet, and the haze was measured by a haze meter (model HM-150, manufactured by Colorcon, village) to obtain a haze H1 (%). Next, the reinforcing films obtained in examples and comparative examples were stored at 60 ℃ and 90% RH for 1 week, then left at 23 ℃ for 30 minutes and returned to room temperature, and after peeling off the release sheet, the haze of the remaining reinforcing film was measured in the same manner, and the haze H2 (%) was determined. Using the obtained value of the haze, the haze change rate Δ H (%) (H2-H1)/(H1) × 100 was calculated.

< Total light transmittance >

The reinforcing film obtained in examples or comparative examples was peeled off from the release sheet, and the transmittance at 580nm was measured using a spectrophotometer (model U-4100, manufactured by Hitachi Ltd.).

< adhesion to PET film >

The reinforcing film (width 25 mm. times. length 140mm) from which the release sheet was peeled was attached to a glass-lined PET film "Lumiror S10# 25" (manufactured by Toray Industries, Inc.) by reciprocating 1 time with a 2kg hand roller. Then, it was left at an ambient temperature of 23 ℃ for 30 minutes.

The evaluation sample obtained as described above was measured with a tensile tester. As the tensile testing machine, the product name "Autograph AG-Xplus HS 6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. After the test piece for evaluation was mounted on the tensile testing machine, the tensile test was started. The conditions for the tensile test were as follows: peeling angle: 180 degrees, peeling speed (stretching speed): 300 mm/min. The load when the reinforcing film was peeled from the PET film was measured, and the average load at that time was taken as the adhesion force of the reinforcing film to the PET film.

< adhesion to PET film (after heating at 60 ℃ C.. times.60 minutes) >

The reinforcing film (width 25 mm. times. length 140mm) from which the release sheet was peeled was attached to a glass-lined PET film "Lumiror S10# 25" (manufactured by Toray Industries, Inc.) by reciprocating 1 time with a 2kg hand roller. Then, the mixture was left at an ambient temperature of 60 ℃ for 60 minutes.

< Rainbow spots >

The reinforcing films obtained in examples and comparative examples were peeled and laminated so that the transmission axis direction of the polarizing plate was parallel to the MD direction of the film substrate. The other polarizing plate is disposed on the reinforcing film so as to be crossed with respect to the polarizing plate bonded to the reinforcing film. The lower side of one polarizing plate was irradiated with light from a fluorescent lamp, and the transmitted light was visually observed to evaluate whether or not rainbow unevenness occurred. The case where no rainbow spots were observed was regarded as OK, and the case where rainbow spots were observed was regarded as NG.

[ production example 1 ]: production of (meth) acrylic Polymer (1)

2-ethylhexyl acrylate (Nippon Shokubai co., ltd.): 65 parts of N-vinyl pyrrolidone (Nippon Shokubai Co., manufactured by Ltd.): 15 parts of hydroxyethyl acrylate (manufactured by Toyo Synthesis Co., Ltd.): 13 parts of methyl methacrylate (manufactured by Mitsubishi gas chemical corporation): 7 parts of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part, ethyl acetate: 156 parts by weight of a solution of (meth) acrylic polymer (1) having a weight-average molecular weight of 70 ten thousand (solid content concentration: 40% by weight) was prepared by conducting polymerization for 10 hours while introducing nitrogen gas while slowly stirring and maintaining the liquid temperature in the flask at about 63 ℃.

[ production example 2 ]: production of (meth) acrylic Polymer (2)

In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, butyl acrylate (Nippon Shokubai co., ltd.): 100 parts of acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 7.5 parts of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (2) solution having a weight-average molecular weight of 70 ten thousand (solid content concentration: 40% by weight) was prepared by conducting polymerization for 10 hours while introducing nitrogen gas while slowly stirring and maintaining the liquid temperature in the flask at about 63 ℃.

[ production example 3 ]: production of (meth) acrylic Polymer (3)

2-ethylhexyl acrylate (Nippon Shokubai co., ltd.): 96 parts of hydroxyethyl acrylate (manufactured by Toyo Synthesis Co., Ltd.): 4 parts of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part, ethyl acetate: 156 parts by weight of a solution of (meth) acrylic polymer (3) having a weight average molecular weight of 50 ten thousand (solid content concentration: 40% by weight) was prepared by conducting polymerization for 10 hours while introducing nitrogen gas while slowly stirring and maintaining the liquid temperature in the flask at about 63 ℃.

[ production example 4 ]: production of (meth) acrylic oligomer (4)

The glass transition temperature of cyclohexyl methacrylate [ homopolymer (polycyclohexyl methacrylate) ] as a monomer component was measured: 66 ℃ C. ]: 95 parts by weight, acrylic acid: 5 parts by weight of 2-mercaptoethanol as a chain transfer agent: 3 parts by weight of 2, 2' -azobisisobutyronitrile as a polymerization initiator: 0.2 parts by weight, and toluene as a polymerization solvent: 103.2 parts by weight of the mixture was put into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymer system in this manner, the temperature was raised to 70 ℃ and the reaction was carried out for 3 hours, and further, the reaction was carried out at 75 ℃ for 2 hours to prepare a solution of (meth) acrylic oligomer (4) having a weight average molecular weight of 4000 (solid content concentration: 50 wt%).

[ production example 5 ]: production of (meth) acrylic oligomer (5)

100 parts by weight of toluene and dicyclopentanyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical industries, Ltd.) were put into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, a condenser, and a dropping funnel: 60 parts by weight, Methyl Methacrylate (MMA): 40 parts by weight, and methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. Further, after stirring at 70 ℃ for 1 hour under a nitrogen atmosphere, 2' -azobisisobutyronitrile: 0.2 part by weight, reacted at 70 ℃ for 2 hours, then at 80 ℃ for 4 hours, and then at 90 ℃ for 1 hour to prepare a solution of (meth) acrylic oligomer (5) having a weight average molecular weight of 4000 (solid content concentration: 51 wt%).

[ production example 6 ]: production of (meth) acrylic oligomer (6)

100 parts by weight of toluene, 40 parts by weight of Methyl Methacrylate (MMA), 20 parts by weight of Butyl Methacrylate (BMA), 20 parts by weight of 2-ethylhexyl methacrylate (2-EHMA), 17 parts by weight of a polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174ASX, manufactured by shin-Etsu chemical Co., Ltd.) having a functional group equivalent of 900g/mol, 3 parts by weight of a polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174DX, manufactured by shin-Etsu chemical Co., Ltd.) having a functional group equivalent of 4600g/mol, and 0.51 part by weight of methyl thioglycolate as a chain transfer agent were put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Further, after stirring at 70 ℃ for 1 hour under a nitrogen atmosphere, 0.2 part by weight of azobisisobutyronitrile as a thermal polymerization initiator was added, and after reacting at 70 ℃ for 2 hours, 0.1 part by weight of azobisisobutyronitrile as a thermal polymerization initiator was added, followed by reacting at 80 ℃ for 5 hours, to prepare a solution of (meth) acrylic oligomer (6) having a weight average molecular weight of 21300 (solid content concentration: 50 wt%).

[ production example 7 ]: production of (meth) acrylic adhesive composition (1)

To the solution of the (meth) acrylic polymer (1) obtained in production example 1, Coronate HL (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent was added in an amount of 1.0 part by weight in terms of solid content to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the mixture was diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disperser to prepare a (meth) acrylic adhesive composition (1).

[ production example 8 ]: production of (meth) acrylic adhesive composition (2)

To the solution of the (meth) acrylic polymer (2) obtained in production example 2, 0.075 parts by weight in terms of solid content of tetra d-C (manufactured by mitsubishi gas chemical) as a crosslinking agent and 20 parts by weight in terms of solid content of the solution of the (meth) acrylic oligomer (4) obtained in production example 4 were added, based on 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and the solution was diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a disperser to prepare a (meth) acrylic pressure-sensitive adhesive composition (2).

[ production example 9 ]: production of (meth) acrylic adhesive composition (3)

To the solution of the (meth) acrylic polymer (3) obtained in production example 3, 0.1 part by weight in terms of solid content of Coronate HL (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 5 parts by weight in terms of solid content of the solution of the (meth) acrylic oligomer (5) obtained in production example 5 were added, and the solution was diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a dispersing machine to prepare a (meth) acrylic adhesive composition (3).

[ production example 10 ]: production of (meth) acrylic adhesive composition (4)

To the solution of the (meth) acrylic polymer (3) obtained in production example 3, 0.1 part by weight in terms of solid content of Coronate HL (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 7.5 parts by weight in terms of solid content of the solution of the (meth) acrylic oligomer (5) obtained in production example 5 were added, and the solution was diluted with ethyl acetate so that the solid content of the whole was 25% by weight and stirred by a disperser, to prepare a (meth) acrylic adhesive composition (4).

[ production example 11 ]: production of (meth) acrylic adhesive composition (5)

To the solution of the (meth) acrylic polymer (3) obtained in production example 3, 0.1 part by weight in terms of solid content of Coronate HL (Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 10 parts by weight in terms of solid content of the solution of the (meth) acrylic oligomer (5) obtained in production example 5 were added, and the solution was diluted with ethyl acetate so that the total solid content was 25% by weight, and stirred with a dispersing machine to prepare a (meth) acrylic adhesive composition (5).

[ production example 12 ]: production of (meth) acrylic adhesive composition (6)

To the solution of the (meth) acrylic polymer (3) obtained in production example 3, Coronate HL (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent was added in an amount of 4.0 parts by weight in terms of solid content to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (3), and the mixture was diluted with ethyl acetate so that the solid content of the whole was 25% by weight and stirred with a dispersing machine to prepare a (meth) acrylic adhesive composition (6).

[ production example 13 ]: production of (meth) acrylic adhesive composition (7)

To the solution of the (meth) acrylic polymer (1) obtained in production example 1, 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1) and 1.0 part by weight in terms of solid content of a solution of the (meth) acrylic oligomer (6) obtained in production example 6 as a crosslinking agent (Coronate HL (manufactured by Nippon Polyurethane Industry co., ltd.) and 2.0 parts by weight in terms of solid content of the solution of the (meth) acrylic polymer (1) were added, and the solution was diluted with ethyl acetate so that the solid content of the whole was 25% by weight and stirred by a disperser to prepare a (meth) acrylic adhesive composition (7).

[ production example 14 ]: production of (meth) acrylic adhesive composition (8)

To the solution of the (meth) acrylic polymer (1) obtained in production example 1, 2.5 parts by weight in terms of solid content of Coronate HL (manufactured by Nippon Polyurethane Industry co., ltd.) as a crosslinking agent and 2.5 parts by weight in terms of solid content of the solution of the (meth) acrylic oligomer (6) obtained in production example 6 were added, and the solution was diluted with ethyl acetate so that the solid content of the whole was 25% by weight and stirred by a disperser to prepare a (meth) acrylic adhesive composition (8).

[ production example 15 ]: production of coating composition for Forming antireflection layer

In a 200mL glass container, ethanol: 60g of an aqueous dispersion sol of ZnO fine particles (average primary particle size)Particle size: 20nm, average aggregate particle size: 40nm, solid content conversion concentration: 20% by weight): 30g of tetraethoxysilane (SiO)₂Solid content concentration: 29% by weight): 10g, an aqueous ammonia solution was added to set the pH to 10, and the mixture was stirred at 20 ℃ for 6 hours to obtain a dispersion of core-shell particles (solid content concentration: 6% by weight): 100 g. In the obtained dispersion of core-shell particles: 100g of a strong acid cation exchange resin (total exchange capacity: 2.0meq/mL or more) was added to 100g of the solution, the mixture was stirred for 1 hour to adjust pH to 4, and then the strong acid cation exchange resin was removed by filtration to obtain SiO₂A dispersion of spherical hollow fine particles. The obtained dispersion was concentrated by ultrafiltration to a solid content concentration of 20% by weight. The spherical hollow fine particles are secondarily aggregated. The shell of the spherical hollow fine particles had a thickness of 5nm and an average primary particle diameter of 1/6. The spherical hollow fine particles had an average aggregate particle diameter of 40nm and an aspect ratio of 1.0.

The obtained dispersion of spherical hollow fine particles (solid content concentration: 20% by weight) was placed in a 200mL glass container: 2g of a dispersion of fibrous solid fine particles (IPA-ST-UP, average aggregate particle diameter (average primary particle diameter) of 90nm, aspect ratio of 7.0, and solid content concentration of 15% by weight, manufactured by Nissan chemical industries Co., Ltd.): 2g, ethanol: 90g, silicic acid oligomer solution (solid content concentration: 5% by weight): 6g, and stirred for 10 minutes, thereby obtaining a coating composition for forming an antireflection layer.

[ production example 16 ]: production of TAC film substrate (A) with antireflection layer

The coating composition for forming an antireflection layer obtained in production example 15 was applied to one surface of a cellulose triacetate (hereinafter, sometimes referred to as "TAC") film (TG60UL, manufactured by FUJIFILM Corporation), and the resultant film was subjected to spin coating at a rotation speed of 200rpm for 60 seconds to make uniform, and then dried at 200 ℃ for 30 minutes to form an antireflection layer having a film thickness of 100 nm. Thus, a cellulose triacetate film substrate having an antireflection layer was obtained.

[ production example 17 ]: production of PET film substrate (B) with anti-reflection layer

The coating composition for forming an antireflection layer obtained in production example 15 was applied to one surface of a polyethylene terephthalate (hereinafter, sometimes referred to as "PET") film (manufactured by lumiror U48, Toray Industries, inc.), was subjected to spin coating at a rotation speed of 200rpm for 60 seconds to uniformize the coating composition, and then dried at 200 ℃ for 30 minutes to form an antireflection layer having a film thickness of 100 nm. Thus, a polyethylene terephthalate film substrate having an anti-reflection layer was obtained.

[ production example 18 ]: production of surface protective film (C)

The (meth) acrylic adhesive composition (7) obtained in production example 13 was applied to a polyester resin substrate (trade name: "lumiror S10", thickness 38 μm, manufactured by Toray Industries, inc.) by a supply roll so that the thickness after drying was 21 μm, cured at a drying temperature of 130 ℃ for a drying time of 30 seconds, and dried. In this manner, an adhesive layer is produced on the substrate. Then, a silicone-treated surface of a release sheet (product name "MRF 25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, on which silicone treatment was applied, was bonded to the surface of the obtained pressure-sensitive adhesive layer, to obtain a surface-protecting film (C). The obtained surface protection film (C) was aged at room temperature for 7 days.

[ example 1]

The (meth) acrylic pressure-sensitive adhesive composition (1) was applied to a silicone-treated surface of a release sheet (product name "MRF 25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) composed of a polyester resin having a thickness of 25 μm, which had been silicone-treated on one surface thereof so that the thickness thereof after drying was 25 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes. In this manner, the pressure-sensitive adhesive layer formed from the (meth) acrylic pressure-sensitive adhesive composition (1) was provided on the silicone-treated surface. Next, the surface of the TAC film substrate (a) having the antireflection layer, on which the antireflection layer is not formed, is bonded to the surface of the obtained adhesive layer, thereby obtaining a reinforcing film (1). The obtained reinforcing film (1) was aged at room temperature for 7 days. The results are shown in Table 1.

[ example 2]

A reinforcing film (2) was obtained in the same manner as in example 1 except that the base material was changed to a TAC film (TG60UL, manufactured by FUJIFILM Corporation) as shown in table 1. The results are shown in Table 1.

[ example 3 ]

A reinforcing film (3) was obtained in the same manner as in example 1, except that the substrate was changed to a polyimide (hereinafter, sometimes referred to as "PI") film (Neoprene S-100, manufactured by Mitsubishi gas chemical corporation) as shown in Table 1. The results are shown in Table 1.

[ example 4 ]

A reinforcing film (4) was obtained in the same manner as in example 1, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2) as shown in table 1. The results are shown in Table 1.

[ example 5 ]

A reinforcing film (5) was obtained in the same manner as in example 2, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2) as shown in table 1. The results are shown in Table 1.

[ example 6 ]

A reinforcing film (6) was obtained in the same manner as in example 1, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to a (meth) acrylic pressure-sensitive adhesive composition (7) as shown in table 1. The results are shown in Table 1.

[ example 7 ]

A reinforcing film (7) was obtained in the same manner as in example 2, except that the (meth) acrylic adhesive composition (1) was changed to a (meth) acrylic adhesive composition (7) as shown in table 1. The results are shown in Table 1.

[ example 8 ]

A reinforcing film (8) was obtained in the same manner as in example 3, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to a (meth) acrylic pressure-sensitive adhesive composition (7) as shown in table 1. The results are shown in Table 1.

[ example 9 ]

A reinforcing film (9) was obtained in the same manner as in example 1, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to a (meth) acrylic pressure-sensitive adhesive composition (8) as shown in table 1. The results are shown in Table 1.

[ example 10 ]

A reinforcing film (10) was obtained in the same manner as in example 2, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to a (meth) acrylic pressure-sensitive adhesive composition (8) as shown in table 1. The results are shown in Table 1.

[ example 11 ]

A reinforcing film (11) was obtained in the same manner as in example 3, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to a (meth) acrylic pressure-sensitive adhesive composition (8) as shown in table 1. The results are shown in Table 1.

[ Table 1]

[ example 12 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (1) obtained in example 1, to obtain a reinforcing film (12) with a surface protection film.

[ example 13 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (2) obtained in example 2, to obtain a reinforcing film (13) with a surface protection film.

[ example 14 ]

The surface protection film (C) obtained in production example 18 was bonded to the substrate of the reinforcing film (3) obtained in example 3, to obtain a reinforcing film (14) with a surface protection film.

[ example 15 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (4) obtained in example 4, to obtain a reinforcing film (15) with a surface protection film.

[ example 16 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (5) obtained in example 5, to obtain a reinforcing film (16) with a surface protection film.

[ example 17 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (6) obtained in example 6, to obtain a reinforcing film (17) with a surface protection film.

[ example 18 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (7) obtained in example 7, to obtain a reinforcing film (18) with a surface protection film.

[ example 19 ]

The surface protection film (C) obtained in production example 18 was bonded to the substrate of the reinforcing film (8) obtained in example 8, to obtain a reinforcing film (19) with a surface protection film.

[ example 20 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (9) obtained in example 9, to obtain a reinforcing film (20) with a surface protection film.

[ example 21 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (10) obtained in example 10, to obtain a reinforcing film (21) with a surface protection film.

[ example 22 ]

The surface protection film (C) obtained in production example 18 was bonded to the base material of the reinforcing film (11) obtained in example 11, to obtain a reinforcing film (22) with a surface protection film.

[ comparative example 1]

The (meth) acrylic pressure-sensitive adhesive composition (3) was applied to a silicone-treated surface of a release sheet (product name "MRF 25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, which was silicone-treated on one surface thereof so that the thickness after drying was 25 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes. In this manner, the pressure-sensitive adhesive layer formed of the (meth) acrylic pressure-sensitive adhesive composition (3) was provided on the silicone-treated surface. Next, the surface of the TAC film substrate (a) having the antireflection layer, on which the antireflection layer was not formed, was bonded to the surface of the obtained adhesive layer, thereby obtaining a reinforcing film (C1). The obtained reinforcing film (C1) was aged at room temperature for 7 days. The results are shown in Table 2.

[ comparative example 2]

A reinforcing film (C2) was obtained in the same manner as in comparative example 1, except that the base material was changed to a TAC film (TG60UL, manufactured by FUJIFILM Corporation) as shown in table 2. The results are shown in Table 2.

[ comparative example 3 ]

A reinforcing film (C3) was obtained in the same manner as in comparative example 1, except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4) as shown in table 2. The results are shown in Table 2.

[ comparative example 4 ]

A reinforcing film (C4) was obtained in the same manner as in comparative example 2, except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (4) as shown in table 2. The results are shown in Table 2.

[ comparative example 5 ]

A reinforcing film (C5) was obtained in the same manner as in comparative example 1, except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5) as shown in table 2. The results are shown in Table 2.

[ comparative example 6 ]

A reinforcing film (C6) was obtained in the same manner as in comparative example 2, except that the (meth) acrylic pressure-sensitive adhesive composition (3) was changed to the (meth) acrylic pressure-sensitive adhesive composition (5) as shown in table 2. The results are shown in Table 2.

[ comparative example 7 ]

A reinforcing film (C7) was obtained in the same manner as in example 1, except that the substrate was changed to a PET film substrate (B) having an antireflection layer as shown in table 2. The results are shown in Table 2.

[ comparative example 8 ]

A reinforcing film (C8) was obtained in the same manner as in example 1, except that the substrate was changed to a PET film (lumiror U48, manufactured by Toray Industries, inc.) as shown in table 2. The results are shown in Table 2.

[ comparative example 9 ]

A reinforcing film (C9) was obtained in the same manner as in comparative example 7, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2) as shown in table 2. The results are shown in Table 1.

[ comparative example 10 ]

A reinforcing film (C10) was obtained in the same manner as in comparative example 8, except that the (meth) acrylic pressure-sensitive adhesive composition (1) was changed to the (meth) acrylic pressure-sensitive adhesive composition (2) as shown in table 2. The results are shown in Table 1.

[ Table 2]

Industrial applicability

The reinforcing film and the reinforcing film with a surface protective film of the present invention can be typically used in the fields of optical members and electronic members.

Description of the reference numerals

1000 reinforcing film with surface protective film

100 reinforcing film

200 surface protective film

10 substrate layer A1

20 adhesive layer A2

30 functional layer a3

40 base material layer B1

50 adhesive layer B2

60 Release sheet

70 functional layer B3

Claims

1. A reinforcing film comprising a substrate layer A1 and an adhesive layer A2,

2. The reinforcing film according to claim 1, wherein a haze change rate after 1 week of storage of the reinforcing film in an environment of 60 ℃ and 90% RH is 10.0% or less.

3. The reinforcing film according to claim 1 or 2, wherein the total light transmittance of the reinforcing film is 80% or more.

4. The reinforcing film according to any one of claims 1 to 3, wherein the adhesive strength to a PET film at a peel angle of 180 degrees and a peel speed of 300 mm/min after the adhesive layer A2 is stuck to a PET film and left at 23 ℃ for 30 minutes is 0.30N/25mm or more.

5. The reinforcing film according to any one of claims 1 to 4, which is attached to an adherend, the adherend being an optical member or an electronic member.

6. An optical member with a reinforcing film or an electronic member with a reinforcing film, comprising the reinforcing film according to any one of claims 1 to 4.

7. A reinforcing film with a surface-protecting film, which comprises a surface-protecting film on the substrate layer A1 side of the reinforcing film according to any one of claims 1 to 4.

8. A method of using a reinforcing film with a surface protective film, comprising exposing the pressure-sensitive adhesive layer A2 of the reinforcing film with a surface protective film according to claim 6 or 7, adhering the pressure-sensitive adhesive layer A2 to an adherend, and then peeling off the surface protective film.