TW202120643A - Reinforcing film - Google Patents

Abstract

A reinforcing film which can be stuck to an optical member or electronic member, and which suppresses a change in phase difference and does not reduce inspectability when said optical member or electronic member is inspected through the reinforcing film. Also provided is a reinforcing film-equipped optical member or reinforcing film-equipped electronic member which is equipped with such a reinforcing film. Further provided are a surface protection film-equipped reinforcing film obtained by providing such a reinforcing film with a surface protection film, and a method for using such a surface protection film-equipped reinforcing film. A reinforcing film according to an embodiment of the present invention which contains a substrate layer A1 and an adhesive layer A2, wherein the absolute value of the rate of change in the in-plane phase difference (R0) at a wavelength of 590nm after storing the reinforcing film in a 60 DEG C, 90%RH environment for one week is 20.0% or less.

Description

Reinforcing film

The present invention relates to a reinforcing film.

In order to impart rigidity and impact resistance to optical components and electronic components represented by organic EL (Electroluminescence) panels, LCD (liquid crystal display, liquid crystal display device) panels, touch panels, etc., the A reinforcement film is bonded to the exposed surface side of an optical member, an electronic member, etc. for reinforcement (Patent Document 1).

Furthermore, in order to prevent damage to the surface during processing, assembly, inspection, transportation, etc., the above-mentioned reinforcing film may be used in a state where a surface protection film is attached to the exposed surface of the reinforcing film in advance. When surface protection is not required, the self-reinforcing film peels off such a surface protection film (Patent Document 2).

Such a reinforcing film is attached to an optical member or an electronic member, and the optical member or an electronic member may be inspected through the reinforcing film.

However, when the reinforcing film is attached to an optical component or an electronic component and stored in a harsh environment for a long time, the phase difference of the reinforcing film will change, and therefore, the inspection performance will be reduced due to the occurrence of iris unevenness.

As mentioned above, the reinforcing film can be attached to an optical member or an electronic member and the optical member or electronic member will be inspected through it. Therefore, the key point of improvement of the reinforcing film is as follows, that is, when it is attached to an optical member or When electronic components are stored in a harsh environment for a long time, the retardation change of the reinforcing film is suppressed. Prior art literature Patent literature

Patent Document 1: Japanese Patent No. 6366199 Patent Document 2: Japanese Patent Laid-Open No. 2016-17109

[The problem to be solved by the invention]

The subject of the present invention is to provide a reinforcing film that can be attached to an optical member or an electronic member, and when the optical member or electronic member is inspected through the reinforcing film, the phase difference change is suppressed, and the inspection performance is not reduced . Furthermore, it provides an optical member with a film for reinforcement or an electronic member with a film for reinforcement which is provided with such a film for reinforcement. Furthermore, it provides a reinforcement film with a surface protection film provided with a surface protection film on such a reinforcement film, and provides a method of using the reinforcement film with a surface protection film. [Technical means to solve the problem]

The reinforcing film of the embodiment of the present invention includes a base layer A1 and an adhesive layer A2, and the reinforcing film is stored in an environment of 60°C and 90%RH for 1 week. The in-plane retardation at a wavelength of 590 nm The absolute value of the rate of change of (R _{0) is 20.0% or less.}

In one embodiment, the haze change rate after storing the above-mentioned reinforcing film in an environment of 60° C. and 90% RH for 1 week is 10.0% or less.

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

In one embodiment, the reinforcing film of the embodiment of the present invention is used when the adhesive layer A2 is attached to the PET film and placed at 23°C for 30 minutes. The peeling angle is 180 degrees and the peeling speed is 300 mm/min. Adhesion to PET film is 0.30 N/25 mm or more.

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

The optical member with a reinforcing film or the electronic member with a reinforcing film of the embodiment of the present invention includes the reinforcing film of the embodiment of the present invention.

The reinforcing film with a surface protective film of the embodiment of the present invention is provided with a surface protective film on the base layer A1 side of the reinforcing film of the embodiment of the present invention.

The method of using the reinforcing film with a surface protection film of the present invention is to expose the adhesive layer A2 included in the reinforcing film with a surface protection film of the embodiment of the present invention, and stick the adhesive layer A2 to the adhered Body, and then peel off the above-mentioned surface protective film. [Effects of Invention]

According to the present invention, it is possible to provide a reinforcing film that can be attached to an optical member or an electronic member, and when the optical member or electronic member is inspected through the reinforcing film, the phase difference change is suppressed, and the inspection performance is not reduced . In addition, it is possible to provide an optical member with a reinforcing film or an electronic member with a reinforcing film provided with such a reinforcing film. Furthermore, it is possible to provide a reinforcement film with a surface protection film provided with a surface protection film on such a reinforcement film, and provide a method of using the reinforcement film with a surface protection film.

When "mass" is expressed in this manual, it can also be renamed as "weight", which is usually used as a unit of weight. On the contrary, when "weight" is expressed in this manual, it can also be renamed as the SI system used to express weight. The "quality" of the unit.

When "(meth)acrylic acid" is expressed in this manual, it means "acrylic acid and/or methacrylic acid". When "(meth)acrylate" is expressed, it means "acrylate and/or methacrylate". ", when the expression "(meth)allyl" means "allyl and/or methallyl", when the expression "(meth) acrolein" means "acrolein and/ Or methacrolein".

"1. Reinforcing film" The reinforcing film of the present invention includes a base layer A1 and an adhesive layer A2. As long as the reinforcing film of the present invention has a base layer A1 and an adhesive layer A2, it may have any suitable other layer within a range that does not impair the effects of the present invention. Typically, the reinforcing film of the present invention includes a base layer A1 and an adhesive layer A2.

On the surface of the adhesive layer A2, for the purpose of protection, the following release sheet can also be provided.

In order to provide various functions on the surface of the base layer A1, the following functional layer A3 may be provided.

As the thickness of the reinforcing film, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. The thickness is preferably 5 μm to 800 μm, more preferably 10 μm to 650 μm, still more preferably 20 μm to 550 μm, and particularly preferably 25 μm to 450 μm.

One embodiment of the reinforcing film is shown in Fig. 1 and includes a base layer A1 (10) and an adhesive layer A2 (20).

Regarding the reinforcing film of the present invention, the absolute value of the change rate of _{the in-plane retardation (R 0} ) at a wavelength of 590 nm after storing the reinforcing film in an environment of 60° C. and 90% RH for 1 week is 20.0% Below, it is preferably 15.0% or less, more preferably 12.0% or less, still more preferably 10.0% or less, and particularly preferably 9.5% or less. If the absolute value of the rate of change of the in-plane retardation (R ₀ ) at the wavelength of 590 nm is within the above-mentioned range, a reinforcing film can be provided for inspecting optical or electronic components through the reinforcing film. Checkability will not decrease.

Regarding the reinforcing film of the present invention, the haze change rate after storing the reinforcing film in an environment of 60°C and 90%RH for 1 week is preferably 10.0% or less, more preferably 7.0% or less, and more preferably 6.0% or less, more preferably 5.0% or less, particularly preferably 4.0% or less, most preferably 3.5% or less. If the haze change rate is within the above-mentioned range, it is possible to provide a reinforcing film that does not further reduce the inspection performance when an optical member or an electronic member is inspected 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, still more preferably 85% or more, and particularly preferably 88% or more. If the total light transmittance of the reinforcing film is within the above-mentioned range, it is possible to provide a reinforcing film that does not further reduce the inspection performance when the optical member or electronic member is inspected through the reinforcing film.

<1-1. Base material layer A1> As the base material layer A1, a base material formed of any suitable material can be used according to the purpose within a range that does not impair the effects of the present invention. Examples of such materials include resin sheets, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foamed sheets, laminates of these (especially laminates containing resin sheets), and the like.

Examples of the resin constituting the resin sheet include: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polymethyl Acrylic resins such as methyl acrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfide, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene -Vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamide (aromatic polyamide), polyimide (PI), polyvinyl chloride (PVC), polyvinyl acetate , Polyphenylene sulfide (PPS), fluorine resin, polyether ether ketone (PEEK), cyclic olefin polymer, etc.

Examples of non-woven fabrics include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics containing manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics, and ester-based resin non-woven fabrics.

The base material layer A1 may be only one layer, or two or more layers.

As the thickness of the base material layer A1, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, still more preferably 15 μm to 350 μm, and particularly preferably 20 μm to 300 μm.

The total light transmittance of the substrate layer A1 is preferably 90% or more, more preferably 91% or more, still more preferably 92% or more, and particularly preferably 93% or more. If the total light transmittance of the base layer A1 is within the above-mentioned range, it is possible to provide a reinforcing film that does not further reduce the inspection performance when the optical member or electronic member is inspected through the reinforcing film.

The base material layer A1 may also contain an antistatic agent. As the base material layer A1 containing an antistatic agent, for example, a resin sheet kneaded with an antistatic agent can be used. Such a resin sheet can be formed from a composition for forming a base layer A1 containing a resin and an antistatic agent.

The base layer A1 itself can also function as an antistatic agent. For example, when metal foil is used as the material of the base layer A1, the base layer A1 itself can function as an antistatic agent.

The substrate layer A1 may be surface-treated. Examples of surface treatments include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with a primer.

As the organic coating material, for example, materials described in Plastic Hard Coating Material II (CMC Publishing, (2004)) can be cited. As such an organic coating material, a urethane-based polymer is preferable, and a polyacrylate urethane, a polyester urethane, or these precursors are more preferable. The reason is that it is easy to be applied and applied to the substrate layer A1, and various materials can be selected industrially and can be obtained economically. Examples of such a urethane-based polymer include a polymer comprising 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 also contain chain extenders such as polyamines, anti-aging agents, oxidation stabilizers, etc. as optional additives.

The base material layer A1 may also contain any suitable other additives according to the purpose within a range that does not impair the effect of the present invention.

＜1-2. Adhesive layer A2＞ As the thickness of the adhesive layer A2, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 1 μm to 300 μm, more preferably 2 μm to 250 μm, still more preferably 4 μm to 200 μm, and particularly preferably 5 μm to 150 μm.

The adhesive layer A2 may be only one layer, or two or more layers.

The adhesive layer A2 may also contain conductive components. There may be only one type of conductive component, or two or more types.

The adhesive layer A2 is attached to the PET film and placed at 23°C for 30 minutes. The peeling angle is 180 degrees and the peeling speed is 300 mm/min. The adhesion to the PET film is preferably 0.30 N/25 mm or more, more preferably It is 1 N/25 mm to 40 N/25 mm, more preferably 5 N/25 mm to 35 N/25 mm, and particularly preferably 10 N/25 mm to 30 N/25 mm.

The adhesive layer A2 is attached to the PET film and placed at 60°C for 60 minutes. The peeling angle is 180 degrees and the peeling speed is 300 mm/min. The adhesion to the PET film is preferably 10 N/25 mm or more, more preferably It is 10 N/25 mm to 40 N/25 mm, more preferably 15 N/25 mm to 35 N/25 mm, and particularly preferably 20 N/25 mm to 30 N/25 mm.

The adhesive layer A2 is formed of the adhesive composition a2. As long as it is a method that can form the adhesive composition a2 into a layer, the adhesive layer A2 can be obtained by any suitable method. For example, the adhesive layer A2 can be exemplified by the following methods: apply the adhesive composition a2 on any suitable substrate, heat, etc., active energy rays (ultraviolet rays, etc.) irradiation and drying as necessary, and make it as necessary Hardened, and an adhesive layer is formed on the substrate. Examples of such coating methods include: gravure roll coating, reverse roll coating, touch roll coating, dip roll coating, bar coating, knife coating, air knife coating, spray coating, Cut-off wheel coating, direct coating, roller brush coating and other methods.

In terms of further exhibiting the effects of the present invention, the adhesive composition a2 preferably contains a polymer component.

The polymer component is preferably at least one selected from acrylic polymers, urethane polymers, and silicone polymers. Hereinafter, an acrylic polymer will be described as a representative example.

Acrylic polymers are what can be called a so-called basic polymer in the field of acrylic adhesives. There may be only one type of acrylic polymer, or two or more types.

The content ratio of the acrylic polymer in the adhesive composition a2 is calculated in terms of solid content, and is preferably 60% by weight to 99.999% by weight, more preferably 65% by weight to 99.99% by weight, and still more preferably 70% by weight ~99.9% by weight, particularly preferably 75% to 99.9% by weight, most preferably 80% to 99.9% by weight.

As the acrylic polymer, any suitable acrylic polymer can be used within a range that does not impair the effects of the present invention.

In terms of further exhibiting the effects of the present invention, the weight average molecular weight of the acrylic polymer is preferably 300,000 to 2.5 million, more preferably 350,000 to 2 million, and still more preferably 400,000 to 1.8 million, Especially preferably, it is 500,000 to 1.5 million.

In terms of further exhibiting the effects of the present invention, the acrylic polymer is preferably an acrylic polymer formed by polymerizing the composition (A), the composition (A) comprising (a component) alkane Alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group of the base ester part, (component b) is selected from the group consisting of (meth)acrylate having OH group and (meth)acrylic acid At least one of them.

(a component) and (b component) may be only 1 type each independently, and may be 2 or more types.

Examples of alkyl (meth)acrylates having 4 to 12 carbon atoms in the alkyl ester moiety (component a) include n-butyl (meth)acrylate and isobutyl (meth)acrylate , 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Isodecyl meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. Among these, in terms of further exhibiting the effects of the present invention, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate, 2-Ethylhexyl acrylate.

As at least one (component b) selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, for example, hydroxyethyl (meth)acrylate and (meth) (Meth)acrylate, (meth)acrylic acid, etc. having OH groups such as hydroxypropyl acrylate and hydroxybutyl (meth)acrylate. Among these, in terms of further exhibiting the effects of the present invention, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred.

The composition (A) may contain copolymerizable monomers other than the (a) component and (b) component. The copolymerizable monomer may be only one type or two or more types. Examples of such copolymerizable monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. The alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms. The (meth)acrylic acid alkyl ester; itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and the anhydrides (for example, maleic anhydride, itaconic anhydride and other monomers containing acid anhydride groups ) And other monomers containing carboxyl groups (except (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(methyl) Acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, etc. Monomers containing amino groups; (meth)aminoethyl acrylate, dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate and other monomers containing amine groups; (A Monomers containing epoxy groups such as glycidyl acrylate and methyl glycidyl (meth)acrylate; monomers containing cyano groups such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidine Ketones, (meth)acrylic acid, N-vinyl piperidone, N-vinyl piperidine, N-vinyl pyrrole, N-vinylimidazole, vinyl pyridine, vinyl pyrimidine, vinyl pyridine Heterocyclic-containing vinyl monomers such as azoles; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl allyl phosphate; cyclohexyl maleimide , Isopropyl maleimide and other monomers containing iminium groups; isocyanate 2-methacryloxyethyl and other monomers containing isocyanate groups; cyclopentyl (meth)acrylate , (Meth)acrylates with alicyclic hydrocarbon groups such as cyclohexyl (meth)acrylate, iso-(meth)acrylate, etc.; phenyl (meth)acrylate, phenoxyethyl (meth)acrylate , (Meth)acrylic acid esters with aromatic hydrocarbon groups such as benzyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; ethylene, butadiene Alkenes and dienes such as olefins, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ethers; vinyl chloride, etc.

As the copolymerizable monomer, a multifunctional monomer may also be used. The multifunctional single system refers to a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenic unsaturated group, any suitable ethylenic unsaturated group can be adopted within a range that does not impair the effect of the present invention. Examples of such ethylenically unsaturated groups include radically polymerizable functional groups such as vinyl groups, propenyl groups, isopropenyl groups, vinyl ether groups (vinyloxy groups), and allyl ether groups (allyloxy groups). . Examples of polyfunctional monomers include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, three Methylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate , Polyester acrylate, acrylic urethane, etc. Such a polyfunctional monomer may be only one type, or may be two or more types.

As the copolymerizable monomer, alkoxyalkyl (meth)acrylate may also be used. Examples of alkoxyalkyl (meth)acrylates include: 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxy (meth)acrylate Triethylene glycol ester, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (meth) 4-ethoxybutyl acrylate and the like. The alkoxyalkyl (meth)acrylate may be only one type or two or more types.

In terms of further exhibiting the effect of the present invention, the content of the alkyl (meth)acrylate (component a) whose alkyl group has 4 to 12 carbon atoms in the alkyl ester moiety is relative to the content of the acrylic polymer The total amount of monomer components (100% by weight) is preferably 30% by weight or more, more preferably 35% to 99% by weight, still more preferably 40% to 98% by weight, particularly preferably 50% to 96% by weight.

In terms of further exhibiting the effects of the present invention, the content of at least one (component b) selected from the group consisting of (meth)acrylates having OH groups and (meth)acrylic acid is relative to the composition The total amount of monomer components (100% by weight) of the acrylic polymer is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, still more preferably 2% by weight to 20% by weight, and particularly preferably 3% by weight to 15% by weight.

The composition (A) may contain any suitable other ingredients within a range that does not impair the effects of the present invention. Examples of such other components include polymerization initiators, chain transfer agents, solvents, and the like. The content of these other ingredients can be any suitable content within the range that does not impair the effect of the present invention.

The polymerization initiator can be a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) according to the type of polymerization reaction. The polymerization initiator may be only one type or two or more types.

The thermal polymerization initiator is preferably used when obtaining an acrylic polymer by solution polymerization. Examples of such thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators (for example, diphenylmethyl peroxide, tertiary butyl peroxymaleate). Etc.), redox system polymerization initiator, etc. Among these thermal polymerization initiators, the azo-based initiators disclosed in Japanese Patent Laid-Open No. 2002-69411 are particularly preferred. Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator is not likely to remain in the acrylic polymer as a part of the cause of the gas generated by heating (outgassing). Examples of the azo polymerization initiator include: 2,2'-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter Sometimes called AMBN), 2,2'-azobis(2-methylpropionic acid)dimethyl, 4,4'-azobis-4-cyanovaleric acid, etc.

系光聚合起始劑等。The photopolymerization initiator is preferably used when obtaining an acrylic polymer by active energy ray polymerization. As the photopolymerization initiator, for example, benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α-ketol-based photopolymerization initiator, aromatic sulfonyl chloride-based photopolymerization initiator, Initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator , 9-oxysulfur 𠮿

Department of photopolymerization initiator and so on.

系光聚合起始劑，例如可列舉：9-氧硫𠮿

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、十二烷基9-氧硫𠮿

等。Benzoin ether-based photopolymerization initiators include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenyl Ethane-1-one, anisole methyl ether, etc. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylbenzene. Base ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. Examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1 -Ketones etc. As an aromatic sulfonyl chloride-based photopolymerization initiator, for example, 2-naphthalenesulfonyl chloride and the like can be cited. As a photoactive oxime-type photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime etc. are mentioned, for example. As the benzoin-based photopolymerization initiator, for example, benzoin and the like can be cited. As the benzyl photopolymerization initiator, for example, benzyl and the like can be cited. As the benzophenone-based photopolymerization initiator, for example, benzophenone, benzophenone benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinyl bis Benzophenone, α-hydroxycyclohexyl phenyl ketone, etc. Examples of the ketal-based photopolymerization initiator include benzyl dimethyl ketal. As 9-oxysulfur 𠮿

Is a photopolymerization initiator, for example: 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, Isopropyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, Dodecyl 9-oxysulfur 𠮿

Wait.

The adhesive composition a2 may also include a crosslinking agent. By using a crosslinking agent, the cohesive force of the acrylic adhesive can be improved, and the effect of the present invention can be further exhibited. There may be only one type of crosslinking agent, or two or more types.

As the crosslinking agent, in addition to multifunctional isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, and peroxide-based crosslinking agents, urea-based crosslinking agents and metal alkoxide-based crosslinking agents can also be cited. Crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, azoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent Wait. Among these, at least one selected from the group consisting of a multifunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent (component c) is preferred in terms of further exhibiting the effects of the present invention .

Examples of polyfunctional isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate. ; Cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-toluene diisocyanate, 2,6 -Aromatic polyisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. As the multifunctional isocyanate-based crosslinking agent, for example, trimethylolpropane/toluene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexa Methylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene Commercial products such as diisocyanate adducts (manufactured by Mitsui Chemicals Co., Ltd., trade name "Takenate 110N").

As epoxy crosslinking agents (multifunctional epoxy compounds), for example, N,N,N',N'-tetraglycidyl metaxylylenediamine, diglycidylaniline, 1,3-bis (N,N-Diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl Glycerol ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol anhydride polyglycidyl ether Glyceryl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl isocyanurate-tris(2-hydroxyethyl) isocyanurate , Resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. As the epoxy-based crosslinking agent, commercially available products such as the brand name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can also be cited.

The content of the crosslinking agent in the adhesive composition a2 can be within a range that does not impair the effect of the present invention, and any suitable content can be adopted. As such a content, in terms of further exhibiting the effects of the present invention, for example, relative to the solid content (100 parts by weight) of the acrylic polymer, it is preferably 0.005 parts by weight to 20 parts by weight, more preferably 0.05 parts by weight to 18 parts by weight, more preferably 0.01 parts by weight to 15 parts by weight, and particularly preferably 0.1 parts by weight to 10 parts by weight.

The adhesive composition a2 may contain any suitable other ingredients within a range that does not impair the effect 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 phenol, etc.), anti-aging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments or dyes, etc.), foils, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, Plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, preservatives, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

The adhesive composition a2 preferably does not contain the oligomer (X), and the oligomer (X) is obtained from a monomer composition containing an acrylic monomer having a cyclic structure of three or more rings as the main component. In this case, the content ratio of the acrylic monomer having a cyclic structure of three or more rings relative to 100 parts by weight of all monomer components contained in the monomer composition for obtaining the oligomer (X) is preferable It is 50 parts by weight or more, more preferably 60 parts by weight to 99 parts by weight, still more preferably 70 parts by weight to 98 parts by weight, and particularly preferably 80 parts by weight to 96 parts by weight. By making the adhesive composition a2 not contain the oligomer (X), it is possible to provide a reinforcing film that does not further reduce the inspection performance when inspecting optical or electronic components through the reinforcing film. The compound (X) is obtained from a monomer composition containing an acrylic monomer having a cyclic structure of three or more rings as the main component.

Examples of acrylic monomers having a cyclic structure with three or more rings include: dicyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, dicyclopentyl methacrylate, and methacrylic acid Dicyclopentyloxyethyl, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 2-methyl-2 methacrylate -Adamantyl ester, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, etc.

There may be only one type of acrylic monomer having a cyclic structure of three or more rings, or two or more types.

In the monomer composition for obtaining the oligomer (X), in addition to the acrylic monomer having a cyclic structure of three or more rings, other monomers may also be included. There may be only one type of such other monomers, or two or more types.

Examples of other monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate , Isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (meth) Heptyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Alkyl (meth)acrylates such as decyl (meth)acrylate and isodecyl (meth)acrylate; glycidyl (meth)acrylate and methylglycidyl (meth)acrylate contain epoxy groups The acrylic monomers; vinyl acetate, vinyl propionate and other vinyl ester monomers; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. Contain hydroxyl Monomers; (meth) methoxy ethyl acrylate, (meth) ethoxy ethyl acrylate and other (meth) acrylic acid alkoxy alkyl ester monomers; ethylene, propylene, isoprene, Olefin monomers such as butadiene; vinyl ether monomers such as vinyl ether, etc.

Examples of other monomers include 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, hexyl di(meth)acrylate and other multifunctional mono body.

As other monomers, monomers containing nitrogen atoms (for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tertiary (meth)acrylic acid) can also be cited. Amino alkyl (meth)acrylate monomers such as butylaminoethyl; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, (N-substituted) amide-based monomers such as acrylamide and N-hydroxy(meth)acrylamide; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; 2-methyl isocyanate Monomers containing isocyanate groups, such as propylene oxyethyl, etc.).

The adhesive composition a2 may also contain an oligomer (Y) other than the oligomer (X). However, in terms of further exhibiting the effect of the present invention, the content of the oligomer (Y) is preferably smaller.

In terms of further exhibiting the effects of the present invention, the content ratio of the oligomer (Y) in the adhesive composition a2 relative to 100 parts by weight of the acrylic polymer contained in the adhesive composition a2 is preferably It is 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 25 parts by weight or less.

The oligomer (Y) is preferably an oligomer obtained from a monomer composition containing an acrylic monomer having a cyclic structure of less than two rings as the main component, and containing relative to the monomer component The total amount of 100 parts by weight is 1 part by weight to 10 parts by weight of the carboxyl group-containing monomer.

As the cyclic structure below the bicyclic ring, any of an aromatic ring and a non-aromatic ring may be used, but a non-aromatic ring is preferred. As the aromatic ring, for example, an aromatic hydrocarbon ring (for example, a benzene ring, a condensed carbocyclic ring in naphthalene, etc.), various aromatic heterocyclic rings, and the like are mentioned. Examples of the non-aromatic ring include: non-aromatic alicyclic rings (cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; cycloolefin rings such as cyclohexene ring Rings, etc.), non-aromatic bridged rings (for example, bicyclic hydrocarbon rings in pinane, pinene, quinane, norquinane, norene, etc.), and the like.

Examples of acrylic monomers having a cyclic structure below the bicyclic ring include: (meth)cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, and (meth)(meth)acrylates such as phenyl (meth)acrylate. Aryl acrylate, phenoxyethyl (meth)acrylate and other aryloxyalkyl (meth)acrylates, benzyl (meth)acrylate and other aralkyl (meth)acrylates, styrene, α -Ethylene unsaturated monomers having a cyclic structure in the molecule, such as styrene-based monomers such as methyl styrene.

As an acrylic monomer having a cyclic structure of less than two rings, preferred examples include (meth)acrylates having non-aromatic rings, such as cyclohexyl methacrylate, iso(meth)acrylate, etc. From the viewpoint of transparency, cyclohexyl methacrylate is more preferable.

There may be only one type of acrylic monomer having a cyclic structure of less than two rings, or two or more types.

The content ratio of the acrylic monomer having a cyclic structure below two rings to 100 parts by weight of all monomer components contained in the monomer composition for obtaining the oligomer (Y) is preferably 50 parts by weight to 99 Parts by weight, more preferably 70 parts by weight to 99 parts by weight, still more preferably 80 parts by weight to 98 parts by weight, particularly preferably 90 parts by weight to 97 parts by weight, most preferably 92 parts by weight to 96 parts by weight.

The oligomer (Y) may also contain a carboxyl group-containing monomer as a monomer component. Such carboxyl group-containing monomers are the same as carboxyl group-containing monomers that can constitute acrylic polymers, for example (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. . In addition, the acid anhydrides of the monomers containing carboxyl groups (for example, monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride) can also include monomers containing carboxyl groups.

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

In the monomer composition used to obtain the oligomer (Y), in addition to the acrylic monomer having a cyclic structure of less than two rings, other monomers may also be included. There may be only one type of such other monomers, or two or more types.

Examples of other monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate , Isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (meth) Heptyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Alkyl (meth)acrylates such as decyl (meth)acrylate and isodecyl (meth)acrylate; glycidyl (meth)acrylate and methylglycidyl (meth)acrylate contain epoxy groups The acrylic monomers; vinyl acetate, vinyl propionate and other vinyl ester monomers; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc. Contain hydroxyl Monomers; (meth) methoxy ethyl acrylate, (meth) ethoxy ethyl acrylate and other (meth) acrylic acid alkoxy alkyl ester monomers; ethylene, propylene, isoprene, Olefin monomers such as butadiene; vinyl ether monomers such as vinyl ether, etc.

As other monomers, for example, hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl diacrylate, Alcohol di(meth)acrylate, pentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, two Multifunctional such as pentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di(meth)acrylate, hexyl di(meth)acrylate, etc. monomer.

As other monomers, monomers containing nitrogen atoms (for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tertiary (meth)acrylic acid) can also be cited. Amino alkyl (meth)acrylate monomers such as butylaminoethyl; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, (N-substituted) amide-based monomers such as acrylamide and N-hydroxy(meth)acrylamide; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; 2-methyl isocyanate Monomers containing isocyanate groups, such as propylene oxyethyl, etc.). However, such monomers containing nitrogen atoms will cause the adhesive to turn yellow under heating, so when it is not necessary to use it, it is better not to use it.

The oligomer (X) and the oligomer (Y) can be prepared by any suitable polymerization method within a range that does not impair the effects of the present invention. The polymerization method of acrylic polymer includes, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by ultraviolet irradiation. In terms of transparency, water resistance, cost, etc., it is preferably Solution polymerization method.

The polymerization initiator, chain transfer agent, etc. that can be used in the polymerization may be any suitable ones within a range that does not impair the effects of the present invention.

The amount of the polymerization initiator used can be any suitable amount within a range that does not impair the effect of the present invention. As such a usage amount, for example, it is preferable that it is 0.1 weight%-15 weight% with respect to the total amount of monomer components.

The use amount of the chain transfer agent can be any suitable amount within the range that does not impair the effect of the present invention. As such a usage amount, for example, it is preferable that it is 0.01 weight%-15 weight% with respect to the total amount of monomer components.

In the solution polymerization method, various common 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-heptane; cyclohexane and methylcyclohexane Alicyclic hydrocarbons such as alkanes; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. The solvent may be only one type or two or more types.

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

The weight average molecular weight of the oligomers (X) and (Y) can be controlled according to the type and amount of polymerization initiator and chain transfer agent, the temperature and time during polymerization, and the monomer concentration, monomer dropping rate, etc. .

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

The adhesive composition a2 may optionally contain ultraviolet absorbers, antioxidants, light stabilizers, anti-aging agents, adhesion imparting agents, plasticizers, softeners, fillers, colorants (pigments or dyes, etc.), and surfactants as needed , Antistatic agents and other well-known additives.

＜1-3. Peeling sheet＞ On the surface of the adhesive layer A2, for the purpose of protection, a release sheet can also be provided. The release sheet may be one layer, or two or more layers.

The thickness of the release sheet is preferably 5 μm to 300 μm, more preferably 10 μm to 200 μm, and still more preferably 10 μm to 150 μm in terms of further exhibiting the effects of the present invention. It is preferably 10 μm to 130 μm, and most preferably 20 μm to 120 μm.

The release sheet contains a resin base film.

Examples of resin base films include polyester resins including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT). The plastic film; including polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), etc. with α-olefin as monomer Composition of olefin resin plastic film; plastic film containing polyvinyl chloride (PVC); plastic film containing vinyl acetate resin; plastic film containing polycarbonate (PC); plastic film containing polyphenylene sulfide (PPS) Plastic film; plastic film containing polyamide (nylon), wholly aromatic polyamide (aromatic polyamide) and other amide resins; plastic film containing polyimide resin; containing polyether ether ketone ( PEEK) plastic film; including polyethylene (PE), polypropylene (PP) and other olefin resins; including polytetrafluoroethylene, polychlorotrifluoroethylene, polyfluoroethylene, polyvinylidene fluoride, tetrafluoroethylene Plastic films of fluorine-based resins such as ethylene-hexafluoropropylene copolymer and chlorofluoroethylene-vinylidene fluoride copolymer.

The resin base film may have only one layer, or two or more layers. The resin base film may also be stretched.

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

The resin base film may also contain any suitable additives within a range that does not impair the effects of the present invention.

In order to improve the releasability of the self-adhesive layer A2, the release sheet may have a release layer. When the release sheet has a release layer, the release layer side is directly laminated on the adhesive layer A2.

The forming material of the release layer can be any suitable forming material within a range that does not impair the effect of the present invention. Examples of such forming materials include silicone-based release agents, fluorine-based release agents, long-chain alkyl-based release agents, and fatty acid amide-based release agents. Among them, a silicone-based release agent is preferred. The release layer can be formed in the form of a coating layer.

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

The release layer may be only one layer, or two or more layers.

As the silicone release layer, for example, an addition reaction type silicone resin can be cited. Specific examples of the addition reaction type silicone resin include: KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T manufactured by Shin-Etsu Chemical Co., Ltd.; Toshiba Silicone TPR-6700, TPR-6710, TPR-6721 manufactured by the company; SD7220, SD7226 manufactured by Toray Dow Corning, etc. The coating amount of the silicone release layer (after drying) is preferably 0.01 g/m ² ～2 g/m ² , more preferably 0.01 g/m ² ～1 g/m ² , and still more preferably 0.01 g/m ² ～0.5 g/m ² .

The release layer can be formed, for example, by coating the above-mentioned forming material on any suitable layer by a previously known coating method such as reverse gravure coating, bar coating, or die coating. , Usually heat treatment at about 120-200°C to harden it. Furthermore, if necessary, active energy ray irradiation such as heat treatment and ultraviolet irradiation may be used in combination.

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 that does not impair the effect of the present invention. The thickness is preferably 1 nm to 1000 nm, more preferably 5 nm to 900 nm, still more preferably 7.5 nm to 800 nm, and particularly preferably 10 nm to 700 nm.

The antistatic layer may be only one layer, or two or more layers.

As the antistatic layer, as long as it is a layer that can exert an antistatic effect, any suitable antistatic layer can be used within a range that does not impair the effect of the present invention. As such an antistatic layer, an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer is preferable. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on a resin base film. As a specific coating method, a roll coating method, a bar coating method, a gravure coating method, etc. are mentioned.

As the conductive polymer, any suitable conductive polymer can be used within a range that does not impair the effects of the present invention. As such a conductive polymer, for example, a conductive polymer in which a π-conjugated conductive polymer is doped with a polyanion, etc. can be cited. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyethyl acrylate sulfonic acid, and polymethacrylic acid carboxylic acid. There may be only one type of conductive polymer, or two or more types.

＜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, another embodiment of the reinforcing film is shown in FIG. 2 and includes a functional layer A3 (30), a base layer A1 (10), and an adhesive layer A2 (20).

The functional layer A3 is a layer that can be set arbitrarily, and is a layer that can impart various functions to the reinforcing film.

As the thickness of the functional layer A3, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, still more preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.

The functional layer A3 may be only one layer, or two or more layers.

As the functional layer A3, any suitable functional layer can be adopted within a range that does not impair the effects of the present invention. As such a functional layer, for example, an antistatic layer, an anti-reflection layer, an anti-glare layer, a hard coat layer, etc. can be cited, and the anti-reflection layer can be selected in terms of further exhibiting the effect of the present invention.

As the anti-reflection layer, any suitable anti-reflection layer can be used within a range that does not impair the effect of the present invention. As such an anti-reflection layer, for example, the anti-reflection layer described in Japanese Patent Application Laid-Open No. 2019-144577 and the like can be cited.

As the functional layer A3, in order to exhibit an antistatic effect, an antistatic layer can also be preferably selected.

In the case of selecting both the anti-reflection layer and the anti-static layer as the functional layer A3, in terms of further exhibiting the function of the anti-reflection layer, it is preferable to arrange the anti-static layer on the base layer A1 side.

As the antistatic layer, as long as it is a layer that can exert an antistatic effect, any suitable antistatic layer can be used within a range that does not impair the effect of the present invention. As such an antistatic layer, an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on any suitable substrate layer is preferred. Specifically, for example, it is an antistatic layer formed by coating a conductive coating liquid containing a conductive polymer on the substrate layer A1. As a specific coating method, a roll coating method, a bar coating method, a gravure coating method, etc. are mentioned.

As the conductive polymer, any suitable conductive polymer can be used within a range that does not impair the effects of the present invention. As such a conductive polymer, for example, a conductive polymer in which a π-conjugated conductive polymer is doped with a polyanion, etc. can be cited. Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of polyanions include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyethyl acrylate sulfonic acid, and polymethacrylic acid carboxylic acid.

<1-5. Uses of reinforcing film, optical components with reinforcing film, electronic components with reinforcing film> The reinforcing film of the present invention is attached to an adherend as any suitable member. Typically, the reinforcing film of the present invention is attached to an adherend as an optical member or an electronic member. In this case, the exposed surface side of the adhesive layer A2 of the reinforcing film of the present invention is attached to the adherend as an optical member or an electronic member. In this way, an optical member with a reinforcing film or an electronic member with a reinforcing film of the present invention is obtained. That is, the optical member with a film for reinforcement of the present invention or an electronic member with a film for reinforcement of the present invention includes the film for reinforcement of the present invention.

"2. Surface protective film" The surface protection film is arranged on the base layer A1 side of the reinforcing film. When the base material layer A1 has the functional layer A3, a surface protective film is arranged on the functional layer A3 side.

As the thickness of the surface protection film, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, still more preferably 15 μm to 350 μm, and particularly preferably 20 μm to 300 μm.

The surface protection film includes a base material layer B1 and an adhesive layer B2. As long as the surface protection film has the base material layer B1 and the adhesive layer B2, it can have any suitable other layers within a range that does not impair the effects of the present invention.

On the surface of the adhesive layer B2, for the purpose of protection, a release sheet can also be provided.

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

As the thickness of the surface protection film, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 5 μm to 500 μm, more preferably 10 μm to 450 μm, still more preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm.

One embodiment of the surface protection film is shown in FIG. 3 and includes a base layer B1 (40), an adhesive layer B2 (50), and a release sheet (60).

One embodiment of the surface protection film is shown in FIG. 4 and includes 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 can be used according to the purpose within a range that does not impair the effects of the present invention. Examples of such a material include those exemplified in the item of <1-1. Base material layer A1>.

The base material layer B1 may have only one layer, or two or more layers.

As the thickness of the substrate layer B1, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 4 μm to 350 μm, more preferably 8 μm to 325 μm, still more preferably 12 μm to 290 μm, and particularly preferably 15 μm to 205 μm.

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

The base material layer B1 itself can 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 substrate layer B1 may be surface-treated. Examples of surface treatments include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with a primer.

Examples of the organic coating material include those exemplified in the item of <1-1. Base material layer A1>.

The base material layer B1 may also contain any suitable other additives according to the purpose within a range that does not impair the effects of the present invention.

＜2-2. Adhesive layer B2＞ As the thickness of the adhesive layer B2, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. As such a thickness, it is preferably 1 μm to 150 μm, more preferably 2 μm to 125 μm, still more preferably 3 μm to 110 μm, and particularly preferably 5 μm to 95 μm.

As the adhesive layer B2, an adhesive layer containing any suitable adhesive can be used within a range that does not impair the effect of the present invention. As such an adhesive, for example, an adhesive that constitutes an adhesive layer described in Japanese Patent Laid-Open No. 2019-127526 can be cited. Preferably, the adhesive described in the publication can be selected from acrylic adhesives and urethanes. At least one of the group consisting of ester-based adhesives and silicone-based adhesives.

＜2-3. Peeling sheet＞ On the surface of the adhesive layer B2, for the purpose of protection, a release sheet can also be provided. The release sheet may be one layer, or two or more layers.

Regarding the release sheet that the surface protective film may have, the description in the item of <1-3. Release sheet> can be cited.

＜2-4. Functional layer B3＞

The surface protection film may also include a functional layer B3, a substrate layer B1, and an adhesive layer B2 in sequence.

The functional layer B3 is a layer that can be set arbitrarily, and is a layer that can impart various functions to the reinforcing film.

As the thickness of the functional layer B3, any suitable thickness can be adopted according to the purpose within a range that does not impair the effect of the present invention. The thickness is preferably 1 nm to 1000 nm, more preferably 2 nm to 800 nm, still more preferably 5 nm to 400 nm, and particularly preferably 10 nm to 200 nm.

The functional layer B3 may be only one layer, or two or more layers.

Regarding the functional layer B3, please refer to the description in the item <1-4. Functional layer A3>.

"3. Reinforcing film with surface protective film" The reinforcing film with a surface protective film of the present invention is provided with a surface protective film on the base layer A1 side of the reinforcing film of the present invention. When the reinforcing film of the present invention further has a 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 protection film of the present invention has a reinforcing film and a surface protection film. As long as the reinforcing film with a surface protective film of the present invention has a reinforcing film and a surface protective film, it may have any suitable other layer within the range that does not impair 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 an adhesive layer A2, and the surface protective film includes a base layer B1 and an adhesive layer B2.

As the thickness of the reinforcing film with a surface protective film of the present invention, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. The thickness is preferably 9 μm to 1300 μm, more preferably 20 μm to 1050 μm, still more preferably 35 μm to 900 μm, and particularly preferably 45 μm to 750 μm.

The reinforcing film with a surface protective film of the present invention can be formed by combining the reinforcing film and the surface protective film with the base layer A1 (when the base layer A1 further has a functional layer A3, the functional layer A3) and the surface The adhesive layer B2 of the protective film (when a release sheet is provided on the adhesive layer B2, the adhesive layer B2 exposed after the release sheet is peeled off) is directly laminated to obtain it.

One embodiment of the reinforcing film with a surface protection film of the present invention is as follows: As shown in FIG. 5, a reinforcing film including a base layer A1 (10) and an adhesive layer A2 (20) and a reinforcing film including a base The surface protection film of the material layer B1 (40) and the adhesive layer B2 (50) is laminated with the substrate layer A1 (10) and the adhesive layer B2 (50) directly.

"4. Use form of reinforcing film" The reinforcing film of the present invention is typically attached to an adherend as an optical member or an electronic member. Specifically, the exposed surface of the adhesive layer A2 of the reinforcing film of the present invention is attached to the adherend as an optical member or an electronic member. When a peeling sheet is provided on the surface of the adhesive layer A2, the adhesive layer A2 exposed by peeling the peeling sheet is attached to the adherend as an optical member or an electronic member.

Examples of the above-mentioned adherend as an optical member or an electronic member include LED (Light Emitting Diode), micro LED, mini LED, and OLED (Organic Light Emitting Diode). As such an adherend, OLED is representative.

In terms of further utilizing the effect exhibited by the reinforcing film of the present invention, the above-mentioned OLED is preferably at least one selected from the group consisting of a foldable member, a flexible member, and a rollable member.

The foldable member is a (foldable) member having a movable bending portion, the flexible member is a member that can bend, and the crimpable member is a member that can be crimped.

"5. How to use the reinforcing film with surface protective film" The method of using the laminated film with surface protective film of the present invention is to expose the adhesive layer A2 of the reinforcing film with surface protective film of the present invention, attach the adhesive layer A2 to the adherend, and then peel it off Surface protection film. In the reinforcing film with a surface protection film of the present invention, when a release sheet is provided on the surface of the adhesive layer A2, first, the release sheet is peeled off to expose one of the adhesive layer surfaces of the adhesive layer A2 , Attach the surface of the adhesive layer to the adherend. Then, the surface protective film was peeled off.

In this way, a member obtained by attaching the reinforcing film to the adherend is obtained. Example

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited in any way by these examples. In addition, the test and evaluation methods in Examples etc. are as follows. Furthermore, in the case of "parts", if there is no special record, it means "parts by weight", and in the case of "%", if there is no special record, it means "weight" %".

＜Determination of weight average molecular weight＞ The weight average molecular weight is determined by the gel permeation chromatography (GPC) method. Specifically, a brand name "HLC-8120GPC" (manufactured by Tosoh Co., Ltd.) was used as a GPC measuring device, and the measurement was performed under the following conditions, and it was calculated from a standard polystyrene conversion value. (Molecular weight measurement conditions) ・Sample concentration: 0.2% by weight (tetrahydrofuran solution) ・Sample injection volume: 10 μL ・Column: Trade name "TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)" (manufactured by Tosoh Co., Ltd.) ・Reference column: brand name "TSKgel SuperH-RC (1 piece)" (manufactured by Tosoh Corporation) ・Eluent: Tetrahydrofuran (THF) ・Flow rate: 0.6 mL/min ・Detector: Differential Refractometer (RI) ・Column temperature (measurement temperature): 40°C

<The absolute value of the rate of change of the in-plane retardation at a wavelength of 590 nm> The peeling sheet was peeled from the reinforcing film obtained in the examples or comparative examples, and polarized light and a retardation measurement system (manufactured by Axometrics, "AxoScan" _{), the in-plane retardation R 0} from the substrate side was measured at a measurement wavelength of 590 nm, and it was set as the in-plane retardation R ₀ 1 (nm). Then, the reinforcing film obtained in the examples or comparative examples was stored in an environment of 60°C and 90%RH for 1 week, and then placed at 23°C for 30 minutes to return to room temperature. After peeling off the sheet, the In the same manner, the in-plane retardation R ₀ from the substrate side was measured for the remaining reinforcing film, and it was set as the in-plane retardation R ₀ 2 (nm). Using the obtained values of the in-plane phase difference R ₀ 1 (nm) and the in-plane phase difference R ₀ 2 (nm), calculate the absolute value ΔR _{0 of the} rate of change of the in-plane phase difference (R _{0) at a wavelength of 590 nm} (nm)=|(R ₀ 2－R ₀ 1)/(R ₀ 1)×100|.

＜Haze change rate＞ The peeling sheet was peeled from the reinforcing film obtained in the examples or comparative examples, and the haze was measured with a haze meter (manufactured by Murakami Color Co., Ltd., model: HM-150) to obtain the haze H1 (%). Then, the reinforcing film obtained in the examples or comparative examples was stored in an environment of 60°C and 90%RH for 1 week, and then placed at 23°C for 30 minutes to return to room temperature, and after peeling off the peeling sheet, The haze of the remaining reinforcing film was measured in the same way, and the haze H2 (%) was obtained. Using the obtained haze value, calculate the haze change rate ΔH(%)=(H2-H1)/(H1)×100.

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

＜Adhesion to PET film＞ The reinforcing film (width 25 mm × length 140 mm) from which the peeling sheet was peeled off was bonded to the glass-backed PET film "Lumirror S10#25" (Toray Co., Ltd.) with a 2 kg hand roller back and forth once. Co., Ltd. manufacture). After that, it was placed at an ambient temperature of 23°C for 30 minutes. The evaluation sample obtained in the above-mentioned manner was measured by a tensile testing machine. As the tensile tester, the trade name "Automatic Stereograph AG-X plus HS 6000 mm/min High Speed Model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions of the tensile test are as follows: peel angle: 180 degrees, peel speed (tensile speed): 300 mm/min. The load when the reinforcing film was peeled from the above-mentioned PET film was measured, and the average load at this time was used as the adhesive force of the reinforcing film to the PET film.

＜Adhesion to PET film (60℃×60 minutes after heating)＞ The reinforcing film (width 25 mm × length 140 mm) from which the peeling sheet was peeled off was reciprocated once with a 2 kg hand pressing roller and bonded to the glass-backed PET film "Lumirror S10#25" (Toray Manufactured by Co., Ltd.). After that, it was placed at an ambient temperature of 60°C for 60 minutes. The evaluation sample obtained in the above-mentioned manner was measured by a tensile testing machine. As the tensile tester, the trade name "Automatic Stereograph AG-X plus HS 6000 mm/min High Speed Model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions of the tensile test are as follows: peel angle: 180 degrees, peel speed (tensile speed): 300 mm/min. The load when the reinforcing film was peeled from the above-mentioned PET film was measured, and the average load at this time was used as the adhesive force of the reinforcing film to the PET film.

＜Uneven rainbow＞ The peeling sheet was peeled from the reinforcing film obtained in the example or the comparative example, and bonded so that the transmission axis direction of the polarizing plate was parallel to the MD direction of the film base material. The other polarizing plate is arranged on the reinforcing film so that the polarizing plate attached to the reinforcing film becomes a cross-polarized light. The fluorescent lamp light is irradiated from the underside of a polarizing plate, and the transmitted light is visually inspected to evaluate whether there is rainbow unevenness. If the rainbow unevenness is not confirmed, it is recorded as OK, and the rainbow unevenness is confirmed as NG.

[Production Example 1]: Production of (meth)acrylic polymer (1) Add 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 65 parts, N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.) into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser ): 15 parts, hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 13 parts, methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 7 parts, 2,2'-azobisiso as a polymerization initiator Butyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts, ethyl acetate: 156 parts by weight, slowly stirred and introduced nitrogen, the liquid temperature in the flask was maintained at around 63°C, polymerization reaction was carried out for 10 hours to prepare the weight average molecular weight 700,000 (meth)acrylic polymer (1) solution (solid content = 40% by weight).

[Production Example 2]: Production of (meth)acrylic polymer (2) Add butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts, acrylic acid (manufactured by Toagosei Co., Ltd.): 7.5 parts in a four-necked flask equipped with a stirring blade, thermometer, nitrogen introduction tube, and condenser, as a polymerization initiator 2,2'-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts, ethyl acetate: 156 parts by weight, slowly stir and introduce nitrogen, and keep the liquid temperature in the flask at around 63°C. The polymerization reaction was carried out for 10 hours to prepare a solution of (meth)acrylic polymer (2) with a weight average molecular weight of 700,000 (solid content = 40% by weight).

[Production Example 3]: Production of (meth)acrylic polymer (3) Add 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 96 parts, hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts in a four-necked flask equipped with a stirring blade, thermometer, nitrogen introduction tube, and condenser 2. 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts, ethyl acetate: 156 parts by weight, slowly stirred and introduced nitrogen, and the liquid temperature in the flask The temperature was maintained at around 63° C., and the polymerization reaction was carried out for 10 hours to prepare a solution of (meth)acrylic polymer (3) with a weight average molecular weight of 500,000 (solid content concentration = 40% by weight).

[Production Example 4]: Production of (meth)acrylic oligomer (4) Cyclohexyl methacrylate as a monomer component [Glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66°C]: 95 parts by weight, acrylic acid: 5 parts by weight, as 2 of chain transfer agents -Mercaptoethanol: 3 parts by weight, 2,2'-azobisisobutyronitrile as polymerization initiator: 0.2 parts by weight, and toluene as polymerization solvent: 103.2 parts by weight, put into a separable flask, and introduce nitrogen , And stir for 1 hour. In this way, after removing oxygen in the polymerization system, the temperature was raised to 70°C, and the reaction was carried out for 3 hours, and then the reaction was carried out at 75°C for 2 hours to prepare a (meth)acrylic oligomer (4) with a weight average molecular weight of 4000 Solution (solid content concentration = 50% by weight).

[Production Example 5]: Production of (meth)acrylic oligomer (5) Put 100 parts by weight of toluene and dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.) into a four-necked flask equipped with a stirring blade, thermometer, nitrogen introduction tube, condenser, and 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. Then, after stirring for 1 hour at 70°C in a nitrogen atmosphere, 0.2 parts by weight of 2,2'-azobisisobutyronitrile was added as a polymerization initiator, and the reaction was carried out at 70°C for 2 hours, and then at 80°C. After the reaction was carried out for 4 hours at °C, the reaction was carried out at 90 °C for 1 hour to prepare a solution of (meth)acrylic oligomer (5) with a weight average molecular weight of 4000 (solid content concentration = 51% by weight).

[Production Example 6]: Production of (meth)acrylic oligomer (6) Put 100 parts by weight of toluene, 40 parts by weight of methyl methacrylate (MMA), and 20 parts by weight of butyl methacrylate (BMA) into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, a condenser, and a dropping funnel. Parts, 20 parts by weight of 2-ethylhexyl methacrylate (2-EHMA), functional group equivalent of 900 g/mol containing polyorganosiloxane skeleton methacrylate monomer (trade name: X-22 -174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 17 parts by weight, functional group equivalent of 4600 g/mol containing polyorganosiloxane skeleton methacrylate monomer (trade name: X-22-174DX, Shin-Etsu Chemical Industrial Co., Ltd.) 3 parts by weight and 0.51 parts by weight of methyl thioglycolate as a chain transfer agent. Then, after stirring for 1 hour at 70°C in a nitrogen atmosphere, 0.2 parts by weight of azobisisobutyronitrile as a thermal polymerization initiator was added, and the reaction was carried out at 70°C for 2 hours, and then added as a thermal polymerization initiator. 0.1 parts by weight of azobisisobutyronitrile, and then reacted at 80°C for 5 hours to prepare a solution of (meth)acrylic oligomer (6) with a weight average molecular weight of 21,300 (solid content = 50% by weight) ).

[Production Example 7]: Production of (meth)acrylic adhesive composition (1) To the solution of the (meth)acrylic polymer (1) obtained in Production Example 1, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1) was added, and the solid content 1.0 part by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, diluted with ethyl acetate so that the total solid content becomes 25% by weight, and stirred by a disperser to prepare (former Base) 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (2) was added, and the solid content 0.075 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, and (meth)acrylic oligomer (4) obtained in Production Example 4 converted to 20 parts by weight of solid content The solution was diluted with ethyl acetate so that the solid content of the entire solution became 25% by weight, and stirred with a disperser to prepare a (meth)acrylic 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (3) was added, and the solid content Converted to 0.1 parts by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, and a solution of the (meth)acrylic oligomer (5) obtained in Production Example 5 converted to a solid content of 5 parts by weight , Dilute with ethyl acetate so that the total solid content becomes 25% by weight, and stir with a disperser 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (3) was added, and the solid content Converted to 0.1 parts by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, and 7.5 parts by weight of solid content converted to a solution of the (meth)acrylic oligomer (5) obtained in Production Example 5 , Dilute with ethyl acetate so that the total solid content becomes 25% by weight, and stir with 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (3) was added, and the solid content Converted to 0.1 parts by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, and 10 parts by weight of solid content converted to a solution of the (meth)acrylic oligomer (5) obtained in Production Example 5 , Dilute with ethyl acetate so that the total solid content becomes 25% by weight, and stir with a disperser 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (3) was added, and the solid content Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was converted to 4.0 parts by weight, diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to prepare (former Base) 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 relative to the solution of the (meth)acrylic polymer (1) was added, and the solid content A solution of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent converted into 1.0 part by weight, and a solution of the (meth)acrylic oligomer (6) obtained in Production Example 6 converted into 2.0 parts by weight of solid content It was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with 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, 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1) was added, and the solid content Converted into 2.5 parts by weight of Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, and 2.5 parts by weight of solid content converted to a solution of the (meth)acrylic oligomer (6) obtained in Production Example 6 , Dilute with ethyl acetate so that the total solid content becomes 25% by weight, and stir with a disperser to prepare a (meth)acrylic adhesive composition (8).

[Manufacturing Example 15]: Manufacturing of coating composition for forming anti-reflective layer In a 200 mL glass container, put ethanol: 60 g, water-dispersed sol of ZnO particles (average primary particle size: 20 nm, average aggregate particle size) : 40 nm, solid content conversion concentration: 20% by weight): 30 g, tetraethoxysilane (SiO ₂ solid content concentration: 29% by weight): 10 g, an aqueous ammonia solution is added to adjust the pH to 10, at 20 Stir for 6 hours at °C to obtain a dispersion of core-shell particles (solid content concentration: 6 wt%): 100 g. Add 100 g of strong acid cation exchange resin (total exchange capacity: 2.0 meq/mL or more) to the obtained dispersion of core-shell particles: 100 g, stir for 1 hour to make the pH 4, and filter to remove the strong acid cation The exchange resin is removed, and a dispersion of spherical hollow particles _{containing SiO 2 is obtained.} The obtained dispersion was concentrated by ultrafiltration to a solid content concentration of 20% by weight. Spherical hollow particles condense for the second time. The thickness of the shell of the spherical hollow particles is 5 nm, which is 1/6 of the average primary particle size. The average aggregate particle size of the spherical hollow particles is 40 nm, and the aspect ratio is 1.0. Put the obtained dispersion of spherical hollow particles (solid content: 20% by weight) in a 200 mL glass container: 2 g, dispersion of fibrous solid particles (manufactured by Nissan Chemical Industry Co., Ltd., IPA- ST-UP, average aggregate particle size (average primary particle size): 90 nm, aspect ratio: 7.0, solid content concentration: 15% by weight): 2 g, ethanol: 90 g, silicic acid oligomer solution (solid Component concentration: 5% by weight): 6 g, stirred for 10 minutes to obtain a coating composition for forming an anti-reflection layer.

[Production Example 16]: Production of TAC film substrate (A) with anti-reflection layer The coating composition for forming an anti-reflection layer obtained in Production Example 15 was applied to one side of a cellulose triacetate (hereinafter, sometimes referred to as "TAC") film (TG60UL, manufactured by Fuji Film Co., Ltd.) at a rotation speed of 200 rpm After spin coating for 60 seconds and homogenization, it was dried at 200° C. for 30 minutes to form an anti-reflection layer with a film thickness of 100 nm. In this way, a cellulose triacetate film substrate with an anti-reflection layer was obtained.

[Manufacturing Example 17]: Manufacturing of PET film substrate (B) with anti-reflection layer The coating composition for forming an anti-reflection layer obtained in Production Example 15 was applied to one side of a polyethylene terephthalate (hereinafter, sometimes referred to as "PET") film (Lumirror U48, manufactured by Toray) , Spin coating at 200 rpm for 60 seconds to homogenize, and then dry at 200°C for 30 minutes to form an anti-reflection layer with a film thickness of 100 nm. In this way, a polyethylene terephthalate film substrate with an anti-reflection layer is obtained.

[Manufacturing Example 18]: Manufacturing of surface protective film (C) The (meth)acrylic adhesive composition (7) obtained in Production Example 13 was applied to a substrate containing polyester resin (trade name: "Lumirror S10", thickness 38 μm, manufactured by Toray Corporation), cured and dried under the conditions of a drying temperature of 130°C and a drying time of 30 seconds. In this way, an adhesive layer is formed on the substrate. Then, a 25 μm thick polyester resin-containing peeling sheet (trade name "MRF25", 25 μm thick, manufactured by Mitsubishi Chemical Co., Ltd.) is attached to the surface of the obtained adhesive layer. ) The polysiloxy-treated surface to obtain a surface protective film (C). The obtained surface protective film (C) was aged at room temperature for 7 days.

[Example 1] The (meth)acrylic adhesive composition (1) was applied to a 25 μm thick release sheet containing polyester resin (trade name "MRF25", thickness 25μm, made by Mitsubishi Chemical Co., Ltd.) is cured and dried under the conditions of a drying temperature of 130°C and a drying time of 3 minutes. In this way, an adhesive layer formed of the (meth)acrylic adhesive composition (1) is provided on the silicone-treated surface. Then, the surface of the TAC film base material (A) with the anti-reflection layer on which the anti-reflection layer is not applied is attached to the surface of the obtained adhesive layer to obtain 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] As shown in Table 1, except that the base material was changed to a TAC film (TG60UL, manufactured by Fuji Film Co., Ltd.), the same procedure as in Example 1 was carried out to obtain a reinforcing film (2). The results are shown in Table 1.

[Example 3] As shown in Table 1, the base material was changed to polyimide (hereinafter, sometimes referred to as "PI") film (Neopulim S-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.), except that it was the same as in Example 1 In this way, a reinforcing film (3) is obtained. The results are shown in Table 1.

[Example 4] As shown in Table 1, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (2), it was performed in the same manner as in Example 1. Obtain a reinforcing film (4). The results are shown in Table 1.

[Example 5] As shown in Table 1, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (2), it was performed in the same manner as in Example 2. Obtain a reinforcing film (5). The results are shown in Table 1.

[Example 6] As shown in Table 1, the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (7), except that it was performed in the same manner as in Example 1. Obtain a reinforcing film (6). The results are shown in Table 1.

[Example 7] As shown in Table 1, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (7), it was performed in the same manner as in Example 2. Obtain a reinforcing film (7). The results are shown in Table 1.

[Example 8] As shown in Table 1, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (7), it was performed in the same manner as in Example 3. Obtain a reinforcing film (8). The results are shown in Table 1.

[Example 9] As shown in Table 1, the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (8), except that it was performed in the same manner as in Example 1. Obtain a reinforcing film (9). The results are shown in Table 1.

[Example 10] As shown in Table 1, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (8), it was performed in the same manner as in Example 2. Obtain a reinforcing film (10). The results are shown in Table 1.

[Example 11] As shown in Table 1, the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (8), except that it was performed in the same manner as in Example 3. Obtain a reinforcing film (11). The results are shown in Table 1.

[Table 1] Reinforcing film Reinforcing film transmittance (@580 nm) [%] Adhesion to PET film 300 mm/min [N/25 mm]-without surface protection film Adhesion to PET film at 60℃×60 minutes after 300 mm/min [N/25 mm]-without surface protection film In-plane phase difference (R ₀ )(@590 nm) [nm] Haze [%] Uneven rainbow Substrate Adhesive Polymer or oligomer (parts) Crosslinking agent (parts) With anti-reflective layer No anti-reflective layer TAC transmittance: 94.8% TAC transmittance: 92.5% PI transmittance: 89.8% (Meth) acrylic polymer (1) (Meth) acrylic polymer (2) (Meth) acrylic polymer (3) (Meth) acrylic oligomer (4) (Meth) acrylic oligomer (5) (Meth) acrylic oligomer (6) C/HL T/C Initial R ₀ 1 (%) 60℃90% R ₀ 2(%) after 1 week Change rate (absolute value) ∆R ₀ (%) Initial H1 (%) 60℃90% H2(%) after 1 week Change rate ∆H(%) Example 1 ● (Meth) acrylic adhesive composition (1) 100 - - - - - 1.0 - 94.9 13.0 - 0.77 0.71 7.79 0.60 0.61 1.7 OK Example 2 ● 92.5 14.0 - 1.50 1.40 6.67 0.60 0.61 1.7 OK Example 3 ● 89.8 14.2 - 23.56 23.19 1.57 0.45 0.46 2.2 OK Example 4 ● (Meth) acrylic adhesive composition (2) - 100 - 20 - - - 0.08 95.0 26.0 - 0.78 0.71 8.97 0.42 0.43 2.4 OK Example 5 ● 92.6 21.0 - 1.50 1.37 8.67 0.39 0.40 2.6 OK Example 6 ● (Meth) acrylic adhesive composition (7) 100 - - - - 2.0 1.0 - 94.8 1.2 22.3 0.78 0.72 7.69 0.61 0.62 1.6 OK Example 7 ● 92.4 1.2 23.2 1.51 1.41 6.62 0.61 0.62 1.6 OK Example 8 ● 89.7 1.2 24.1 23.57 23.20 1.57 0.46 0.47 2.2 OK Example 9 ● (Meth) acrylic adhesive composition (8) 100 - - - - 2.5 2.5 - 94.8 0.45 14.5 0.79 0.73 7.59 0.61 0.62 1.6 OK Example 10 ● 92.5 0.41 14.1 1.50 1.40 6.67 0.62 0.63 1.6 OK Example 11 ● 89.8 0.47 14.9 23.54 23.19 1.49 0.47 0.48 2.1 OK

[Example 12] The surface protective film (C) obtained in Manufacturing Example 18 was attached to the substrate of the reinforcing film (1) obtained in Example 1 to obtain a reinforcing film (12) with a surface protective film.

[Example 13] The surface protective film (C) obtained in Manufacturing Example 18 was attached to the substrate of the reinforcing film (2) obtained in Example 2 to obtain a reinforcing film (13) with a surface protective film.

[Example 14] The surface protective film (C) obtained in Manufacturing Example 18 was attached to the substrate of the reinforcing film (3) obtained in Example 3 to obtain a reinforcing film (14) with a surface protective film.

[Example 15] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (4) obtained in Example 4 to obtain a reinforcing film (15) with a surface protective film.

[Example 16] The surface protective film (C) obtained in Manufacturing Example 18 was attached to the substrate of the reinforcing film (5) obtained in Example 5 to obtain a reinforcing film (16) with a surface protective film.

[Example 17] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (6) obtained in Example 6 to obtain a reinforcing film (17) with a surface protective film.

[Example 18] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (7) obtained in Example 7 to obtain a reinforcing film (18) with a surface protective film.

[Example 19] The surface protective film (C) obtained in Manufacturing 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 protective film.

[Example 20] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (9) obtained in Example 9 to obtain a reinforcing film (20) with a surface protective film.

[Example 21] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (10) obtained in Example 10 to obtain a reinforcing film (21) with a surface protective film.

[Example 22] The surface protective film (C) obtained in Manufacturing Example 18 was bonded to the substrate of the reinforcing film (11) obtained in Example 11 to obtain a reinforcing film (22) with a surface protective film.

[Comparative Example 1] The (meth)acrylic adhesive composition (3) was applied to a 25 μm thick release sheet containing polyester resin (trade name) that was treated with silicone on one side so that the thickness after drying became 25 μm "MRF25", thickness 25 μm, made by Mitsubishi Chemical Co., Ltd.) is cured and dried under the conditions of a drying temperature of 130°C and a drying time of 3 minutes. In this way, an adhesive layer formed of the (meth)acrylic adhesive composition (3) is provided on the silicone-treated surface. Then, the surface of the TAC film base material (A) with the anti-reflection layer on which the anti-reflection layer is not applied is attached to the surface of the obtained adhesive layer to obtain 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] As shown in Table 2, except that the base material was changed to a TAC film (TG60UL, manufactured by Fuji Film Co., Ltd.), the same procedure as in Comparative Example 1 was carried out to obtain a reinforcing film (C2). The results are shown in Table 2.

[Comparative Example 3] As shown in Table 2, except that the (meth)acrylic adhesive composition (3) was changed to the (meth)acrylic adhesive composition (4), it was performed in the same manner as in Comparative Example 1. Obtain a reinforcing film (C3). The results are shown in Table 2.

[Comparative Example 4] As shown in Table 2, except that the (meth)acrylic adhesive composition (3) was changed to the (meth)acrylic adhesive composition (4), it was performed in the same manner as in Comparative Example 2. Obtain a reinforcing film (C4). The results are shown in Table 2.

[Comparative Example 5] As shown in Table 2, the (meth)acrylic adhesive composition (3) was changed to the (meth)acrylic adhesive composition (5), and it was performed in the same manner as in Comparative Example 1, except that the (meth)acrylic adhesive composition (3) was changed to the (meth)acrylic adhesive composition (5). Obtain a reinforcing film (C5). The results are shown in Table 2.

[Comparative Example 6] As shown in Table 2, except that the (meth)acrylic adhesive composition (3) was changed to the (meth)acrylic adhesive composition (5), it was performed in the same manner as in Comparative Example 2. Obtain a reinforcing film (C6). The results are shown in Table 2.

[Comparative Example 7] As shown in Table 2, except that the base material was changed to the PET film base material (B) having an anti-reflection layer, the same procedure as in Example 1 was carried out to obtain a reinforcing film (C7). The results are shown in Table 2.

[Comparative Example 8] As shown in Table 2, except that the base material was changed to a PET film (Lumirror U48, manufactured by Toray Co., Ltd.), the same procedure as in Example 1 was carried out to obtain a reinforcing film (C8). The results are shown in Table 2.

[Comparative Example 9] As shown in Table 2, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (2), it was performed in the same manner as in Comparative Example 7. Obtain a reinforcing film (C9). The results are shown in Table 1.

[Comparative Example 10] As shown in Table 2, except that the (meth)acrylic adhesive composition (1) was changed to the (meth)acrylic adhesive composition (2), it was performed in the same manner as in Comparative Example 8. Obtain a reinforcing film (C10). The results are shown in Table 1.

[Table 2] Reinforcing film Reinforcing film transmittance (@580 nm) [%] Adhesion to PET film 300 mm/min [N/25 mm]-without surface protection film In-plane phase difference (R ₀ )(@590 nm) [nm] Haze [%] Uneven rainbow Substrate Adhesive Polymer or oligomer (parts) Crosslinking agent (parts) With anti-reflective layer No anti-reflective layer PET transmittance: 95.1% TAC transmittance: 94.8% PET transmittance: 90.1% TAC transmittance: 92.5% PI transmittance: 89.8% (Meth) acrylic polymer (1) (Meth) acrylic polymer (2) (Meth) acrylic polymer (3) (Meth) acrylic oligomer (4) (Meth) acrylic oligomer (5) (Meth) acrylic oligomer (6) C/HL T/C Initial R ₀ 1 (%) 60℃90% R ₀ 2(%) after 1 week Change rate (absolute value) ∆R ₀ (%) Initial H1 (%) 60℃90% H2(%) after 1 week Change rate ∆H(%) Comparative example 1 ● (Meth) acrylic adhesive composition (3) - - 100 - 5 - 0.1 - 94.4 12.0 0.74 0.30 59.46 7.73 10.00 29.4 OK Comparative example 2 ● 91.3 11.0 1.63 1.28 21.47 2.86 3.35 17.1 OK Comparative example 3 ● (Meth) acrylic adhesive composition (4) - - 100 - 7.5 - 0.1 - 94.0 8.4 0.85 0.22 74.12 12.10 17.05 40.9 OK Comparative example 4 ● 91.8 13.0 1.37 0.92 32.85 17.84 20.10 12.7 OK Comparative example 5 ● (Meth) acrylic adhesive composition (5) - - 100 - 10 - 0.1 - 93.3 11.0 0.86 0.23 73.26 28.26 31.20 10.4 OK Comparative example 6 ● 90.0 9.4 1.00 0.79 21.00 11.76 13.68 16.3 OK Comparative example 7 ● (Meth) acrylic adhesive composition (1) 100 - - - - - 1.0 - 95.2 13.0 4,583.99 4,558.29 0.56 0.48 0.49 2.1 NG Comparative example 8 ● 90.2 14.0 4585.88 4,562.10 0.52 0.94 0.96 2.1 NG Comparative example 9 ● (Meth) acrylic adhesive composition (2) - 100 - 20 - - 0.08 95.1 26.0 4,612.22 4680.00 1.47 0.29 0.30 3.4 NG Comparative example 10 ● 90.3 21.0 4,614.44 4,676.39 1.34 0.80 0.82 2.5 NG [Industrial availability]

The field in which the reinforcing film of the present invention and the reinforcing film with a surface protection film can be used is typically the field of optical components and electronic components.

10: Substrate layer A1 20: Adhesive layer A2 30: Functional layer A3 40: Substrate layer B1 50: Adhesive layer B2 60: peel off sheet 70: Functional layer B3 100: Reinforcing film 200: Surface protective film 1000: Reinforcing film with surface protective film

Fig. 1 is a schematic cross-sectional view of an embodiment of a reinforcing film according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of another embodiment of the reinforcing film according to the embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of an embodiment of a surface protection film. Fig. 4 is a schematic cross-sectional view of another embodiment of the surface protection film. Fig. 5 is a schematic cross-sectional view of an embodiment of a reinforcing film with a surface protection film of the present invention.

10: Substrate layer A1

20: Adhesive layer A2

100: Reinforcing film

Claims (10)

A reinforcing film comprising a substrate layer A1 and an adhesive layer A2. After storing the reinforcing film in an environment of 60°C and 90%RH for 1 week, the in-plane retardation (R) at a wavelength of 590 nm ₀ ) The absolute value of the rate of change is 20.0% or less. Such as the reinforcing film of claim 1, wherein the above-mentioned reinforcing film has a haze change rate of 10.0% or less after being stored in an environment of 60°C and 90% RH for 1 week. Such as the reinforcing film of claim 1, wherein the total light transmittance of the above reinforcing film is 80% or more. Such as the reinforcing film of claim 2, wherein the total light transmittance of the above reinforcing film is 80% or more. The reinforcing film according to any one of claims 1 to 4, wherein the adhesive layer A2 is attached to the PET film and placed at 23°C for 30 minutes at a peeling angle of 180 degrees and a peeling speed of 300 mm/min Its adhesion to PET film is 0.30 N/25 mm or more. The reinforcing film according to any one of claims 1 to 4, which is attached to an adherend as an optical member or an electronic member. Such as the reinforcing film of claim 5, which is attached to an adherend as an optical member or an electronic member. An optical member with a reinforcing film or an electronic member with a reinforcing film, which is provided with the reinforcing film according to any one of claims 1 to 5. A reinforcing film with a surface protection film, which is provided with a surface protection film on the base layer A1 side of the reinforcing film according to any one of claims 1 to 5. A method of using a reinforcing film with a surface protection film, which exposes the adhesive layer A2 provided in the reinforcing film with a surface protection film as in claim 8 or 9, and attaches the adhesive layer A2 to the substrate Adhesive body, and then peel off the surface protection film.

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