CN117130087A

CN117130087A - Organic EL display device with protective film

Info

Publication number: CN117130087A
Application number: CN202310553731.8A
Authority: CN
Inventors: 矢野央人; 吴大钊
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2022-05-25
Filing date: 2023-05-16
Publication date: 2023-11-28
Also published as: TW202403362A; JP2023174579A; KR20230164592A

Abstract

The invention provides an organic EL display device with a protective film, which has a through hole in the surface, and is not easy to damage the vicinity of the through hole of an organic EL display panel when the protective film is peeled off. The organic EL display device with a protective film of the present invention includes a protective film and an organic EL display device, the protective film having a through hole in a plan view, the protective film being laminated on an observation side of the organic EL display device so as to be peelable, the organic EL display device including an organic EL display panel and a circularly polarizing plate laminated on the observation side of the organic EL display panel via an adhesive layer, the organic EL display panel including a main body portion and a sealing layer laminated on the observation side of the main body portion, and satisfying the formulas (1) and (2).

Description

Organic EL display device with protective film

Technical Field

The present invention relates to an organic EL display device with a protective film.

Background

Patent document 1 proposes a polarizing plate with a protective film, in which a protective film capable of being peeled off is bonded to a polarizing plate. After the polarizing plate is attached to the liquid crystal cell, the protective film is peeled off.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication 2016-170383

Disclosure of Invention

Problems to be solved by the invention

An organic EL display device used for a smart phone or the like may be provided with a through hole for a camera hole. In an organic EL display device having a through hole in a plane, when peeling off a protective film, damage (for example, peeling off a main body portion and a sealing layer) may occur in the vicinity of the through hole of an organic EL display panel.

The object of the present invention is to provide an organic EL display device with a protective film, which has a through hole in the surface and is not easy to damage the vicinity of the through hole of an organic EL display panel when the protective film is peeled off.

Means for solving the problems

The present invention provides the following organic EL display device with a protective film.

[1] An organic EL display device with a protective film, comprising a protective film and an organic EL display device,

has a through hole in a top view,

the protective film is laminated on the observation side of the organic EL display device in a peelable manner,

the organic EL display device comprises an organic EL display panel and a circularly polarizing plate laminated on the observation side of the organic EL display panel via an adhesive layer,

the organic EL display panel includes a main body and a sealing layer laminated on the viewing side of the main body,

the sealing force between the main body and the sealing layer is P _EL [N/25mm]Setting the bending rigidity of the circular polarizing plate as S _PL [N·m]The bending rigidity of the protective film is S _PF [N·m]Setting F as a peeling force when peeling the protective film from the circularly polarizing plate at a peeling speed of 18 m/min _PF [N/25mm]When the following formula is satisfied:

(1)P _EL ≤0.10[N/25mm]

(2)0.10[25mm/N]≤S _PL /(S _PF ×F _PF )。

[2] the organic EL display device with a protective film according to [1], wherein the circularly polarizing plate is a laminate of a liquid crystal cured polarizer layer and a liquid crystal cured retardation layer.

[3] The organic EL display device with a protective film according to [1] or [2], wherein the diameter of the through hole is 1mm or more.

[4] The organic EL display device with a protective film according to any one of [1] to [3], wherein a thickness of the circularly polarizing plate is 120 μm or less.

Effects of the invention

According to the present invention, it is possible to provide an organic EL display device with a protective film having a through hole in a plane, which is less likely to cause damage in the vicinity of the through hole of the organic EL display panel when the protective film is peeled off.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of the organic EL display device with a protective film according to the present invention.

Fig. 2 is a schematic plan view of the organic EL display device with a protective film of the present invention.

Fig. 3 is a schematic cross-sectional view illustrating peeling of the protective film.

Fig. 4 is a schematic cross-sectional view illustrating peeling of the protective film.

Fig. 5 is a schematic cross-sectional view showing another example of the layer structure of the organic EL display device with a protective film according to the present invention.

Fig. 6 is a schematic diagram for explaining a method of evaluating bending resistance.

Description of the reference numerals

1 organic EL display device with protective film, 10 protective film, 20 organic EL display device, 30 circular polarizing plate, 40 adhesive layer, 50 organic EL display panel, 51 sealing layer, 52 main body portion, 60, 80 linear polarizing plate, 61, 83 polarizing layer, 62, 63 protective film, 70 retardation plate, 81 hard coat layer, 82 alignment film, 84 overcoat layer, 100 stage, 200 through hole

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the scale of each component shown in the drawings is not necessarily identical to the scale of the actual component, and is appropriately adjusted for easy understanding of the components.

< organic EL display device with protective film >)

The organic EL display device with a protective film of the present invention includes a protective film and an organic EL display device, and has a through hole in a plan view. The protective film is laminated on the observation side of the organic EL display device in a peelable manner. The organic EL display device includes an organic EL display panel and a circularly polarizing plate laminated on the viewing side of the organic EL display panel via an adhesive layer. The organic EL display panel includes a main body and a sealing layer laminated on the observation side of the main body, wherein the adhesion force between the main body and the sealing layer is P _EL [N/25mm]The bending rigidity of the circular polarizing plate is S _PL [N·m]Setting the bending rigidity of the protective film as S _PF [N·m]The peeling force when peeling the protective film from the circularly polarizing plate at a speed of 18 m/min was set to F _PF [N/25mm]When the following formula is satisfied:

(1)P _EL ≤0.10[N/25mm]

(2)0.10[25mm/N]≤S _PL /(S _PF ×F _PF )。

fig. 1 shows an example of the layer structure of the organic EL display device with a protective film according to the present invention. The organic EL display device 1 with a protective film shown in fig. 1 includes a protective film 10 and an organic EL display device 20. The organic EL display device 20 includes a circularly polarizing plate 30, an adhesive layer 40, and an organic EL display panel 50. The circularly polarizing plate 30 includes a linearly polarizing plate 60 and a phase difference plate 70. The linear polarization plate 60 includes a polarization layer 61 and protective films 62 and 63. The organic EL display panel 50 includes a sealing layer 51 and a main body 52. Although not shown, the organic EL display device 1 with a protective film may further include a bonding layer for bonding the layers.

As shown in fig. 2, the organic EL display device 1 with a protective film has a through hole 200 in a plane in a plan view. The number of the through holes may be 1 or 2 or more. The diameter of the through hole may be, for example, 1mm or more, preferably 1mm or more and 50mm or less, and more preferably 1mm or more and 30mm or less.

The organic EL display device 1 with a protective film can be used as a mobile device such as a smart phone or a tablet computer, a television, a digital photo frame, an electronic billboard, a measuring instrument, office equipment, medical equipment, electronic computer equipment, or the like.

[ 1 ]

The organic EL display device 1 with a protective film is used after peeling the protective film 10 at the time of use. The protective film 10 is peeled from the organic EL display device 20 generally while maintaining its original shape. In the organic EL display device 1 with the protective film, the adhesion force P between the sealing layer 51 and the main body 52 was found _EL (hereinafter also referred to as P) _EL ) When the formula (1) is satisfied, the protective film 10 tends to be damaged easily in the vicinity of the through-hole when peeled off. P (P) _EL For example, may be 0.09[ N/25mm ]]Hereinafter, the thickness may be 0.08[ N/25mm ]]Below or 0.07[ N/25mm ]]The following is given. P (P) _EL Preferably 0.01[ N/25mm ]]The above. P (P) _EL The measurement can be performed according to the method described in the example column below.

[ 2 ]

By making the organic EL display device 1 with a protective film satisfy the formula (2), even when the formula (1) is satisfied, there is a tendency that damage is less likely to occur in the vicinity of the through-holes of the organic EL display panel when the protective film 10 is peeled off.

Peeling of the protective film will be described with reference to fig. 3. The organic EL display device with a protective film 1 shown in fig. 3 (a) includes a protective film 10 and an organic EL display device 20. As shown in fig. 3 (b), the protective film 10 is pulled up in the direction of arrow a to start peeling. Thereafter, as shown in fig. 3 (c), a peeling force is applied to the protective film 10, and the protective film 10 is peeled in the direction of arrow B. The protective film 10 peeled from the circularly polarizing plate 1 was removed. The force applied to the protective film 10 at the time of peeling may be applied by holding the end of the protective film 10 or by holding a peeling tape attached to the surface of the protective film 10.

As shown in fig. 4, it has been found that when the protective film is peeled with the peeling force F, when the force in the direction perpendicular to the film surface of the peeling force F is F t, the force in the parallel direction is F//, and the peeling angle between the end of the protective film 10 and the organic EL display device 20 is θ, the peeling force F t and the peeling angle θ are reduced, and therefore, when the protective film 10 is peeled, damage is less likely to occur in the vicinity of the through hole of the organic EL display panel 50. When the organic EL display device 1 with the protective film satisfies the formula (2), the peeling force F Σ and the peeling angle θ are liable to be reduced, and as a result, there is a tendency that damage is not liable to occur in the vicinity of the through hole of the organic EL display panel 50.

Bending stiffness S in circular polarizing plate 30 _PL (hereinafter also referred to as S _PL ) In the case of smaller amounts, the effect of the formula (2) becomes remarkable, and is preferably 10.0n·m or less, more preferably 5.0n·m or less, and still more preferably 2.0n·m or less. By making S _PL When bending is repeated, the circularly polarizing plate can be prevented from forming cracks or flaws in any layer. S is S _PL Usually 0.10 N.m or more. S is S _PF The measurement can be performed according to the method described in the example column below.

Bending stiffness S of the protective film 10 _PF (hereinafter also referred to as S _PF ) Preferably 10.0 N.m or less, more preferably 5.0 N.m or less, and even more preferably 2.0 N.m or less. S is S _PF Usually 1.0 N.m or more. S is S _PF The measurement can be performed according to the method described in the example column below.

Peel force F at the time of peeling the protective film 10 from the circularly polarizing plate 30 in the direction of arrow B at a speed of 18 m/min _PF [N/25mm](hereinafter also referred to as F) _PF ) Preferably 1.00N/25mm or less, more preferably 0.80N/25mm or less, and still more preferably 0.50N/25mm or less. F (F) _PF Typically 0.20N/25mm or more. F (F) _PF The measurement can be performed according to the method described in the example column below.

The left side of the formula (2) is preferably 0.12[25mm/N ] or more. The right side of the formula (2) is preferably 0.15[25mm/N ] or more, more preferably 2.0[25mm/N ] or more.

[ protective film ]

The surface of the protective film 10 (typically, the surface of a protective film or a hard coat layer described later) can be protected by laminating the protective film on one side of the organic EL display device 20, preferably on the linear polarization plate 60 side of the circular polarization plate 30, so as to be capable of being peeled off.

The protective film 10 is composed of, for example, a base film and an adhesive layer laminated thereon. The protective film 10 can be peeled off together with the adhesive layer provided in the protective film 10. The pressure-sensitive adhesive layer included in the protective film 10 can be described as a pressure-sensitive adhesive layer in the adhesive layer described later. Examples of the method for laminating the protective film 10 so as to be peelable include a method for adjusting the type and thickness of the pressure-sensitive adhesive layer. The thickness of the pressure-sensitive adhesive layer of the protective film 10 is preferably 2 μm or more and 30 μm or less, more preferably 5 μm or more and 20 μm or less.

The resin constituting the base film may be, for example, the following thermoplastic resin: polyethylene resins such as polyethylene; polypropylene resins such as polypropylene; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; a polycarbonate resin. Polyester resins such as polyethylene terephthalate are preferable. The thickness of the base film may be, for example, 10 μm or more and 150 μm or less, preferably 15 μm or more and 70 μm or less, and more preferably 20 μm or more and 50 μm or less.

The thickness of the protective film 10 may be, for example, 20 μm or more and 150 μm or less. When the thickness of the protective film 10 is 60 μm or more, the bending rigidity S of the protective film 10 is provided _PF Tend to increase. The thickness of the protective film 10 is preferably 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less.

[ organic EL display device ]

The organic EL display device 20 sequentially stacks a circularly polarizing plate 30, an adhesive layer 40, and an organic EL display panel 50. The circularly polarizing plate 30 may be bonded in contact with the adhesive layer 40. The organic EL display panel 50 may be attached in contact with the adhesive layer 40. The circularly polarizing plate 30 may be bonded to the sealing layer 51 side of the organic EL display panel 50 with the adhesive layer 40. The circularly polarizing plate 30 may be disposed on the viewing side of the organic EL display panel 50.

[ circular polarizing plate ]

The circularly polarizing plate 30 may include a linearly polarizing plate 60 and a phase difference plate 70. Although not shown, the linear polarization plate 60 and the phase difference plate 70 may be bonded via a bonding layer described later.

(Linear polarization plate)

The linear polarization plate 60 includes a polarization layer 61 and protective films 62 and 63. The polarizing layer 61 and the protective films 62 and 63 may be bonded via a bonding layer described later, preferably via an aqueous adhesive layer. The linear polarization plate may have a protective film on both sides of the polarization layer as shown in fig. 1, or may have a protective film on only one side of the polarization layer.

(protective film)

The protective films 62, 63 may have a function of protecting the polarizing layer 61 and the like. The protective films 62, 63 may be thermoplastic resin films having light transmittance (preferably optical transparency), and may be films containing, for example, the following resins: a polyolefin resin such as a linear polyolefin resin (polypropylene resin or the like) and a cyclic polyolefin resin (norbornene resin or the like); cellulose resins such as triacetylcellulose and diacetylcellulose; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; a polycarbonate resin; (meth) acrylic resins such as methyl methacrylate resins; a polystyrene resin; polyvinyl chloride resin; acrylonitrile-butadiene-styrene based resin; acrylonitrile-styrene resin; a polyvinyl acetate resin; polyvinylidene chloride-based resins; a polyamide resin; polyacetal resin; modified polyphenylene ether resin; polysulfone-based resin; polyether sulfone resin; polyarylate-based resins; a polyamideimide resin; polyimide resin, and the like.

Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resins (polyethylene resins as homopolymers of ethylene and copolymers mainly composed of ethylene) and polypropylene resins (polypropylene resins as homopolymers of propylene and copolymers mainly composed of propylene), and copolymers containing 2 or more chain olefins.

The cyclic polyolefin resin is a general term for a resin in which a cyclic olefin is polymerized as a polymerization unit, and examples thereof include resins described in JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Specific examples of the cyclic polyolefin resin include a ring-opened (co) polymer of a cyclic olefin, an addition polymer of a cyclic olefin, a copolymer (typically, a random copolymer) of a cyclic olefin and a chain olefin such as ethylene or propylene, a graft polymer obtained by modifying the copolymer with an unsaturated carboxylic acid or a derivative thereof, and a hydrogenated product thereof. Among them, a norbornene resin using a norbornene monomer such as norbornene and polycyclic norbornene monomer as the cyclic olefin is preferably used.

The polyester resin is a resin having an ester bond other than the cellulose ester resin described below, and is generally a resin containing a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. As the polycarboxylic acid or derivative thereof, a 2-membered dicarboxylic acid or derivative thereof may be used, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalate. As the polyhydric alcohol, a 2-membered diol may be used, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. As a representative example of the polyester resin, polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol, is given.

The (meth) acrylic resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer. Specific examples of the (meth) acrylic resin include poly (meth) acrylates such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymer; methyl methacrylate- (meth) acrylate copolymers; methyl methacrylate-acrylate- (meth) acrylic acid copolymers; methyl (meth) acrylate-styrene copolymer (MS resin, etc.); copolymers of methyl methacrylate and compounds having alicyclic hydrocarbon groups (e.g., methyl methacrylate-cyclohexyl methacrylate copolymers, methyl methacrylate- (meth) norbornyl acrylate copolymers, etc.). Preferably, poly (meth) acrylic acid C such as poly (meth) acrylic acid methyl ester is used _1-6 The polymer containing an alkyl ester as a main component is more preferably methyl methacrylate as a main component (50 mass% or more and 100 mass% or less, preferably 70 mass% or more and 1 mass% or less00 mass% or less) of a methyl methacrylate-based resin.

The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Further, copolymers thereof and resins in which a part of the hydroxyl groups is modified with other substituents may be mentioned. Among them, cellulose triacetate (triacetyl cellulose) is particularly preferable.

The polycarbonate resin is an engineering plastic comprising a polymer obtained by bonding monomer units via carbonate groups.

The thickness of the protective films 62, 63 is usually 1 μm or more and 100 μm or less, but is preferably 5 μm or more and 60 μm or less, more preferably 5 μm or more and 40 μm or less, still more preferably 10 μm or more and 20 μm or less from the viewpoints of strength, handleability and the like.

The protective films 62 and 63 may have a retardation function for the purpose of viewing angle compensation or the like, and in this case, the films themselves may have a retardation function, a retardation layer may be provided separately, or a combination of both.

The protective films 62, 63 may have ultraviolet absorption capability for the purpose of improving the light resistance of the polarizing layer 61. In this case, the film itself may have ultraviolet absorbing ability, or may have an ultraviolet absorbing layer separately, or may be a combination of both.

The protective films 62 and 63 may be made of the same kind of thermoplastic resin or different kinds of thermoplastic resin. The thicknesses may be the same or different. Further, the same phase difference characteristics may be provided, or different phase difference characteristics may be provided.

The protective films 62 and 63 may have a surface treatment layer (coating layer) such as a hard coat layer (HC layer), an antiglare layer, a light diffusion layer, an antireflection layer, a low refractive index layer, an antistatic layer, and an antifouling layer, which will be described later, on the outer surfaces thereof (surfaces opposite to the polarizing plate). The thickness of the protective film includes the thickness of the surface treatment layer.

The polarizing layer 61 and the protective films 62 and 63 are preferably bonded via an adhesive layer described later. The adhesives forming the adhesive layer may be the same type or different types. For example, the adhesive may be bonded to one surface with an aqueous adhesive and bonded to the other surface with an active energy ray-curable adhesive.

In order to improve the adhesiveness between the polarizing layer 61 and the protective films 62 and 63, the surface of each of the bonding surfaces may be subjected to a surface activation treatment described later before bonding the polarizing layer 61 to the protective films 62 and 63.

(hard coat)

The thickness of the hard coat layer (HC layer) is not particularly limited, but is preferably 2 to 100 μm, for example. If the thickness of the hard coat layer (HC layer) is less than 2 μm, it is difficult to ensure sufficient scratch resistance. On the other hand, if the thickness of the hard coat layer (HC layer) is more than 100 μm, the bending resistance may be lowered, and curling may occur due to curing shrinkage.

The hard coat layer (HC layer) can be formed by curing a composition for a hard coat layer (HC layer) containing a reactive material that forms a crosslinked structure by irradiation of active energy rays or thermal energy, and is preferably a composition cured by irradiation of active energy rays.

The active energy ray is defined as an energy ray capable of decomposing a compound that generates an active species to generate the active species. Examples of the active energy ray include visible light, ultraviolet light, infrared light, X-ray, α -ray, β -ray, γ -ray, and electron beam. Of these, ultraviolet rays are particularly preferable.

The composition for a hard coat layer (HC layer) contains at least 1 polymer of a radical polymerizable compound and a cation polymerizable compound. The radical polymerizable compound is a compound having a radical polymerizable group. The radical polymerizable group of the radical polymerizable compound may be any functional group capable of undergoing radical polymerization, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specifically, vinyl, (meth) acryl and the like are exemplified.

In the case where the radical polymerizable compound has 2 or more radical polymerizable groups, the radical polymerizable groups may be the same or different from each other. The number of radical polymerizable groups in 1 molecule of the radical polymerizable compound is preferably 2 or more in view of increasing the hardness of the hard coat layer (HC layer).

As the radical polymerizable compound, a compound having a (meth) acryloyl group is preferable from the viewpoint of high reactivity, and a compound called a polyfunctional acrylate monomer having 2 to 6 (meth) acryloyl groups in 1 molecule, an oligomer called epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, having a molecular weight of several (meth) acryloyl groups in a molecule of several hundreds to thousands, can be preferably used. Preferably, the resin composition contains 1 or more selected from epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate.

The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group. The number of the cationically polymerizable groups in 1 molecule of the cationically polymerizable compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer (HC layer). The cationically polymerizable compound is preferably a compound having at least 1 of an epoxy group and an oxetanyl group as the cationically polymerizable group.

From the viewpoint of small shrinkage accompanying polymerization, cyclic ether groups such as epoxy groups and oxetanyl groups are preferable. In addition, the compound having an epoxy group among cyclic ether groups has an advantage that it is easy to obtain various structural compounds, the durability of the resulting hard coat layer (HC layer) is not adversely affected, and the compatibility with radical polymerizable compounds is also easy to control.

Further, the oxetanyl group among the cyclic ether groups has advantages such as a higher polymerization degree than the epoxy group, low toxicity, and an acceleration of the network formation rate of the resulting hard coat layer (HC layer) from the cationically polymerizable compound, and the formation of an independent network without leaving unreacted monomers in the film even in the region where the compound is mixed with the radically polymerizable compound.

Examples of the cation polymerizable compound having an epoxy group include alicyclic epoxy resins obtained by epoxidizing polyglycidyl ethers of polyhydric alcohols having an alicyclic ring or compounds containing a cyclohexene ring or a cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid; aliphatic epoxy resins such as polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl (meth) acrylates; glycidyl ethers produced by reacting epichlorohydrin with bisphenol such as bisphenol a, bisphenol F, or hydrogenated bisphenol a, or an alkylene oxide adduct or a derivative thereof such as caprolactone adduct, or a glycidyl ether type epoxy resin derived from bisphenol as a novolac epoxy resin or the like.

The composition for a hard coat layer (HC layer) may further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical polymerization initiators, and cationic polymerization initiators, and may be appropriately selected from these. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating, and generate radicals or cations to promote radical polymerization and cationic polymerization.

The radical polymerization initiator may be any one capable of releasing a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating. Examples of the thermal radical polymerization initiator include organic peroxides such as hydrogen peroxide and perbenzoic acid, azo compounds such as azobisbutyronitrile, and the like.

Examples of the active energy ray radical polymerization initiator include a Type1 radical polymerization initiator that generates radicals by decomposition of molecules and a Type2 radical polymerization initiator that generates radicals by a hydrogen abstraction reaction in the presence of a tertiary amine, and these may be used alone or in combination.

The cationic polymerization initiator may be any one capable of releasing a substance that initiates cationic polymerization by at least one of irradiation with active energy rays and heating. As the cationic polymerization initiator, an aromatic iodonium salt, an aromatic sulfonium salt, a cyclopentadienyl iron (II) complex or the like can be used. They can initiate cationic polymerization by either irradiation with active energy rays or heating depending on the difference in structure, or can initiate cationic polymerization by either.

The polymerization initiator may be contained in an amount of 0.1 to 10% by weight relative to the whole (100% by weight) of the composition for a hard coat layer (HC layer). If the content of the polymerization initiator is less than 0.1% by weight, the curing cannot be sufficiently advanced, and it is difficult to achieve mechanical properties and adhesion of the finally obtained coating film. On the other hand, if the content of the polymerization initiator is more than 10% by weight, there are cases where adhesion failure, cracking phenomenon and curling phenomenon due to curing shrinkage occur.

The composition for a hard coat layer (HC layer) may further contain at least one selected from a solvent and an additive. The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the polymerizable compound and the polymerization initiator and known as a solvent of a composition for a hard coat layer (HC layer) in the art. The additive may further contain inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

(polarizing layer)

Examples of the polarizing layer 61 include a stretched film or a stretched layer having a dichroic dye adsorbed thereto, and a polarizing plate layer obtained by applying a dichroic dye and curing the same. When the polarizing plate layer includes a base film and an alignment film described later, the polarizing plate layer is referred to as a polarizing layer.

Specifically, iodine and a dichroic organic dye may be used as the dichroic dye. Examples of the dichroic organic dye include azo dyes. Examples of the azo dye include a dichroic direct dye containing a disazo compound such as c.i. direct RED 39 and a dichroic direct dye containing a compound such as trisazo or tetraazo.

(stretched film or stretched layer having a dichroic dye adsorbed thereto)

The stretched film having the dichroic dye adsorbed thereto can be generally produced by a process of uniaxially stretching a polyvinyl alcohol resin film, a process of adsorbing the dichroic dye by dyeing the polyvinyl alcohol resin film with the dichroic dye, a process of treating the polyvinyl alcohol resin film having the dichroic dye adsorbed thereto with an aqueous boric acid solution, and a process of washing with water after the treatment with the aqueous boric acid solution.

The thickness of the stretched film to which the dichroic dye is adsorbed may be, for example, 2 μm or more and 40 μm or less, or may be 5 μm or more and 20 μm or less, or may be 15 μm or less, or may be 10 μm or less.

The polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate resin, a copolymer of vinyl acetate and other monomer copolymerizable therewith may be used in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with an aldehyde may be used. The polymerization degree of the polyvinyl alcohol resin is usually 1000 to 10000, preferably 1500 to 5000.

The stretched layer having the dichroic dye adsorbed thereto can be generally produced by a process of applying a coating liquid containing the polyvinyl alcohol resin to a base film, a process of uniaxially stretching the obtained laminated film, a process of dyeing the uniaxially stretched laminated film polyvinyl alcohol resin layer with the dichroic dye to adsorb the dichroic dye and then producing a polarizing plate layer, a process of treating the film having the dichroic dye adsorbed thereto with an aqueous boric acid solution, and a process of washing with water after the treatment with the aqueous boric acid solution.

The base film may be peeled off from the stretched layer to which the dichroic dye is adsorbed, if necessary. The material and thickness of the base film may be the same as those of the thermoplastic resin film described later.

(polarizing plate layer obtained by coating and curing a dichroic dye)

Examples of the polarizer layer obtained by applying and curing the dichroic dye include a liquid crystal cured polarizer layer containing a cured product of a polymerizable liquid crystal compound, such as a layer obtained by applying and curing a composition containing a polymerizable liquid crystal compound and a dichroic dye to a base film. The substrate film may be provided with an alignment film on one surface. The thickness of the alignment film may be, for example, 5nm or more and 1 μm or less. By using a polarizing plate layer obtained by applying and curing a dichroic dye, end discoloration when the circularly polarizing plate is placed in a high-temperature and high-humidity environment can be suppressed.

The polarizing layer 61 may be incorporated into the linear polarizing plate 60 together with the base film, or may be incorporated into the linear polarizing plate 60 after the base film is peeled off from the polarizing plate layer formed by coating and curing the dichroic dye. As the base film, the above-described thermoplastic resin films can be used as a description of the material and thickness of the protective films 62 and 63. The base film may have the above-described hard coat layer (HC layer) formed as a protective layer on at least one surface.

The polarizer layer obtained by coating and curing the dichroic dye may have an overcoat layer (OC layer).

The thickness of the polarizing plate layer obtained by applying and curing the dichroic dye is usually 10 μm or less, preferably 8 μm or less, and more preferably 5 μm or less.

Fig. 5 shows a layer structure of the organic EL display device with a protective film in the case where the polarizing layer 61 is a polarizing plate layer formed by applying and curing a dichroic dye. The organic EL display device 3 with a protective film shown in fig. 5 includes a protective film 10 and an organic EL display device 20. The organic EL display device 20 includes a circularly polarizing plate 30, an adhesive layer 40, and an organic EL display panel 50. The circularly polarizing plate 30 includes a linearly polarizing plate 80 and a phase difference plate 70, and the linearly polarizing plate 80 includes a hard coat layer 81, an alignment film 82, a polarizing layer 83 as a liquid crystal cured polarizing plate layer, and an overcoat layer 84 in this order. The organic EL display panel 50 includes a sealing layer 51 and a main body 52. The layers may be bonded via a bonding layer (not shown) described below.

(phase plate)

The retardation plate 70 may include, for example, at least 1 retardation layer selected from the group consisting of a 1/2 wavelength retardation layer, a 1/4 wavelength retardation layer, and a positive C plate, and preferably at least 1 retardation layer selected from the group consisting of a 1/4 wavelength retardation layer and a 1/2 wavelength retardation layer. The retardation plate 70 may be, for example, a 1/2 wavelength retardation layer, a 1/4 wavelength retardation layer, a positive C plate, or a retardation layer laminate obtained by laminating these layers. When 2 or more retardation layers are laminated, the retardation layers may be bonded to each other by a bonding layer described later. The 1/4 wavelength retardation layer preferably has inverse wavelength dispersibility.

The reverse wavelength dispersibility is an optical property in which the in-plane retardation value of the liquid crystal at a short wavelength is smaller than the in-plane retardation value of the liquid crystal at a long wavelength, and the optical film preferably satisfies the following formulas (i) and (ii). Re (λ) represents an in-plane phase difference value with respect to light having a wavelength of λnm.

Re(450)/Re(550)≤1 (i)

1≤Re(630)/Re(550) (ii)

The 1/2 wavelength retardation layer is a layer in which Re (λ) =λ/2 is satisfied, and is preferably achieved at a wavelength of 550nm, among these, in any wavelength in the visible light region. In the 1/2 wavelength retardation layer, re (550) is preferably 200 nm.ltoreq.Re (550). Ltoreq.330 nm, more preferably 220 nm.ltoreq.Re (550). Ltoreq.300 nm. The 1/4 wavelength retardation layer is a layer in which Re (λ) =λ/4 is satisfied, and it is only required to be achieved at any wavelength in the visible light region, and it is preferable to be achieved at a wavelength of 550 nm. In the 1/4 wavelength retardation layer, re (550) is preferably 100 nm.ltoreq.Re (550). Ltoreq.160 nm, and Re (550) is more preferably 110 nm.ltoreq.Re (550). Ltoreq.150 nm.

When the refractive index in the slow axis direction (direction in which the refractive index in the plane is maximum) in the film plane is nx, the refractive index in the direction orthogonal to the slow axis in the plane is ny, and the refractive index in the thickness direction is nz, the positive C plate satisfies the following relationship.

nz＞nx≈ny

The above "≡" includes not only the case where the two are identical but also the case where the two are substantially identical.

When the retardation plate 70 is a retardation layer laminate, the 1 st retardation layer and the 2 nd retardation layer may be included. One of the retardation layers constituting the retardation layer laminate may be a 1/4 wavelength retardation layer, and the other may be a 1/2 wavelength retardation layer. For example, the 1 st retardation layer and the 2 nd retardation layer may be a 1/4 wavelength retardation layer and a 1/2 wavelength retardation layer, respectively. One of the retardation layers constituting the retardation layer laminate may be a 1/4 wavelength retardation layer having inverse wavelength dispersibility, and the other may be a positive C plate. For example, the 1 st phase difference layer and the 2 nd phase difference layer are respectively a 1/4 wavelength phase difference layer and a positive C plate having inverse wavelength dispersibility. The 1 st phase difference layer and the 2 nd phase difference layer may each have inverse wavelength dispersibility. The 1 st retardation layer and the 2 nd retardation layer are preferably bonded via an adhesive layer described later.

The retardation plate 70 may include a liquid crystal cured retardation layer as the retardation layer. The liquid crystal cured retardation layer is a layer having retardation characteristics, and is a layer containing a cured product of a polymerizable liquid crystal compound polymerized and cured in an aligned state. The retardation plate 70 may have only 1 liquid crystal cured retardation layer, or may have 2 or more liquid crystal cured retardation layers.

The liquid crystal cured retardation layer can be formed by coating a composition for forming a liquid crystal layer containing a polymerizable liquid crystal compound on a base film, drying the composition, and polymerizing the polymerizable liquid crystal compound. The composition for forming a liquid crystal layer may be coated on an alignment film formed on a base film. The thermoplastic resin film described above can be used as the base film.

Examples of the polymerizable liquid crystal compound include a rod-like polymerizable liquid crystal compound and a disk-like polymerizable liquid crystal compound, and one of them may be used, or a mixture containing both of them may be used. When the rod-shaped polymerizable liquid crystal compound is oriented horizontally or vertically with respect to the base film, the optical axis of the polymerizable liquid crystal compound coincides with the long axis direction of the polymerizable liquid crystal compound. When the disk-shaped polymerizable liquid crystal compound is aligned, the optical axis of the polymerizable liquid crystal compound is present in a direction perpendicular to the disk surface of the polymerizable liquid crystal compound. For example, a polymerizable liquid crystal compound described in JP-A-11-513019 (claim 1 and the like) can be suitably used as the rod-shaped polymerizable liquid crystal compound. The disk-shaped polymerizable liquid crystal compound can be suitably used as the polymerizable liquid crystal compound described in JP-A2007-108732 (paragraphs [0020] to [0067 ]), JP-A2010-244038 (paragraphs [0013] to [0108 ]).

In order to make the liquid crystal cured retardation layer formed by polymerizing the polymerizable liquid crystal compound exhibit an in-plane retardation, the polymerizable liquid crystal compound may be oriented in an appropriate direction. When the polymerizable liquid crystal compound is rod-shaped, the optical axis of the polymerizable liquid crystal compound is aligned horizontally with respect to the plane of the substrate film, whereby an in-plane retardation is exhibited, and in this case, the optical axis direction coincides with the slow axis direction. When the polymerizable liquid crystal compound has a discotic shape, the optical axis of the polymerizable liquid crystal compound is aligned horizontally with respect to the plane of the substrate film, whereby the in-plane retardation is exhibited, and in this case, the optical axis is orthogonal to the slow axis. The alignment state of the polymerizable liquid crystal compound can be adjusted by a combination of the alignment film and the polymerizable liquid crystal compound.

The polymerizable liquid crystal compound has at least 1 polymerizable group and has liquid crystallinity. In the case where 2 or more polymerizable liquid crystal compounds are used in combination, at least 1 type of polymerizable group having 2 or more in the molecule is preferable. The polymerizable group is a group participating in polymerization reaction, and is preferably a photopolymerizable group. The photopolymerizable group herein means a group capable of participating in polymerization reaction by utilizing a living radical, an acid, or the like generated by a photopolymerization initiator described later. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxiranyl, oxetanyl, styryl, and allyl groups. Among them, acryloyloxy, methacryloyloxy, ethyleneoxy, ethyleneoxide, and oxetanyl groups are preferable, and acryloyloxy is more preferable. The liquid crystallinity of the polymerizable liquid crystal compound may be either thermotropic liquid crystal or lyotropic liquid crystal, or nematic liquid crystal or smectic liquid crystal when the thermotropic liquid crystal is classified into ordered ones.

The phase difference plate 70 may include an alignment film. The alignment film has an alignment regulating force for aligning the polymerizable liquid crystal compound in a desired direction. The alignment film may be a vertical alignment film in which the molecular axis of the polymerizable liquid crystal compound is aligned vertically with respect to the base film, a horizontal alignment film in which the molecular axis of the polymerizable liquid crystal compound is aligned horizontally with respect to the base film, or an oblique alignment film in which the molecular axis of the polymerizable liquid crystal compound is oriented obliquely with respect to the base film. When the retardation plate 70 includes 2 or more alignment films, the alignment films may be the same or different from each other.

As the alignment film, an alignment film having solvent resistance that is not dissolved by application or the like of a composition for forming a liquid crystal layer containing a polymerizable liquid crystal compound and heat resistance for heat treatment for removal of a solvent and alignment of a polymerizable liquid crystal compound is preferable. Examples of the alignment film include an alignment polymer layer made of an alignment polymer, a photo-alignment polymer layer made of a photo-alignment polymer, and a groove alignment film having a concave-convex pattern and a plurality of grooves (grooves) on the layer surface.

The thickness of the liquid crystal cured retardation layer provided in the retardation plate 70 may be 0.1 μm or more, or 0.5 μm or more, or 1 μm or more, or 2 μm or more, and preferably 10 μm or less, or 8 μm or less, or 5 μm or less.

(adhesive layer)

The adhesive layer 40 may have a function of being interposed between the circularly polarizing plate 30 and the organic EL display panel 50 to join the two. The adhesive layer 40 may be described as an adhesive layer in the adhesive layer described later. The thickness of the adhesive layer 40 is preferably 5 μm or more and 70 μm or less, more preferably 10 μm or more and 50 μm or less.

(bonding layer)

The bonding layer may be an adhesive layer or an adhesive layer. The bonding layer may be, for example, a bonding of a linear polarizing plate to a retardation plate, or a bonding of a 1 st retardation layer to a 2 nd retardation layer constituting the retardation layer laminate.

The pressure-sensitive adhesive layer may be composed of a pressure-sensitive adhesive composition containing a resin such as a (meth) acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin as a main component. Among them, an adhesive composition containing a (meth) acrylic resin as a base polymer excellent in transparency, weather resistance, heat resistance and the like is suitable. The adhesive composition may be an active energy ray-curable type or a thermosetting type. The thickness of the pressure-sensitive adhesive layer is usually 3 μm or more and 30 μm or less, preferably 3 μm or more and 25 μm or less.

As the (meth) acrylic resin (base polymer) used in the adhesive composition, for example, a polymer or copolymer containing 1 or 2 or more kinds of (meth) acrylic esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate as monomers can be suitably used. The polar monomer is preferably copolymerized with the base polymer. Examples of the polar monomer include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, such as (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.

The adhesive composition may comprise only the above base polymer, but usually also contains a crosslinking agent. Examples of the crosslinking agent include a crosslinking agent that is a metal ion having a valence of 2 or more and forms a metal carboxylate between the metal ion and the carboxyl group; a crosslinking agent which is a polyamine compound and forms an amide bond with a carboxyl group; as a crosslinking agent which is a polyepoxide, a polyhydric alcohol, and forms an ester bond with a carboxyl group; as a crosslinking agent for the polyisocyanate compound and forming an amide bond with the carboxyl group. Among them, polyisocyanate compounds are preferable.

The thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more and 200 μm or less, more preferably 2 μm or more and 100 μm or less, still more preferably 2 μm or more and 80 μm or less, particularly preferably 3 μm or more and 50 μm or less.

Any suitable adhesive may be used as the adhesive constituting the adhesive layer. The adhesive may be an aqueous adhesive, an active energy ray-curable adhesive, or the like.

The thickness of the adhesive at the time of application can be set to any appropriate value. For example, the adhesive layer having a desired thickness is set so as to be obtained after curing or after heating (drying). The thickness of the adhesive layer is preferably 0.01 μm or more and 7 μm or less, more preferably 0.01 μm or more and 5 μm or less, still more preferably 0.01 μm or more and 3 μm or less, and most preferably 0.01 μm or more and 2 μm or less.

Examples of the aqueous adhesive include adhesives containing an aqueous solution of a polyvinyl alcohol resin and aqueous two-part urethane emulsion adhesives. Among them, an aqueous adhesive containing an aqueous solution of a polyvinyl alcohol resin can be suitably used. As the polyvinyl alcohol resin, a polyvinyl alcohol homopolymer obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, may be used, and a polyvinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and another monomer copolymerizable therewith, a modified polyvinyl alcohol polymer obtained by partially modifying hydroxyl groups of these, or the like may be used. The aqueous adhesive may contain a crosslinking agent such as an aldehyde compound (glyoxal or the like), an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, a polyvalent metal salt or the like.

The active energy ray-curable adhesive is an adhesive containing a curable compound that cures by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X rays, and is preferably an ultraviolet ray-curable adhesive.

The curable compound may be a cationically polymerizable curable compound or a radically polymerizable curable compound. Examples of the cationically polymerizable curable compound include an epoxy compound (a compound having 1 or 2 or more epoxy groups in the molecule), an oxetane compound (a compound having 1 or 2 or more oxetane rings in the molecule), and a combination thereof. Examples of the radically polymerizable curable compound include (meth) acrylic compounds (compounds having 1 or 2 or more (meth) acryloyloxy groups in the molecule), other vinyl compounds having radically polymerizable double bonds, and combinations thereof. A cationic polymerizable curable compound and a radical polymerizable curable compound may be used in combination. The active energy ray-curable adhesive generally further includes at least one of a cationic polymerization initiator and a radical polymerization initiator for initiating the curing reaction of the curable compound.

When an active energy ray-curable adhesive to be described later is used as the adhesive, the adhesive is cured by irradiation with active energy rays after bonding. The light source of the active energy ray is not particularly limited, but active energy rays (ultraviolet rays) having a luminescence distribution at a wavelength of 400nm or less are preferable, and specifically, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like are preferably used.

In order to improve the adhesiveness, the bonding surface of at least one of the bonding layer and the layer to be bonded may be subjected to a surface activation treatment. Examples of the surface activation treatment include dry treatments such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment and the like), ozone treatment, UV ozone treatment, and ionizing active radiation treatment (ultraviolet treatment, electron beam treatment and the like). These surface activation treatments may be performed alone or in combination of 2 or more. Among them, corona treatment is preferable. Corona treatment can be carried out, for example, at 1kJ/m ² Above and 50kJ/m ² The following output power was used. The time for performing the corona treatment may be, for example, 1 second or more and 1 minute or less.

[ organic EL display Panel ]

The organic EL display panel 50 is laminated with a sealing layer 51 and a main body 52 in this order. Although not shown, the organic EL display panel 50 may further include a touch sensor, for example, which will be described later.

The sealing layer 51 is made of a material excellent in barrier property and transparency. Examples of the material constituting the sealing layer 51 include epoxy resin, polyurea, and the like. The sealing layer 51 may be formed by applying an epoxy resin (epoxy adhesive) and adhering a barrier sheet thereto.

The sealing layer 51 may be formed directly on the main body 52, or may be bonded to the main body 52 via the bonding layer. In the case where the organic EL display panel 50 includes a touch sensor described later, the touch sensor may be formed directly on the opposite side of the sealing layer 51 from the main body 52, or may be bonded to the sealing layer 51 via the bonding layer described above. In the case where the organic EL display device 1 with a protective film includes a touch sensor, the touch sensor may be disposed between the adhesive layer 40 and the sealing layer 51.

The main body portion 52 may contain an organic EL element as a light-emitting source. The main body 52 may further include, for example, a substrate, an electrode, a planarizing layer, and an insulating layer. The organic EL element may be, for example, an element manufactured continuously by a roll-to-roll process, and may be manufactured by a method described in japanese patent application laid-open No. 2012-169236, for example.

The touch sensor is not limited in detection mode as long as it can detect a touched position, and examples thereof include a resistive film type, a capacitive type, a photo sensor type, an ultrasonic type, an electromagnetic induction coupling type, a surface elastic wave type, and the like. Among them, the capacitive touch sensor can be suitably used in terms of low cost, rapid reaction speed, and thin film.

The touch sensor may include an adhesive layer, a separation layer, a protective layer, and the like between the transparent conductive layer and the base film supporting the transparent conductive layer. The adhesive layer may be an adhesive layer or an adhesive layer. Examples of the substrate film for supporting the transparent conductive layer include a substrate film having a transparent conductive layer formed on one surface by vapor deposition, a substrate film having a transparent conductive layer transferred via an adhesive layer, and the like.

The transparent conductive layer may be a transparent conductive layer containing a metal oxide such as ITO, or may be a metal layer containing a metal such as aluminum, copper, silver, gold, or an alloy thereof. The transparent electrode layer is formed by a coating method such as sputtering, printing, vapor deposition, or the like. A photosensitive resist is formed on the transparent electrode layer, and thereafter, an electrode pattern layer is formed by photolithography. The photosensitive resist may be a negative type photosensitive resist or a positive type photosensitive resist, and may remain after the patterning or may be removed. In the case of forming a film by sputtering, a mask having an electrode pattern shape may be disposed, and sputtering may be performed to form an electrode pattern layer.

The separation layer may be a layer formed over a substrate such as glass, and the transparent conductive layer formed over the separation layer may be separated from the substrate together with the separation layer. The separation layer is preferably an inorganic layer or an organic layer. As a material for forming the inorganic layer, for example, silicon oxide is given. As a material for forming the organic layer, for example, a (meth) acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like can be used. The separation layer may be formed by coating by a known coating method and curing by a method of thermal curing or UV curing or a combination thereof.

The protective layer may be disposed in contact with the transparent conductive layer and serves to protect the conductive layer. The protective layer contains at least one of an organic insulating film and an inorganic insulating film, and these films can be formed by a coating method such as spin coating, sputtering, vapor deposition, or the like.

The insulating layer may be formed of, for example, an inorganic insulating material such as silicon oxide or a transparent organic material such as an acrylic resin. The insulating layer can be formed by applying a known coating method, and then thermally curing, UV curing, thermal drying, vacuum drying, or the like.

Examples of the substrate film of the touch sensor include resin films such as triacetylcellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene naphthalate, polyolefin, polycycloolefin, polycarbonate, polyethersulfone, polyarylate, polyimide, polyamide, polystyrene, and polynorbornene. Polyethylene terephthalate is preferably used from the viewpoint of easy formation of a base film having desired toughness.

The thickness of the base film of the touch sensor is preferably 50 μm or less, more preferably 30 μm or less, from the viewpoint of easy formation of a laminate having excellent bending resistance. The thickness of the substrate film of the touch sensor may be, for example, 5 μm or more.

The touch sensor may be manufactured as follows, for example. In method 1, a base film is first laminated on a substrate via an adhesive layer. A transparent conductive layer patterned by photolithography is formed on a base film. And heating to separate the substrate from the substrate film, thereby obtaining the touch sensor comprising the transparent conductive layer and the substrate film. The substrate is not particularly limited as long as it maintains flatness and has heat resistance, but is preferably a glass substrate.

In method 2, a material for forming a separation layer is first applied to a substrate to form a separation layer. A protective layer is formed by coating on the separation layer as needed. The protective layer may be formed in such a manner that the protective layer is not formed at a portion where the pad pattern layer is formed. A transparent conductive layer patterned by photolithography is formed on the separation layer (or the protective layer). An insulating layer is formed on the transparent conductive layer in such a manner as to fill in the electrode pattern layer. A protective film is laminated on the insulating layer by using a releasable adhesive, and the protective film is transferred from the insulating layer to the separation layer to separate the substrate. The protective film capable of peeling is peeled off, thereby obtaining a touch sensor having an insulating layer/transparent conductive layer/(protective layer)/separation layer in this order.

When the substrate film is included, the thickness of the touch sensor may be, for example, 5 μm or more and 2000 μm or less, or may be 5 μm or more and 100 μm or less.

When the base film is not included, the thickness of the touch sensor is, for example, 0.5 μm or more and 10 μm or less, preferably 5 μm or less.

[ method for manufacturing organic EL display device with protective film ]

The method for manufacturing the organic EL display device with the protective film may include, for example, the steps of:

(a) Step 1, laminating a linear polarizing plate and a phase difference plate to obtain a circular polarizing plate;

(b) A step 2 of laminating a protective film on the circularly polarizing plate obtained in the step 1 to obtain a film laminate;

(c) A step 3 of laminating an adhesive layer on the opposite side of the film laminate obtained in the step 2 to the protective film side to obtain a film laminate with an adhesive layer;

(d) A 4 th step of bonding the film laminate with an adhesive layer obtained in the 3 rd step to an organic EL display panel via the adhesive layer to obtain a film laminate with an organic EL display panel; and

(e) And 5, providing a through hole in the film laminate with the organic EL display panel obtained in the 4 th step, thereby obtaining the organic EL display device with the protective film.

(step 1)

The linear polarizing plate and the retardation plate can be manufactured as described above. The linear polarizing plate and the retardation plate can be bonded via the bonding layer. The bonding surface may be subjected to a surface activation treatment. When the bonding layer is an adhesive layer, bonding can be performed by, for example, peeling one separator from an adhesive sheet having an adhesive layer between 2 peelable separators, bonding the exposed adhesive layer to a retardation plate, and then peeling the other separator and bonding the exposed adhesive layer to a linear polarizing plate. The pressure-sensitive adhesive sheet can be formed, for example, by applying a pressure-sensitive adhesive to a releasable release film to form a pressure-sensitive adhesive layer, and bonding the release film releasable from the pressure-sensitive adhesive layer thereto.

(step 2)

The protective film can be laminated by bonding the adhesive layer side of the protective film to the linear polarizing plate side of the circularly polarizing plate obtained in step 1.

(step 3)

For example, by peeling one release film from the adhesive sheet and bonding the exposed adhesive layer to the retardation plate side of the circularly polarizing plate, the adhesive layer can be laminated.

(step 4)

The organic EL display panel may be bonded via the adhesive layer exposed by peeling the other separator from the film laminate with the adhesive layer.

(step 5)

Specific examples of the method for providing the through-holes in the film laminate with the organic EL display panel include a method for performing punching using a rotary cutting tool such as a drill. The 5 th step may be performed by stacking a plurality of film stacks each having an organic EL display panel.

Examples

The present invention will be described in further detail with reference to examples. In the examples, "%" and "parts" are mass% and parts unless otherwise indicated.

[P _EL Is (are) determined by]

The sealing layer side of the organic EL display panel (panel substitute) used in each example was bonded to alkali-free glass via an adhesive layer. By using an AUTOGRAPH analysis tester (trade name: AGS-50NX, manufactured by Shimadzu corporation), one grip portion of the AUTOGRAPH analysis tester was used to grip alkali-free glass, and the other grip portion was used to grip the body portion, and P was performed at a peeling width of 25mm, a peeling angle of 180℃and a peeling speed of 300mm/min under an atmosphere having a relative humidity of 55% at a temperature of 23 ℃ _EL Is measured.

[S _PL Is (are) determined by]

Bending stiffness S _PL The measurement was performed using a Gurley stiffness tester (manufactured by Xiong Guli machine industry) according to the procedure of the Gurley method of JIS L-1085, 1095, 1913. The circular polarizing plate was cut into a width of 25.4mm and a length of 88.9mm to prepare a sample, and the sample was fixed by using a jig disposed on a movable arm of the apparatus. Thereafter, the position of the sample was adjusted so as to contact the upper end of the measuring rocker, and the movable arm was rotated at a speed of 2rpm, thereby forming a sample on the rocker After tilting, the time when the contact point of the sample and the swinging rod is separated is taken as the maximum deflection of the sample, and the value of the graduated scale arranged at the lower part of the equipment and displayed by the pointer is read as the tilting angle of the swinging rod. At this time, the weight and the mounting position of the weight necessary for measurement are appropriately adjusted according to the deflection of the sample.

Thereafter, bending rigidity S was performed based on the following formula _PL Is calculated by:

[ number 1]

W ₁ : weight of weight in position 1'

W ₂ : weight of weight in position 2'

W ₃ : weight of weight in position 4'

R: maximum indication value of pointer

[S _PF Is (are) determined by]

Except for using a protective film instead of a circular polarizing plate, and S _PL S was measured in the same manner as in the measurement of (a) _PF 。

[F _PF Is (are) determined by]

The organic EL display device with the protective film was cut to a width of 25mm to obtain a measurement sample. The organic EL display panel side of the measurement sample was bonded to the movable stage via an adhesive using a high-speed peeling apparatus (manufactured by the product of the present application). The protective film of the measurement sample was held, and the force at the time of peeling in the 180 ° direction at a peeling speed of 18 m/min was measured, whereby the adhesion force was measured. The measurement was performed at a temperature of 23.+ -. 2 ℃ and a relative humidity of 50.+ -. 5%.

[ measurement of thickness ]

The thickness of the layer was measured using a contact film thickness measuring apparatus (Nikon "MS-5C", co., ltd.). The thickness of the aqueous adhesive layer and the polarizer were measured using a laser microscope (OlS 3000, olympic Co.).

[ evaluation of interlayer peeling ]

The occurrence of interlayer peeling was confirmed when the protective film was peeled at 18 m/min using a high-speed peeling apparatus (manufactured by the company, ltd.) equipped with a movable stage. First, samples prepared based on each example were cut into dimensions of 50×150 (mm). The movable stage and the organic EL display device are fixed by a double-sided tape (Nicetack, nichiba ltd.). Then, the protective film at the short side (50 mm) end of the sample cut in the above was attached with an adhesive tape (CT 405AP-24, manufactured by NICHIBAN Co., ltd., width 24 mm) so as to be bonded to each other in the in-plane direction by a length of 20 mm. Then, the protective film was peeled from the circular polarizing plate at a length of 10mm from the short side end using the adhesive tape, and the adhesive tape was attached to the chuck section disposed in the high-speed peeling apparatus, and the movable stage was adjusted so that 180 ° peeling was formed toward the opposite side end. Thereafter, the protective film was peeled off at a peeling rate of 18 m/min from the edge of the short side facing the opposite side by a high-speed peeling device. Visual confirmation by fluorescent lamp reflection was performed from both sides of the sample after the test, and occurrence of interlayer peeling was confirmed. For the number of tests, 3 times was performed while changing the sample.

[ observation of damp-heat resistance test and decoloration ]

The circularly polarizing plate produced and manufactured in the above was bonded to an alkali-free glass plate via an acrylic adhesive, and then left to stand in an atmosphere of 90% RH at 65℃for 500 hours. Thereafter, a polarizing plate in a relationship of crossed nicols was bonded to the alkali-free glass surface on the opposite side of the optical laminate subjected to the test, and observation was made by an optical microscope to confirm whether discoloration occurred at the end. As an optical microscope, "VHX-500" manufactured by Keyence, inc. was used. The results are shown in Table 1. The evaluation criteria are shown below.

No decolorization: a is that

The method comprises the following steps of: b (B)

[ bending resistance ]

The method for evaluating the bending resistance while referring to fig. 6 is described below. The circular polarizing plate thus produced was cut into dimensions of 10mm on the short side and 100mm on the long side using a super cutter so that the long side became the absorption axis direction of the linear polarizing plate, and was set as a test piece 300. The short side was fixed by bringing the linear polarizer side surface of the test piece into contact with the 2-piece plate jigs 301 and 302 of the bending resistance tester (fig. 6 a). The 2-plate jigs 301 and 302 are both flat-plate jigs, and are arranged parallel to each other. In the fixing, both ends of the test piece were fixed in the longitudinal direction by using a polyimide film tape (made by Toray Dupont) 303, and the distance L1 between the 2-piece plate jigs 301 and 302 was set to 53 mm. Then, when the bending radius r=1.5 mm of the test piece is set, the 2-piece plate jigs 301 and 302 are moved in directions indicated by arrows A1 and A2 (directions approaching each other), respectively, whereby the inter-jig distance L2 is continuously changed to 2R, and the fixed test piece is bent so that the absorption axis direction of the linear polarizer is orthogonal to the bending axis (fig. 6 b). The bending speed was 60rpm, and the number of times of bending until cracks were generated in the film was measured. The results are shown in Table 1. The evaluation criteria are shown below.

The number of bends is greater than 25000: a is that

The bending times are 5000-25000 times: b (B)

The number of bends is less than 5000: c (C)

[ production of protective film (A) ]

(preparation of adhesive composition (1))

Nitrogen was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and the air in the reaction apparatus was replaced with nitrogen. Thereafter, 93 parts of 2-ethylhexyl acrylate, 5.5 parts of 8-hydroxyoctyl acrylate, and 1.5 parts of acrylic acid were added to the reaction apparatus, and 60 parts of a solvent (ethyl acetate) was added. Thereafter, 0.1 part of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and a reaction was performed at 65℃for 6 hours to obtain an acrylic resin solution (1). The weight average molecular weight of the acrylic polymer contained in the acrylic resin solution (1) was about 50 ten thousand in terms of standard polystyrene based on gel permeation chromatography.

After adding 2.0 parts of 1-octylpyridinium dodecylbenzenesulfonate as an antistatic agent to 100 parts of the acrylic polymer contained in the acrylic resin solution (1) and stirring, 1.5 parts of coronete HX (isocyanurate of hexamethylene diisocyanate compound: manufactured by TOHSO corporation) was added and stirred and mixed to obtain an adhesive composition (1).

(production of protective film (A) with Release film)

The adhesive composition (1) was applied to a release film having a thickness of 15 μm formed from a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90℃to remove the solvent, thereby forming a 2 nd adhesive layer having a thickness of 15 μm after drying. Thereafter, a polyethylene terephthalate (PET) film having a thickness of 75 μm, which had been subjected to antistatic treatment and antifouling treatment on one surface, was used as the 1 st base film, and the surface of the PET film opposite to the surface subjected to antistatic treatment and antifouling treatment was laminated on the 2 nd adhesive layer to obtain a barrier film (a) with a barrier film. The layer structure of the protective film (a) with a release film is the protective film (a) (1 st base film/2 nd adhesive layer)/release film.

[ production of protective film (B) ]

A protective film (B) with a separator was obtained by the same procedure as in the production of the surface protective film (1) with a separator except that a polyethylene terephthalate (PET) film having a thickness of 38 μm, on one surface of which antistatic treatment and antifouling treatment were performed, was used as the 1 st base film. The layer structure of the protective film (2) with a release film is the protective film (B) (1 st base film/2 nd adhesive layer)/release film.

[ production of protective film (C) ]

The protective film (C) was obtained by the same method as the protective film D described in the specification of Japanese patent application laid-open No. 2018-173550 (paragraph [0113 ]).

[ production of protective film (D) ]

A protective film (D) was obtained in the same manner as in the protective film (C), except that a polyethylene terephthalate (PET) film having a thickness of 75 μm was used, on one surface of which no antistatic treatment or antifouling treatment was performed.

Production example 1: production of Linear polarization plate A

A polyvinyl alcohol film having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% or more and a thickness of 30 μm was immersed in pure water at 30 ℃ and then immersed in iodine: potassium iodide: the mass ratio of water is 0.02:2: iodine staining was performed in an aqueous solution at 30℃of 100 (hereinafter also referred to as iodine staining step.). Immersing the polyvinyl alcohol film subjected to the iodine dyeing process in potassium iodide: boric acid: the mass ratio of water is 12:5:100 in an aqueous solution at 56.5 ℃ to carry out boric acid treatment (hereinafter also referred to as a boric acid treatment step). The polyvinyl alcohol film subjected to the boric acid treatment step was washed with pure water at 8℃and dried at 65℃to obtain a polarizing plate (thickness 12 μm after stretching) having iodine adsorbed and oriented to polyvinyl alcohol. At this time, stretching is performed in the iodine dyeing step and the boric acid treatment step. The total stretch ratio of the stretch was 5.3 times.

A water-based adhesive was applied to one side of the polarizer, and a triacetyl cellulose (TAC) film (thickness: 25 μm) was attached thereto after corona treatment. Then, a water-based adhesive layer was applied to the opposite side of the polarizing plate to the TAC film side to which the lamination was performed, and a triacetyl cellulose (TAC) film (thickness: 32 μm) with a hard coat layer was laminated after corona treatment, to prepare a linear polarizing plate a.

Production example 2: production of Linear polarization plate B

A water-based adhesive was applied to one side of the polarizing plate produced in production example 1, and a hard-coated cyclic polyolefin resin (COP) film (thickness: 52 μm) was laminated after corona treatment to produce a linear polarizing plate B.

Production example 3: production of Linear polarization plate C

(substrate film)

A triacetyl cellulose (TAC) film (25 μm thick, manufactured by Konica Minolta Co., ltd.) was prepared as a base film.

(composition for Forming an alignment film)

The polymer 1 is a polymer having a photoreactive group including the following structural unit.

[ chemical 1]

The molecular weight of the resulting polymer 1 was determined by GPC and found to be number average molecular weight 28200, mw/Mn was 1.82 and the monomer content was 0.5%.

A solution obtained by dissolving polymer 1 in cyclopentanone at a concentration of 5 mass% was used as the composition for forming an alignment film.

(polymerizable liquid Crystal Compound)

The polymerizable liquid crystal compound represented by the formula (1-6) [ hereinafter also referred to as compound (1-6) ] and the polymerizable liquid crystal compound represented by the formula (1-7) [ hereinafter also referred to as compound (1-7) ].

[ chemical 2]

[ chemical 3]

Compounds (1-6) and (1-7) were synthesized using the methods described in Lub et al, recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

(dichromatic pigment)

As the dichroic dye, an azo dye described in examples of Japanese patent application laid-open No. 2013-101328 represented by the following formulas (2-1 a), (2-1 b) and (2-3 a) is used.

[ chemical 4]

[ chemical 5]

[ chemical 6]

(composition for Forming Linear polarization layer)

The composition for forming a linearly polarized layer was prepared by mixing 75 parts by mass of compound (1-6), 25 parts by mass of compound (1-7), 2.5 parts by mass of each azo dye represented by the above-mentioned formulas (2-1 a), (2-1 b) and (2-3 a) as a dichroic dye, 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369, manufactured by BASF JAPAN company) as a polymerization initiator, and 1.2 parts by mass of polyacrylate compound (manufactured by BYK-361N, BYK-Chemie company) as a leveling agent in 400 parts by mass of toluene as a solvent, and stirring the resultant mixture at 80 ℃ for 1 hour.

(composition for protective layer (OC layer))

The composition for protective layer was prepared by mixing 3 parts by mass of polyvinyl alcohol resin powder (manufactured by Kuraray, average polymerization degree 18000, trade name: KL-318) and 1.5 parts by mass of polyamide epoxy resin (cross-linking agent, manufactured by Sumika Chemtex Co., ltd., trade name: SR650 (30)) with respect to 100 parts by mass of water.

(production of Linear polarization plate C)

Corona treatment is applied to the substrate film. The conditions for the corona treatment were set to an output of 0.3kW and a treatment speed of 3 m/min. Thereafter, the composition for forming an alignment film was applied to the base film by a bar coating method, and dried by heating in a drying oven at 80℃for 1 minute. The obtained dried film was subjected to polarized UV irradiation treatment to form an alignment film. The cumulative light amount measured at 365nm was 100mJ/cm by passing light emitted from a UV irradiation device (SPOTCURE SP-7; manufactured by USHIO Motor Co., ltd.) through a wire grid (UIS-27132 #, manufactured by USHIO Motor Co., ltd.) ² Is subjected to polarized UV treatment. The thickness of the alignment film was 100nm.

The composition for forming a linearly polarized layer was applied to the formed alignment film by a bar coating method, and after drying by heating in a drying oven at 120℃for 1 minute, it was cooled to room temperature. Using the above UV irradiation apparatus to accumulate a light quantity of 1200mJ/cm ² Ultraviolet rays were irradiated to the dried film (365 nm basis), thereby forming linear polarizationA layer. The thickness of the obtained linearly polarized layer was measured by a laser microscope (OLS 3000, olympic Co., ltd.) and found to be 1.8. Mu.m. The laminate comprising "substrate film/alignment film/linear polarization layer" was obtained by the operation described above.

The composition for a protective layer (OC layer) was applied to the linearly polarized layer formed by a bar coating method so that the thickness after drying was 1.0 μm, and dried at 80 ℃ for 3 minutes. The operation as described above gave a linear polarizing plate C comprising "substrate film/alignment film/linear polarizing layer/protective layer (OC layer)".

Production example 4: production of Linear polarization plate D ]

(substrate film)

A polyethylene terephthalate (PET) film (thickness 100 μm) was prepared as a base film.

(composition for protective layer (HC layer))

A composition for a protective layer (HC layer) was prepared by mixing 2.8 parts by mass of 18-functional acryl-containing dendrimer acrylate (Miramer SP1106, miwon), 6.6 parts by mass of 6-functional acryl-containing urethane acrylate (Miramer PU-620D, miwon), 0.5 part by mass of photopolymerization initiator (Irgacure-184, BASF), 0.1 part by mass of leveling agent (BYK-3530, BYK) and 90 parts by mass of Methyl Ethyl Ketone (MEK).

The composition for forming an alignment film, the composition for forming a linearly polarizing layer, and the composition for forming a protective layer (OC layer) are each the composition described in the above item [ linearly polarizing plate C ].

(production of Linear polarization plate D)

The composition for the protective layer (HC layer) was applied to the base film by a bar coating method, and dried by heating in a drying oven at 80 ℃ for 3 minutes. The obtained dried film was irradiated with a UV irradiation apparatus (SPOTCURE SP-7, manufactured by USHIO Motor Co., ltd.) at an exposure of 500mJ/cm ² (365 nm basis) UV light to form a protective layer (HC layer). The thickness of the protective layer (HC layer) was measured by a laser microscope (OLS 3000 manufactured by Olympic Co., ltd.) and found to be 2.0. Mu.m. The laminate containing the "base film/protective layer (HC layer)" was obtained by the operation described above.

The protective layer (HC layer) side of the laminate containing the "base film/protective layer (HC layer)" was subjected to corona treatment 1 time. The conditions for the corona treatment were set to an output of 0.3kW and a treatment speed of 3 m/min. Thereafter, the composition for forming an alignment film was applied onto the protective layer (HC layer) by a bar coating method, and dried by heating in a drying oven at 80 ℃ for 1 minute. The obtained dried film was subjected to polarized UV irradiation treatment to form a 1 st alignment film. The cumulative light amount measured at 365nm was 100mJ/cm by passing light emitted from a UV irradiation device (SPOTCURE SP-7; manufactured by USHIO Motor Co., ltd.) through a wire grid (UIS-27132 #, manufactured by USHIO Motor Co., ltd.) ² Is subjected to polarized UV treatment. The thickness of the alignment film was 100nm.

The composition for forming a linearly polarized layer was applied to the formed alignment film by a bar coating method, and after drying by heating in a drying oven at 120℃for 1 minute, it was cooled to room temperature. Using the above UV irradiation apparatus to accumulate a light quantity of 1200mJ/cm ² (365 nm reference) irradiating ultraviolet rays to the dried film, thereby forming a linearly polarized layer. The thickness of the obtained linearly polarized layer was measured by a laser microscope (OLS 3000, olympic Co., ltd.) and found to be 1.8. Mu.m. The laminate comprising "substrate film/protective layer (HC layer)/alignment film/linear polarization layer" was obtained by the operation described above.

The composition for a protective layer (OC layer) was applied to the formed polarizing layer by a bar coating method so that the thickness after drying was 1.0 μm, and dried at 80 ℃ for 3 minutes. The laminate comprising "substrate film/protective layer (HC layer)/orientation film/linear polarization layer/protective layer (OC layer)" was obtained by operating as described herein. The base film was peeled off immediately before use to obtain a linear polarizing plate D containing "protective layer (HC layer)/alignment film/linear polarizing layer/protective layer (OC layer)".

Production example 5: manufacturing of phase-difference plate

(1/4 wavelength retardation layer 1 production)

A base film comprising a polyethylene terephthalate resin (PET) film (thickness 100 μm) was prepared. An alignment film (thickness: 1 μm) was formed by rubbing treatment on the base film. A composition for forming a liquid crystal layer, which contains a rod-like nematic polymerizable liquid crystal compound (liquid crystal monomer), is applied to an alignment film, and is cured by irradiation of ultraviolet rays while maintaining refractive index anisotropy. In the above-described manner, a 1/4 wavelength retardation layer having a thickness of 1 μm and being inverse wavelength dispersibility of the cured layer of the polymerizable liquid crystal compound was formed on the alignment film of the base film.

(production of positive C plate)

A base film comprising a polyethylene terephthalate resin (PET) film (thickness 38 μm) was prepared. Coating a composition for forming a vertical alignment film on one side of a base film so that the film thickness is 3 μm, and irradiating with 200mJ/cm ² The ultraviolet ray of (2) was used to produce a vertical alignment film. A positive C plate is obtained by applying a composition for positive C plate formation containing a polymerizable liquid crystal compound to a vertical alignment film, drying the composition, and then irradiating the film with Ultraviolet (UV) light to polymerize the polymerizable liquid crystal compound and form a cured layer of the polymerizable liquid crystal compound.

(production of phase-difference plate)

Corona treatment was performed on the surface of the 1/4 wavelength retardation layer on the base film and the surface of the positive C plate on the base film, respectively. The corona treated surfaces were bonded using the active energy ray-curable adhesive prepared above. Thereafter, an ultraviolet irradiation device (manufactured by Fusion UV Systems Co., ltd.) was used from the positive C plate side to accumulate 400mJ/cm of light ² (UV-B) curing the active energy ray-curable adhesive by irradiation with ultraviolet rays to form an adhesive layer. Lamination was performed using a laminator, and an active energy ray-curable adhesive was applied so that the thickness of the cured adhesive layer was 3 μm. Thus, a retardation plate comprising, in order, a base film, an alignment film, a 1/4 wavelength retardation layer, an active energy ray-curable adhesive layer, a positive C plate, a vertical alignment film, and a base film was obtained.

Example 1 >

A circularly polarizing plate was obtained by bonding the 1/4 wavelength retardation layer side of the retardation plate to the TAC film side of the linearly polarizing plate A via an adhesive layer (thickness: 5 μm). Corona treatment is applied to the respective bonding surfaces before bonding. Then, a protection layer is laminated on the linear polarization plate side of the circular polarization plateFilm C. Thereafter, an adhesive layer was laminated on the opposite side of the circularly polarizing plate from the protective film side, to obtain a film laminate with an adhesive layer. Then, in order to achieve the sealing force P at 2 levels _EL The interlayer peeling was evaluated, and the following organic EL display devices a and B with protective films were prepared as follows.

[ organic EL display device A with protective film ]

(Linear polarization layer with diffusion prevention layer)

As a panel substitute for the organic EL display panel, a linear polarization layer with an anti-diffusion layer was prepared as follows.

(preparation of aqueous solution of Water-soluble Polymer)

According to the following synthesis scheme, a water-soluble polymer comprising the following structural units was obtained.

[ chemical 7]

In 400g of dimethyl sulfoxide, 20g of polyvinyl alcohol having a molecular weight of 1000 (manufactured by Wako pure chemical industries, ltd.) and 0.55mg of N, N-dimethyl-4-aminopyridine and 4.6g of triethylamine as nucleophile were dissolved, and the mixture was heated to 60℃while stirring. Thereafter, a solution of 10.5g of methacrylic anhydride dissolved in 50g of dimethyl sulfoxide was added dropwise over 1 hour, and the mixture was heated and stirred at 60℃for 14 hours, whereby the mixture was reacted. After the obtained reaction solution was cooled to room temperature, 481g of methanol was added to the reaction solution and stirred to be thoroughly mixed, whereby the ratio (mass) of the reaction solution to methanol was adjusted to 1:1. 1500mL of acetone was slowly added to the solution, whereby the water-soluble polymer was crystallized by a crystallization method. The resulting solution containing white crystals was filtered, sufficiently washed with acetone, and then vacuum-dried, whereby 20.2g of a water-soluble polymer was obtained. The obtained water-soluble polymer was dissolved in water to prepare a 3 mass% water-soluble polymer aqueous solution.

(preparation of composition for Forming photo-alignment layer)

The following ingredients were mixed, and the resultant mixture was stirred at a temperature of 80 ℃ for 1 hour, thereby obtaining a composition for forming a photo-alignment layer.

Light-oriented polymer [ a polymer represented by the following formula (number average molecular weight: about 28200, mw/Mn: 1.82) ] described in JP-A2013-33249: 2 parts of

[ chemical 8]

Solvent [ o-xylene ]: 98 parts of

(preparation of the 1 st composition)

The following components were mixed and stirred at a temperature of 80℃for 1 hour, thereby obtaining a1 st composition. As the dye having absorption anisotropy, an azo dye represented by the following formula described in examples of Japanese patent application laid-open No. 2013-101328 is used.

A polymerizable liquid crystal compound (A1) represented by the following formula: 75 parts of

[ chemical 9]

/>

A polymerizable liquid crystal compound (A2) represented by the following formula: 25 parts of

[ chemical 10]

Pigment having absorption anisotropy (azo pigment 1) represented by the following formula: 2.5 parts of

[ chemical 11]

Pigment having absorption anisotropy (azo pigment 2) represented by the following formula: 2.5 parts of

[ chemical 12]

Pigment having absorption anisotropy (azo pigment 3) represented by the following formula: 2.5 parts of

[ chemical 13]

Polymerization initiator [ 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butan-1-one (manufactured by Irgacure 369;Ciba Specialty Chemicals Co., ltd.): 6 parts of

Leveling agents [ polyacrylate compounds (BYK-361N; BYK-Chemie Co.) ]: 1.2 parts of

Solvent [ o-xylene ]: 250 parts

(preparation of the 2 nd composition)

The following components were mixed and stirred at a temperature of 80℃for 1 hour, thereby obtaining a composition No. 2.

A polymerizable liquid crystal compound (X1) represented by the following formula: 100 parts of

[ chemical 14]

A polymerizable liquid crystal compound (X2) represented by the following formula: 33 parts of

[ 15]

Polymerization initiator [ 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butan-1-one (Irgacure (registered trademark) 369; manufactured by BASF JAPAN Co.) ]: 8 parts of

Leveling agents [ polyacrylate compounds (BYK-361N; BYK-Chemie Co.) ]: 0.1 part

Reactive additive [ LALOMER LR9000; BASF JAPAN Co.): 6.7 parts of

Solvent [ cyclopentanone ]: 546 parts of

Solvent [ N-methylpyrrolidone ]: 364 parts

(preparation of composition for Forming orientation layer)

A composition for forming an alignment layer was prepared by adding 2-butoxyethanol to SUNEVER SE-610 (commercially available from Nissan chemical Co., ltd.). The content of the solid content relative to the total amount of the composition for forming an alignment layer was 1%, and the content of the solvent was 99%. The amount of solid component of the oriented polymer was scaled according to the nominal concentration of SUNEVER SE-610.

(preparation of composition 3)

The following components were mixed and stirred at 80℃for 1 hour, and then cooled to room temperature to obtain a 3 rd composition. The content shown below is the content of each component relative to the total amount of the 3 rd composition.

A polymerizable liquid crystal compound [ LC242 ] represented by the following formula; BASF Co.): 19.2%

[ 16]

Polymerization initiator [ Irgacure 907; BASF JAPAN Co.): 0.5%

Leveling agent [ BYK-Chemie JAPAN; BYK361N ]: 0.1%

Reactive additive [ Laromer LR-9000; BASF JAPAN Co.): 1.1%

Solvent [ propylene glycol-1-monomethyl ether-2-acetate (PGMEA) ]: 79.1%

(production of Linear polarization layer with diffusion-preventing layer)

A release treated surface of a release polyethylene terephthalate (PET) film (manufactured by UNICHIKA Co., ltd. "FF-50", a single-sided release treated PET film, a thickness of a base material: 50 μm) was coated with a 3 mass% aqueous solution of a water-soluble polymer prepared as described above by a bar coater, and dried at a temperature of 100℃for 2 minutes to form a 1 st diffusion preventing layer having a thickness of 2 μm formed of a film of the water-soluble polymer.

After the surface of the 1 st diffusion preventing layer was subjected to plasma treatment, the composition for forming a photo-alignment layer prepared above was coated by a bar coater to form a coating film. The coated film was dried at 100℃for 2 minutes, whereby the solvent was removed to form a dried film. To the dried film to reach 20mJ/cm ² Polarized ultraviolet light was irradiated to a (313 nm standard) intensity, whereby an orientation restriction force was applied to form a 1 st orientation layer having a thickness of 50 nm.

The composition 1 prepared above was coated on the 1 st alignment layer using a bar coater to form a coating film. Then, the solvent was removed by drying at 110 ℃ for 2 minutes, and after the polymerizable liquid crystal compound was phase-changed to a liquid phase, the liquid crystal compound was cooled to room temperature to change the polymerizable liquid crystal compound to a smectic liquid crystal state. Thereafter, the obtained dried film was subjected to a high-pressure mercury lamp at 1000mJ/cm ² Ultraviolet light was irradiated (365 nm, a 1 st cured layer having a thickness of 3 μm was formed by polymerizing a smectic liquid crystal state of the polymerizable liquid crystal compound contained in the dried film while maintaining the state.

After plasma treatment was performed on the 1 st cured layer, the 3 mass% aqueous solution of the water-soluble polymer prepared above was applied using a bar coater, and dried at 100℃for 2 minutes to form a 2 nd diffusion preventing layer having a thickness of 2 μm formed of a film of the water-soluble polymer, to obtain a linearly polarized layer A with a diffusion preventing layer. The layer structure of the linear polarization layer A with the diffusion preventing layer is a release PET film/a 1 st diffusion preventing layer/a linear polarization layer (a 1 st orientation layer/a 1 st curing layer)/a 2 nd diffusion preventing layer. The release PET film corresponds to the main body of the organic EL display panel, and the 1 st diffusion preventing layer to the 2 nd diffusion preventing layer correspond to the sealing layer. Adhesion force (P) between the release PET film (body part) and the 1 st diffusion preventing layer to the 2 nd diffusion preventing layer (sealing layer) _EL ) 0.03[ N/25mm ]]. In the sealing force P _EL No peeling was generated between the 1 st diffusion preventing layer and the 2 nd diffusion preventing layer in the measurement.

The 2 nd diffusion preventing layer side (sealing layer side) of the linear polarizing layer with diffusion preventing layer (substitute for the organic EL display panel) was bonded to the adhesive layer of the adhesive layer-attached film laminate (linear polarizing plate a, protective film c.) obtained in the above, to produce the protective film-attached organic EL display device a.

[ organic EL display device B with protective film ]

(production of sealing layer with base layer)

A sealing layer with a base material layer was produced as a panel substitute for an organic EL display panel as follows. The surface of a release polyethylene terephthalate (PET) film (FF-50, manufactured by UNICHIKA Co., ltd., single-sided release treated PET film, thickness of the substrate: 50 μm) on the opposite side of the release treated surface was subjected to corona treatment. The composition for forming a photo-alignment layer prepared above was applied to the corona-treated surface by a bar coater, dried at 120℃for 2 minutes, and cooled to room temperature to form a dried film. To the dried film to reach 100mJ/cm ² Polarized ultraviolet light was irradiated to a light intensity of (313 nm standard), and a 2 nd alignment layer having a thickness of 100nm was formed.

The 2 nd composition prepared above was coated on the 2 nd alignment layer using a bar coater to form a coating film. Then, the film was heated and dried at 120℃for 2 minutes, and then cooled to room temperature to obtain a dried film. Thereafter, the dried film was irradiated with an ultraviolet irradiation device at an exposure of 1000mJ/cm ² Ultraviolet rays (365 nm basis), thereby forming a 2 nd cured layer having a thickness of 2 μm obtained by curing the polymerizable liquid crystal compound in a state of being oriented in a horizontal direction with respect to the plane of the 1 st retardation layer, and obtaining a 1 st retardation layer with a base layer. The layer structure of the 1 st retardation layer with the base material layer was a release PET film/1 st retardation layer (2 nd alignment layer/2 nd cured layer). The release PET film at this time corresponds to the main body of the organic EL display panel, and the 1 st retardation layer (2 nd alignment layer/2 nd cured layer) corresponds to the sealing layer. Adhesion force (P) between the release PET film (body part) and the 1 st retardation layer (2 nd orientation layer/2 nd cured layer) (sealing layer) _EL ) Is 0.06[ N/25mm ]]. In the sealing force P _EL No peeling was generated in the 1 st retardation layer (2 nd alignment layer/2 nd cured layer) during the measurement.

The sealing layer side of the sealing layer with the base material layer was bonded to the adhesive layer of the film laminate with an adhesive layer (linear polarization plate a and protective film c) obtained in the above, and an organic EL display device B with a protective film was produced.

After the organic EL display devices a and B with the protective film were provided with the through holes using a drill, the protective film was peeled off, and interlayer peeling was evaluated. The results are shown in Table 1.

Examples 2 to 14 >

The sealing force P was 2 levels in the same manner as in example 1, except that the protective film and the linear polarizing plate shown in table 1 were used _EL The interlayer peeling was evaluated as follows. The results are shown in Table 1.

TABLE 1

In the evaluation of interlayer peeling, the evaluation result was set to be evaluation a when peeling was not observed in all of the 3 tests,

at P _EL Peeling was observed in 1 sheet of linear polarization layer a with diffusion preventing layer =0.03n/25 mm (panel substitute of organic EL display panel), and when peeling was not observed in the remaining all panel substitutes, it was set as evaluation B,

at P _EL The peeling was observed in all of 3 sheets of the linear polarization layer a with diffusion preventing layer (panel substitute for organic EL display panel) of =0.03N/25 mm, and when the peeling was not observed in all of the remaining analog panels, it was set as evaluation C,

at P _EL Linear polarization layer a with diffusion preventing layer =0.03n/25 mm [ panel substitute of organic EL display panel ], P _EL When occurrence of peeling was observed in the sealing layer with base layer of =0.06N/25 mm (substitute for organic EL display panel), it was set as evaluation D,

evaluation E was set when occurrence of peeling was observed in all the substitutes for the organic EL display panel.

Claims

1. An organic EL display device with a protective film, comprising a protective film and an organic EL display device,

the organic EL display device with a protective film has a through hole in a plan view,

the organic EL display panel comprises a main body and a sealing layer laminated on the observation side of the main body,

setting the adhesion force between the main body and the sealing layer as P _EL Setting the bending rigidity of the circular polarizing plate as S _PL Setting the bending rigidity of the protective film as S _PF Setting the peeling force at the peeling speed of 18 m/min from the circular polarizing plate as F _PF When the following formula is satisfied:

(1)P _EL ≤0.10[N/25mm]

(2)0.10[25mm/N]≤S _PL /(S _PF ×F _PF )

wherein P is _EL Is in N/25mm, S _PL Has the unit of N.m, S _PF Has the unit of N.m, F _PF In N/25mm.

2. The organic EL display device with a protective film as claimed in claim 1, wherein,

the circular polarizing plate is a laminate of a liquid crystal cured polarizing plate layer and a liquid crystal cured retardation layer.

3. The organic EL display device with a protective film as claimed in claim 1, wherein,

the diameter of the through hole is more than 1 mm.

4. The organic EL display device with a protective film as claimed in claim 2, wherein,

the diameter of the through hole is more than 1 mm.

5. The organic EL display device with a protective film as claimed in any one of claims 1 to 4, wherein,

the thickness of the circular polarizing plate is 120 μm or less.