KR20230164592A - Organic el display device with protective film - Google Patents

Abstract

[Problem] To provide an organic EL display device having a protection film having through holes in the surface, wherein damage is unlikely to occur in the vicinity of the through holes of the organic EL display panel when the protection film is peeled off. .
[Solution] An organic EL display device including a protection film and an organic EL display device, wherein the protection film has a through hole in plan view, and the protection film is peelably laminated on the viewing side of the organic EL display device. , the organic EL display device includes an organic EL display panel and a circularly polarizing plate laminated on the viewer side of the organic EL display panel through an adhesive layer, and the organic EL display panel includes a main body portion and a seal laminated on the viewer side of the main body portion. An organic EL display device having a protective film that includes a layer and satisfies Equations (1) and (2).

Description

Organic EL display device with protective film {ORGANIC EL DISPLAY DEVICE WITH PROTECTIVE FILM}

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

Patent Document 1 proposes a polarizing plate having a protection film in which a peelable protection film is bonded to the polarizing plate. The protective film is peeled and removed after bonding the polarizing plate to the liquid crystal cell.

Patent Document 1: Japanese Patent Publication No. 2016-170383

Organic EL display devices used in smart phones and the like may be provided with a through hole for a camera hole. In an organic EL display device having a through hole in the plane, when the protective film is peeled off, damage (for example, peeling of the main body and the sealing layer, etc.) occurs near the through hole of the organic EL display panel.

An object of the present invention is to provide an organic EL display device having a protection film having a through hole in the plane, which is unlikely to cause damage near the through hole of the organic EL display panel when the protection film is peeled off. It is provided.

The present invention provides an organic EL display device having the following protective film.

[1] An organic EL display device having a protection film including a protection film and an organic EL display device,

When viewed in plan, it has a through hole,

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

The organic EL display device includes an organic EL display panel and a circularly polarizing plate laminated on a viewing side of the organic EL display panel through an adhesive layer,

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

The adhesion between the main body and the sealing layer is P _EL [N/25 mm], the bending strength of the circular polarizer is S _PL [N m], the bending strength of the protection film is S PF [N m], and the bending strength of the protective film is S _PF [N m]. When the peeling force when peeling the protective film from the circularly polarizing plate at a peeling speed of 18 m/min is set to F _PF [N/25 mm], the following equation:

(1) P _EL ≤0.10[N/25 ㎜]

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

An organic EL display device having a protection film that satisfies the above.

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

[3] An organic EL display device having the protection film according to [1] or [2], wherein the through hole has a diameter of 1 mm or more.

[4] An organic EL display device having the protection film according to any one of [1] to [3], wherein the circularly polarizing plate has a thickness of 120 μm or less.

According to the present invention, there is provided an organic EL display device having a protection film having a through hole in the plane, wherein damage is unlikely to occur in the vicinity of the through hole of the organic EL display panel when the protection film is peeled off. can do.

1 is a schematic cross-sectional view showing an example of the layer structure of an organic EL display device having a protective film of the present invention.
Figure 2 is a schematic plan view of an organic EL display device having the protective film of the present invention.
Figure 3 is a schematic cross-sectional view illustrating peeling of the protective film.
Figure 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 an organic EL display device having the protective film of the present invention.
Figure 6 is a schematic diagram for explaining a method for evaluating bending resistance.

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 drawings below, the scale of each component is appropriately adjusted to make it easier to understand, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.

<Organic EL display device with protective film>

An organic EL display device with a protection film of the present invention includes a protection film and an organic EL display device, and has a through hole in plan view. The protection film is laminated in a peelable manner on the viewing side of the organic EL display device. An organic EL display device includes an organic EL display panel and a circularly polarizing plate laminated on a viewing side of the organic EL display panel through an adhesive layer. The organic EL display panel has a main body and a sealing layer laminated on the viewing side of the main body, and the adhesion between the main body and the sealing layer is P _EL [N/25 mm], and the bending strength of the circular polarizer is S _PL [N. m], when the bending strength of the protect film is S _PF [N m], and the peeling force when peeling the protect film from the circularly polarizing plate at a speed of 18 m/min is F _PF [N/25 mm], ceremony:

(1) P _EL ≤0.10[N/25 ㎜]

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

satisfies.

An example of the layer structure of an organic EL display device having the protective film of the present invention is shown in Fig. 1. The organic EL display device 1 with a protection film shown in FIG. 1 includes a protection 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 linear polarizing plate 60 and a retardation plate 70. The linear polarizer 60 includes a polarizing layer 61 and protective films 62 and 63. The organic EL display panel 50 includes a sealing layer 51 and a body portion 52. Although not shown, the organic EL display device 1 with a protective film may further include a bonding layer for bonding each layer.

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

The organic EL display device 1 with a protective film can be used as mobile devices such as smart phones and tablets, televisions, digital photo frames, electronic signboards, measuring instruments and meters, office equipment, medical equipment, electronic computing equipment, etc. .

[Equation (1)]

The organic EL display device 1 having a protection film is used after peeling the protection film 10 at the time of use. The protection film 10 is usually peeled from the organic EL display device 20 while maintaining its original shape. In the organic EL display device 1 having _{a protection film, when the adhesion P EL (hereinafter also referred to as P EL )} between the sealing layer 51 and the main body 52 satisfies equation (1), the protection film ( 10), it was found that damage tends to occur in the organic EL display panel 50 near the through hole. P _EL may be, for example, 0.09 [N/25 mm] or less, 0.08 [N/25 mm] or less, or 0.07 [N/25 mm] or less. P _EL is preferably 0.01 [N/25 mm] or more. P _EL can be measured according to the method described in the Examples section described later.

[Equation (2)]

The organic EL display device 1 having a protection film satisfies equation (2), so that even in the case where equation (1) is satisfied, when the protection film 10 is peeled off, the organic EL display device 1 closes the through hole of the organic EL display panel. Damage tends to become more difficult to occur.

Peeling of the protective film will be explained with reference to FIG. 3. The organic EL display device 1 with a protection film shown in Fig. 3(a) includes a protection film 10 and an organic EL display device 20. As shown in Fig. 3(b), the protective film 10 is raised in the direction of arrow A to start peeling. After that, as shown in Fig. 3(c), a peeling force is applied to the protection film 10, and the protection film 10 is peeled in the direction of arrow B. The protection film 10 peeled from the circularly polarizing plate 1 is removed. Force may be applied to the protection film 10 during peeling by holding the end of the protection film 10, or by holding the release tape attached to the surface of the protection film 10.

As shown in Figure 4, when peeling the protective film with the peeling force (F), the force in the direction perpendicular to the film surface of the peeling force (F) is F⊥, the force in the parallel direction is F//, and protect. When the peeling angle formed between the end of the film 10 and the organic EL display device 20 is θ, by reducing the peeling force (F⊥) and the peeling angle (θ), when peeling the protective film 10, It has been revealed that 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 a protective film satisfies equation (2), the peeling force (F⊥) and the peeling angle (θ) are easily reduced, and as a result, the organic EL display panel 50 Damage tends to be less likely to occur in the vicinity of the through hole.

The effect of equation (2) becomes significant when the bending strength (S _PL ) (hereinafter also referred to as S _PL ) of the circularly polarizing plate 30 is smaller, and is preferably 10.0 N·m or less, more preferably 5.0 N. ·m or less, more preferably 2.0 N·m or less. By having a small S _PL , it is possible to suppress the occurrence of cracks or cracks in any one layer of the circularly polarizing plate when repeatedly bent. S _PL is usually 0.10 N·m or more. S _PF can be measured according to the method described in the Examples section described later.

The bending strength (S _PF ) (hereinafter also referred to as S _PF ) of the protective film 10 is 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. am. S _PF is usually 1.0 N·m or more. S _PF can be measured according to the method described in the Examples section described later.

The peeling force (F _PF ) [N/25 mm] (hereinafter also referred to as F _PF ) when peeling the protect film 10 from the circularly polarizing plate 30 in the direction of the arrow B at a speed of 18 m/min is Preferably it is 1.00 N/25 mm or less, more preferably 0.80 N/25 mm or less, and even more preferably 0.50 N/25 mm or less. F _PF is usually 0.20 N/25 mm or more. F _PF can be measured according to the method described in the Examples section described later.

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

[Protect Film]

The protection film 10 is peelably laminated on one side of the organic EL display device 20, preferably on the linear polarizer 60 side of the circularly polarizer 30, thereby forming a layer on its surface (typically a protective film or a protective film described later). The surface of the hard coat layer) can be protected.

The protective film 10 is comprised, for example, of a base film and an adhesive layer laminated thereon. The protection film 10 can be peeled and removed for each adhesive layer that the protection film 10 has. Regarding the adhesive layer of the protective film 10, the description of the adhesive layer in the bonding layer described later applies. Methods for laminating the protective film 10 in a peelable manner include, for example, a method of controlling the type and thickness of the adhesive layer. The thickness of the adhesive layer of the protective film 10 is preferably 2 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

Resins constituting the base film include, for example, polyethylene-based resins such as polyethylene; Polypropylene-based resins such as polypropylene; Polyester resins such as polyethylene terephthalate and polyethylene naphthalate; It may be a thermoplastic resin of polycarbonate-based resin. Preferably, it is a polyester resin such as polyethylene terephthalate. 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 protection film 10 is 60 μm or more, the bending strength (S _PF ) of the protection film 10 tends to increase easily. 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]

In the organic EL display device 20, a circularly polarizing plate 30, an adhesive layer 40, and an organic EL display panel 50 are laminated in this order. The circularly polarizing plate 30 may be bonded in contact with the adhesive layer 40. The organic EL display panel 50 may be bonded in contact with the adhesive layer 40 . The circularly polarizing plate 30 can be bonded to the sealing layer 51 side of the organic EL display panel 50 using the adhesive layer 40. The circularly polarizing plate 30 may be disposed on the viewing side of the organic EL display panel 50.

[Circular polarizer]

The circularly polarizing plate 30 may include a linear polarizing plate 60 and a retardation plate 70. Although not shown, the linear polarizer 60 and the retardation plate 70 may be bonded through a bonding layer described later.

(Linear polarizer)

The linear polarizer 60 includes a polarizing layer 61 and protective films 62 and 63. The polarizing layer 61 and the protective films 62 and 63 may be bonded through a bonding layer described later, and are preferably bonded through a water-based adhesive layer. As shown in FIG. 1, the linear polarizing plate may be provided with a protective film on both sides of the polarizing layer, or may be provided with a protective film only on one side of the polarizing layer.

(protective film)

The protective films 62 and 63 may have a function of protecting the polarizing layer 61 and the like. The protective films 62 and 63 are made of a light-transmitting (preferably optically transparent) thermoplastic resin film, such as a chain polyolefin-based resin (polypropylene-based resin, etc.), a cyclic polyolefin-based resin (norbornene-based resin, etc.), and Polyolefin-based resins such as; Cellulose-based resins such as triacetylcellulose and diacetylcellulose; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate-based resin; (meth)acrylic resins such as methyl methacrylate resins; polystyrene-based resin; polyvinyl chloride-based resin; Acrylonitrile, butadiene, and styrene-based resin; Acrylonitrile/styrene-based resin; polyvinyl acetate-based resin; polyvinylidene chloride-based resin; polyamide-based resin; polyacetal resin; Modified polyphenylene ether-based resin; polysulfone-based resin; polyethersulfone-based resin; polyarylate-based resin; polyamideimide-based resin; It may be a film containing a polyimide-based resin or the like.

Examples of the chain polyolefin resin include polyethylene resin (polyethylene resin, which is a homopolymer of ethylene, or copolymer mainly based on ethylene), polypropylene resin (polypropylene resin, which is a homopolymer of propylene, or copolymer mainly based on propylene), and In addition to homopolymers of the same chain olefin, copolymers containing two or more types of chain olefins can be mentioned.

Cyclic polyolefin-based resin is a general term for resins in which cyclic olefin is polymerized as a polymerization unit, for example, Japanese Patent Application Laid-Open No. 1-240517, Japanese Patent Application Laid-Open No. 3-14882, and Japanese Patent Application Laid-Open No. 3-122137. and resins described in the like. Specific examples of the cyclic polyolefin resin include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (typically random copolymers), and these. These are graft polymers modified with unsaturated carboxylic acids or their derivatives, and hydrides thereof. Among them, norbornene-based resins using norbornene-based monomers such as norbornene or polycyclic norbornene-based monomers as cyclic olefins are preferably used.

Polyester-based resin is a resin having an ester bond, excluding the cellulose ester-based resin below, and generally contains a polycondensate of polyhydric carboxylic acid or its derivative and polyhydric alcohol. As the polyhydric carboxylic acid or its derivative, a divalent dicarboxylic acid or a derivative thereof can be used, and examples include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate. As the polyhydric alcohol, a diol can be used, and examples include ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol. Representative examples of polyester resins include polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol.

(meth)acrylic resin is a resin whose main constituent monomer is a compound having a (meth)acryloyl group. Specific examples of (meth)acrylic resin include poly(meth)acrylic acid esters such as polymethyl methacrylate; Methyl methacrylate-(meth)acrylic acid copolymer; Methyl methacrylate-(meth)acrylic acid ester copolymer; Methyl methacrylate-acrylic acid ester-(meth)acrylic acid copolymer; (meth)acrylate methyl-styrene copolymer (MS resin, etc.); It includes copolymers of methyl methacrylate and compounds having an alicyclic hydrocarbon group (e.g., methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate-norbornyl (meth)acrylate copolymer, etc.). Preferably, a polymer containing poly(meth)acrylic acid C _1-6 alkyl ester, such as methyl poly(meth)acrylate, as the main component is used, and more preferably, a polymer containing methyl methacrylate as the main component (not less than 50% by mass or more than 100% by mass) is used. % or less, preferably 70 mass% or more and 100 mass% or less), is used.

Cellulose ester-based resin is an ester of cellulose and fatty acids. Specific examples of cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Additionally, copolymers thereof and those in which part of the hydroxyl group has been modified with another substituent can also be mentioned. Among these, cellulose triacetate (triacetylcellulose) is particularly preferable.

Polycarbonate-based resin is an engineering plastic containing a polymer in which monomer units are bonded through carbonate groups.

The thickness of the protective films 62, 63 is usually 1 μm or more and 100 μm or less, but from the viewpoint of strength, handleability, etc., it is preferably 5 μm or more and 60 μm or less, more preferably 5 μm or more and 40 μm or less, and 10 μm or more. It is more preferable that it is ㎛ or more and 20 ㎛ or less.

The protective films 62 and 63 may be provided with a phase difference function for purposes such as viewing angle compensation. In that case, the films themselves may have a phase difference function, may have a separate phase difference layer, or may be a combination of both.

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

The protective films 62 and 63 may be made of the same type of thermoplastic resin or may be made of different types of thermoplastic resin. Additionally, the thickness may be the same or different. Moreover, they may have the same phase difference characteristics or may have different phase difference characteristics.

The protective films 62 and 63 have a hard coat layer (HC layer), an anti-glare layer, a light diffusion layer, an anti-reflection layer, a low refractive index layer, an anti-static layer, and an anti-fouling layer described later on the outer surface (the surface opposite to the polarizer). It may be provided with the same surface treatment layer (coating layer). In addition, 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 through an adhesive layer described later. The adhesives that form the adhesive layer may be of the same type or may be of different types. For example, one side may be bonded using a water-based adhesive, and the other side may be bonded using an active energy ray-curable adhesive.

In order to improve the adhesion of the polarizing layer 61 and the protective films 62 and 63, prior to bonding the polarizing layer 61 and the protective films 62 and 63, surface activity treatment, which will be described later, is applied to each bonding surface. It may be carried out.

(hard coat layer)

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

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 irradiating active energy rays or thermal energy. It is preferable to cure by .

Active energy rays are defined as energy rays that can generate active species by decomposing compounds that generate active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron rays. Among these, ultraviolet rays are particularly preferable.

The composition for the hard coat layer (HC layer) contains at least one type of polymer among a radically polymerizable compound and a cationically polymerizable compound. A radically polymerizable compound is a compound having a radically polymerizable group. The radical polymerizable group contained in the radically polymerizable compound may be any functional group capable of generating a radical polymerization reaction, and examples thereof include groups containing a carbon-carbon unsaturated double bond. Specifically, vinyl group, (meth)acryloyl group, etc. can be mentioned.

Additionally, when the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different. The number of radically polymerizable groups in one molecule of the radically polymerizable compound is preferably two or more in order to improve the hardness of the hard coat layer (HC layer).

As a radically polymerizable compound, a compound having a (meth)acryloyl group is preferable in terms of high reactivity, and a compound called a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule. Oligomers having several (meth)acryloyl groups in the molecule, such as epoxy (meth)acrylate, urethane (meth)acrylate, or polyester (meth)acrylate, and having a molecular weight of several hundred to several thousand can be preferably used. . It is preferable to include at least one selected from epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate.

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

Cyclic ether groups such as epoxy groups and oxetanyl groups are preferable because shrinkage due to polymerization reaction is small. In addition, compounds having an epoxy group among the cyclic ether groups are easy to obtain as compounds of various structures, do not adversely affect the durability of the obtained hard coat layer (HC layer), and are said to be easy to control compatibility with radically polymerizable compounds. There is an advantage.

In addition, the oxetanyl group among the cyclic ether groups tends to have a higher degree of polymerization compared to the epoxy group, has low toxicity, accelerates the rate of network formation from the cationically polymerizable compound of the obtained hard coat layer (HC layer), and There are advantages such as forming an independent network even in the mixed region without leaving unreacted monomers in the film.

Cationically polymerizable compounds having an epoxy group include, for example, polyglycidyl ethers of polyhydric alcohols having an alicyclic ring, or alicyclic compounds obtained by epoxidizing a cyclohexene ring or cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid. family epoxy resin; Aliphatic epoxy resins such as polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl (meth)acrylate; Glycidyl ethers and novolacs produced by the reaction of bisphenols such as bisphenol A, bisphenol F, and hydrogenated bisphenol A, or their derivatives such as alkylene oxide adducts and caprolactone adducts, and epichlorhydrin. These include epoxy resins, and glycidyl ether type epoxy resins derived from bisphenols.

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

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

Active energy ray radical polymerization initiators include Type 1 radical polymerization initiators, which generate radicals by decomposition of molecules, and Type 2 radical polymerization initiators, which coexist with tertiary amines and generate radicals through hydrogen abstraction-type reactions, and each is used alone. It can also be used alone or in combination.

The cationic polymerization initiator may be capable of releasing a substance that initiates cationic polymerization by at least one of active energy ray irradiation and heating. As a cationic polymerization initiator, aromatic iodonium salt, aromatic sulfonium salt, cyclopentadienyl iron(II) complex, etc. can be used. Depending on the difference in structure, cationic polymerization can be initiated by either irradiation of active energy rays or heating, or by neither.

The polymerization initiator may contain 0.1 to 10% by weight based on the total (100% by weight) of the composition for the hard coat layer (HC layer). If the content of the polymerization initiator is less than 0.1% by weight, curing cannot sufficiently proceed, making it difficult to achieve the mechanical properties or adhesion of the finally obtained coating film. On the other hand, if the content of the polymerization initiator exceeds 10% by weight, poor adhesion, cracking, or curling may occur due to curing shrinkage.

The composition for the hard coat layer (HC layer) may further include one or more selected from the group consisting of solvents and additives. The solvent is capable of dissolving or dispersing the polymerizable compound and the polymerization initiator, and can be used without limitation as long as it is known as a solvent for compositions for hard coat layers (HC layers) in the present technical field. Additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, etc.

(Polarizing layer)

Examples of the polarizing layer 61 include a stretched film or stretched layer to which a dichroic dye is adsorbed, and a polarizer layer formed by applying a dichroic dye and curing it. When the polarizer layer includes a base film and an alignment film, which will be described later, it is referred to as a polarizing layer including these.

As a dichroic dye, specifically, iodine or a dichroic organic dye is used. Examples of dichroic organic dyes include azo dyes. Azo pigments include, for example, dichroic direct dyes containing disazo compounds such as C.I.DIRECT RED 39, and dichroic direct dyes containing compounds such as trisazo and tetrakisazo.

(Stretched film or stretched layer with dichroic dye adsorbed)

Stretched films to which a dichroic dye is adsorbed are usually prepared by uniaxially stretching a polyvinyl alcohol-based resin film, dyeing the polyvinyl alcohol-based resin film with a dichroic dye, and adsorbing the dichroic dye. It can be manufactured through a process of treating the temporarily adsorbed polyvinyl alcohol-based resin film 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, 5 μm or more, 20 μm or less, further 15 μm or less, and further 10 μm or less.

Polyvinyl alcohol-based resin is obtained by saponifying polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable with it is used. Other monomers that can be copolymerized with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol-based resin is usually about 85 mol% or more and 100 mol% or less, and is preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, and preferably 1,500 or more and 5,000 or less.

The stretched layer to which the dichroic dye is adsorbed is usually formed by applying a coating liquid containing the polyvinyl alcohol-based resin on a base film, a step of uniaxially stretching the obtained laminated film, and polyvinyl alcohol of the uniaxially stretched laminated film. A step of dyeing the base resin layer with a dichroic dye to adsorb the dichroic dye to form a polarizer layer, a step of treating the film to which the dichroic dye has been adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with the aqueous boric acid solution. It can be manufactured through

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

(Polarizer layer made by applying dichroic dye and curing it)

As a polarizer layer formed by applying and curing a dichroic dye, a layer obtained by applying a composition containing a polymerizable dichroic dye having liquid crystallinity or a composition containing a polymerizable liquid crystal compound and a dichroic dye to a base film and curing it, etc. A liquid crystal cured polarizer layer containing a cured product of a polymerizable liquid crystal compound can be mentioned. The base film may have an alignment film provided on one side. The thickness of the alignment film may be, for example, 5 nm or more and 1 μm or less. By using a polarizer layer formed by applying and curing a dichroic dye, color fading at the edges can be suppressed when the circularly polarizing plate is placed in a high temperature and high humidity environment.

The polarizing layer 61 may be included in the linear polarizing plate 60 together with the base film, or may be included in the linear polarizing plate 60 by peeling and removing the base film from the polarizer layer formed by applying and curing a dichroic dye. As the base film, the description of the material and thickness of the protective films 62 and 63 applies to the thermoplastic resin film described above. The base film may have the hard coat layer (HC layer) described above formed as a protective layer on at least one side.

The polarizer layer formed by applying and curing a dichroic dye may have an overcoat layer (OC layer).

The thickness of the polarizer layer formed by applying and curing a dichroic dye is usually 10 μm or less, preferably 8 μm or less, and more preferably 5 μm or less.

FIG. 5 shows the layer structure of an organic EL display device with a protection film when the polarizing layer 61 is a polarizing layer formed by applying a dichroic dye and curing it. The organic EL display device 3 with a protection film shown in FIG. 5 includes a protection 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 linear polarizing plate 80 and a retardation plate 70, and the linear polarizing plate 80 includes a hard coat layer 81, an alignment layer 82, and a polarizing layer 83 that is a liquid crystal curing polarizer layer. , the overcoat layer 84 is in this order. The organic EL display panel 50 includes a sealing layer 51 and a body portion 52. Each layer may be joined via a bonding layer (not shown) described later.

(Phase difference plate)

The retardation plate 70 may include, for example, at least one 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 a 1/4 wavelength retardation layer. It includes at least one retardation layer selected from the group consisting of a 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 in which these are laminated. When two or more retardation layers are stacked, the retardation layers may be bonded to each other by a bonding layer described later. The 1/4 wavelength retardation layer preferably has reverse wavelength dispersion.

Inverse wavelength dispersion is an optical characteristic in which the retardation value within the liquid crystal orientation plane at a short wavelength is smaller than the retardation value within the liquid crystal orientation plane at a long wavelength, and preferably, the optical film satisfies the following equations (i) and (ii). It is ordered. Additionally, Re(λ) represents the in-plane retardation value for light with a wavelength of λ nm.

Re(450)/Re(550)≤1 (i)

1≤Re(630)/Re(550) (ii)

The 1/2 wavelength retardation layer is a layer whose Re(λ) satisfies Re(λ)=λ/2, and can be achieved at any wavelength in the visible range, and especially at a wavelength of 550 nm. desirable. For the 1/2 wavelength retardation layer, it is preferable that Re(550) satisfies 200 nm≤Re(550)≤330 nm, and more preferably satisfies 220 nm≤Re(550)≤300 nm. The 1/4 wavelength retardation layer is a layer whose Re(λ) satisfies Re(λ)=λ/4, and can be achieved at any wavelength in the visible range, and especially at a wavelength of 550 nm. desirable. For the 1/4 wavelength retardation layer, it is preferable that Re(550) satisfies 100 nm≤Re(550)≤160 nm, and more preferably satisfies 110 nm≤Re(550)≤150 nm.

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

nz＞nx≒ny

In addition, the above “≒” includes not only the case where both are completely the same, but also the case where the two are substantially the same.

When the retardation plate 70 is a retardation layer laminate, it may include a first retardation layer and a second retardation layer. 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 first retardation layer and the second 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 with reverse wavelength dispersion, and the other may be a positive C plate. For example, the first retardation layer and the second retardation layer are a 1/4 wavelength retardation layer with reverse wavelength dispersion and a positive C plate, respectively. Both the first phase difference layer and the second phase difference layer may have reverse wavelength dispersion. The first retardation layer and the second retardation layer are preferably bonded through an adhesive layer described later.

The retardation plate 70 may include a liquid crystal curing retardation layer as a retardation layer. The liquid crystal curing retardation layer is a layer having retardation characteristics and is a layer containing a cured product obtained by polymerizing and curing a polymerizable liquid crystal compound in an aligned state. The retardation plate 70 may be provided with only one layer of liquid crystal hardening retardation layer, or may be provided with two or more layers of liquid crystal hardening retardation layer.

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

Examples of the polymerizable liquid crystal compound include a rod-shaped polymerizable liquid crystal compound and a disc-shaped polymerizable liquid crystal compound. Either one of these may be used, or a mixture containing both of these may be used. When the rod-shaped polymerizable liquid crystal compound is horizontally or vertically aligned 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 oriented, the optical axis of the polymerizable liquid crystal compound exists in a direction perpendicular to the disk surface of the polymerizable liquid crystal compound. As the rod-shaped polymerizable liquid crystal compound, for example, those described in Japanese Patent Publication No. Hei 11-513019 (Claim 1, etc.) can be suitably used. Disk-shaped polymerizable liquid crystal compounds are described in Japanese Patent Application Laid-Open No. 2007-108732 (paragraphs [0020] to [0067], etc.) and Japanese Patent Application Laid-Open No. 2010-244038 (paragraphs [0013] to [0108], etc.). Those described can be suitably used.

In order for the liquid crystal cured retardation layer formed by polymerizing the polymerizable liquid crystal compound to express 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, in-plane retardation is expressed by aligning the optical axis of the polymerizable liquid crystal compound horizontally with respect to the plane of the base film, and in this case, the optical axis direction and the slow axis direction coincide. When the polymerizable liquid crystal compound is disk-shaped, in-plane retardation is expressed by aligning the optical axis of the polymerizable liquid crystal compound horizontally with respect to the plane of the base film, and in this case, the optical axis and the slow axis are orthogonal. The alignment state of the polymerizable liquid crystal compound can be adjusted by combining an alignment film and the polymerizable liquid crystal compound.

A polymerizable liquid crystal compound is a compound that has at least one polymerizable group and has liquid crystallinity. When using two or more types of polymerizable liquid crystal compounds together, it is preferable that at least one type has two or more polymerizable groups in the molecule. A polymerizable group means a group involved in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction by active radicals or acids generated from a photopolymerization initiator described later. As polymerizable groups, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, styryl group, and allyl group. etc. can be mentioned. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystallinity of the polymerizable liquid crystal compound may be either thermotropic liquid crystal or lyotropic liquid crystal. If thermotropic liquid crystals are classified by degree of order, they may be nematic liquid crystal or smectic liquid crystal.

The retardation plate 70 may include an alignment film. The alignment film has an orientation regulating force that orients the polymerizable liquid crystal compound in a desired direction. The alignment film may be a vertically aligned film in which the molecular axis of the polymerizable liquid crystal compound is vertically aligned with respect to the base film, or may be a horizontally aligned film in which the molecular axis of the polymerizable liquid crystal compound is horizontally aligned with respect to the base film, or the molecular axis of the polymerizable liquid crystal compound may be aligned horizontally with respect to the base film. It may be an inclined alignment film that is obliquely oriented with respect to . When the retardation film 70 includes two or more alignment films, the alignment films may be the same or different from each other.

The alignment film preferably has solvent resistance that does not dissolve when the composition for forming a liquid crystal layer containing a polymerizable liquid crystal compound is applied, and has heat resistance to heat treatment for removal of the solvent or alignment of the polymerizable liquid crystal compound. Examples of the alignment film include an orientation polymer layer formed of an orientation polymer, a photo-alignment polymer layer formed of a photo-alignment polymer, and a groove alignment film having a concavo-convex pattern or 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 ㎛ or more, 0.5 ㎛ or more, 1 ㎛ or more, 2 ㎛ or more, and preferably 10 ㎛ or less, 8 It may be ㎛ or less, and may be 5 ㎛ or less.

(Adhesive layer)

The adhesive layer 40 may be interposed between the circularly polarizing plate 30 and the organic EL display panel 50 and may have a function of bonding the two. Regarding the adhesive layer 40, the description of the adhesive layer in the bonding layer described later applies. The thickness of the adhesive layer 40 is preferably 5 μm or more and 70 μm or less, and 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 can, for example, bond a linear polarizer and a retardation plate, or bond the first retardation layer and the second retardation layer constituting the above-described retardation layer laminate.

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

Examples of the (meth)acrylic resin (base polymer) used in the adhesive composition include (meth)acrylate, such as butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. A polymer or copolymer containing one or two or more types of acrylic acid ester as a monomer is suitably used. It is preferable to copolymerize a polar monomer with the base polymer. Polar monomers include, for example, (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and glycyrrhizate. Monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, etc., such as dil (meth)acrylate, can be mentioned.

The pressure-sensitive adhesive composition may contain only the base polymer, but usually further contains a crosslinking agent. Examples of the crosslinking agent include metal ions of divalence or higher, which form a metal carboxylic acid salt between carboxyl groups; A polyamine compound that forms an amide bond between carboxyl groups; A polyepoxy compound or polyol that forms an ester bond between carboxyl groups; As a polyisocyanate compound, one that forms an amide bond between carboxyl groups is exemplified. Among them, polyisocyanate compounds are preferable.

The thickness of the adhesive layer is preferably 1 μm or more and 200 μm or less, more preferably 2 μm or more and 100 μm or less, more preferably 2 μm or more and 80 μm or less, and especially preferably 3 μm or more and 50 μm or less.

The adhesive constituting the adhesive layer can be any suitable adhesive. As the adhesive, a water-based adhesive, an active energy ray-curable adhesive, etc. can be used.

The thickness when applying the adhesive can be set to any appropriate value. For example, after curing or heating (drying), it is set so that an adhesive layer with a desired thickness is obtained. 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, further preferably 0.01 μm or more and 3 μm or less, and most preferably 0.01 μm or more and 2 μm. It is as follows.

Examples of the water-based adhesive include an adhesive containing an aqueous polyvinyl alcohol-based resin solution and a water-based two-component urethane-based emulsion adhesive. Among them, a water-based adhesive containing an aqueous polyvinyl alcohol-based resin solution is suitably used. Polyvinyl alcohol-based resins include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, and polyvinyl alcohol-based copolymers obtained by saponifying copolymers of vinyl acetate and other monomers copolymerizable with vinyl acetate. , or modified polyvinyl alcohol-based polymers in which their hydroxyl groups are partially modified can be used. The water-based adhesive may contain a crosslinking agent such as an aldehyde compound (glyoxal, etc.), an epoxy compound, a melamine-based compound, a methylol compound, an isocyanate compound, an amine compound, and a polyvalent metal salt.

An active energy ray-curable adhesive is an adhesive containing a curable compound that hardens by irradiation of active energy rays such as ultraviolet rays, visible light, electron beams, or 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. Cationic polymerizable curable compounds include, for example, epoxy-based compounds (compounds having one or two or more epoxy groups in the molecule), oxetane-based compounds (compounds having one or two or more oxetane rings in the molecule), or these. A combination of . Examples of radically polymerizable curable compounds include (meth)acrylic compounds (compounds having one or two or more (meth)acryloyloxy groups in the molecule), other vinyl compounds having a radically polymerizable double bond, or A combination of these can be mentioned. A cationically polymerizable curable compound and a radically polymerizable curable compound may be used together. Active energy ray-curable adhesives usually further include at least one of a cationic polymerization initiator and a radical polymerization initiator for initiating a curing reaction of the curable compound.

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

In order to improve adhesion, surface activation treatment may be applied to at least one of the bonding surfaces of the bonding layer and the bonding layer. Surface activation treatments include dry treatments such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, etc.), ozone treatment, UV ozone treatment, and ionizing active ray treatment (ultraviolet treatment, electron beam treatment, etc.). These surface activation treatments may be performed individually or in combination of two or more. Among them, corona treatment is preferable. Corona treatment can be performed, for example, with an output of 1 kJ/m2 or more and 50 kJ/m2 or less. The time for performing the corona treatment may be, for example, 1 second or more and 1 minute or less.

[Organic EL display panel]

In the organic EL display panel 50, the sealing layer 51 and the main body portion 52 are laminated in this order. Although not shown, the organic EL display panel 50 may further include, for example, a touch sensor to be described later.

The sealing layer 51 is made of a material excellent in barrier properties and transparency. Examples of materials constituting the sealing layer 51 include epoxy resin and polyurea. Additionally, the sealing layer 51 may be formed by coating an epoxy resin (epoxy resin adhesive) and adhering a barrier sheet thereon.

The sealing layer 51 may be formed directly on the main body 52 or may be bonded to the main body 52 through the above-described bonding layer. When the organic EL display panel 50 includes a touch sensor described later, the touch sensor may be formed directly on the side opposite to the main body portion 52 of the sealing layer 51, and may be connected to the sealing layer 51 through the bonding layer described above. ) may be bonded to each other. When 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 52 may include an organic EL element as a light emitting source. The main body 52 may further include, for example, a substrate, an electrode, a planarization layer, and an insulating layer. The organic EL element may be manufactured continuously by, for example, a roll-to-roll process, and can be manufactured, for example, by the method described in Japanese Patent Application Laid-Open No. 2012-169236.

The detection method is not limited as long as the touch sensor is a sensor that can detect the touched position. Examples include touch sensors such as resistive film type, capacitive type, optical sensor type, ultrasonic type, electromagnetic inductive coupling type, and surface acoustic wave type. do. Among them, a capacitive touch sensor is suitably used in terms of low cost, fast response speed, and thin film.

The touch sensor may include an adhesive layer, a separation layer, a protective layer, etc. between the transparent conductive layer and the base film supporting the transparent conductive layer. Examples of the adhesive layer include an adhesive layer and an adhesive layer. Examples of the base film supporting the transparent conductive layer include a base film in which a transparent conductive layer is deposited on one surface, a base film in which the transparent conductive layer is transferred through 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, or vapor deposition. A photosensitive resist is formed on the transparent electrode layer, and then an electrode pattern layer is formed by photolithography. A negative type photosensitive resist or a positive type photosensitive resist is used as the photosensitive resist, and after patterning, the photosensitive resist may remain or may be removed. When manufacturing a film by a sputtering method, a mask having an electrode pattern shape may be placed and sputtering may be performed to form an electrode pattern layer.

The separation layer is formed on a substrate such as glass, and may be a layer for separating the transparent conductive layer formed on the separation layer from the substrate together with the separation layer. The separation layer is preferably an inorganic layer or an organic layer. Examples of materials forming the inorganic layer include silicon oxide. As a material for forming the organic layer, for example, a (meth)acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. can be used. The separation layer can be formed by applying it using a known coating method and curing it by heat curing, UV curing, or a combination thereof.

The protective layer can be provided to protect the conductive layer in contact with the transparent conductive layer. The protective layer includes 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, or vapor deposition.

The insulating layer can be formed of, for example, an inorganic insulating material such as silicon oxide or a transparent organic material such as acrylic resin. The insulating layer can be formed by applying a known coating method, followed by heat curing, UV curing, heat drying, vacuum drying, etc.

As the base film for the touch sensor, triacetylcellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene naphthalate, polyolefin, polycycloolefin, polycarbonate, polyether sulfone, polyarylate, polyimide, polyamide, polystyrene, polynor. Resin films such as bornene can be mentioned. Polyethylene terephthalate is preferably used from the viewpoint of making it easy to construct a base film having the desired toughness.

The base film of the touch sensor preferably has a thickness of 50 μm or less, and more preferably 30 μm or less, from the viewpoint of easy construction of a laminate with excellent bending resistance. The thickness of the base film of the touch sensor may be, for example, 5 μm or more.

A touch sensor can be manufactured, for example, as follows. In the first method, a base film is first laminated on the substrate through an adhesive layer. On the base film, a patterned transparent conductive layer is formed by photolithography. By applying heat, the substrate and the base film are separated, and a touch sensor including the transparent conductive layer and the base film is obtained. The substrate is not particularly limited as long as it maintains flatness and has heat resistance, but is preferably a glass substrate.

In the second method, a material for forming a separation layer is first applied on the substrate to form the separation layer. If necessary, a protective layer is formed on the separation layer by application. A protective layer may be formed in the area where the pad pattern layer is formed to prevent the protective layer from being formed. On the separation layer (or protective layer), a transparent conductive layer patterned by photolithography is formed. On the transparent conductive layer, an insulating layer is formed to bury the electrode pattern layer. A protective film is laminated on the insulating layer with a peelable adhesive, the area from the insulating layer to the separation layer is transferred, and the substrate is separated. By peeling off the peelable protective film, a touch sensor having insulating layer/transparent conductive layer/(protective layer)/separation layer in this order is obtained.

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

When including a base film, the thickness of the touch sensor is, for example, 0.5 ㎛ or more and 10 ㎛ or less, and preferably 5 ㎛ or less.

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

The manufacturing method of an organic EL display device with a protective film includes, for example, the following processes:

(a) The first process of obtaining a circular polarizer by laminating a linear polarizer and a retardation plate,

(b) a second step of obtaining a film laminate by laminating a protection film on the circularly polarizing plate obtained in the first step,

(c) a third step of laminating an adhesive layer on the side opposite to the protection film side of the film laminate obtained in the second step to obtain a film laminate having an adhesive layer,

(d) a fourth step of bonding the film laminate having an adhesive layer obtained in the third step and an organic EL display panel through the adhesive layer to obtain a film laminate having an organic EL display panel, and

(e) A fifth step of providing a through hole in the film laminate having the organic EL display panel obtained in the fourth step to obtain an organic EL display device having a protection film may be included.

(1st process)

The linear polarizer and retardation plate can be manufactured as described above. A linear polarizer and a retardation plate can be bonded through a bonding layer. Surface activation treatment can be applied to the joint surface. When the bonding layer is a pressure-sensitive adhesive layer, for example, from a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer between two pieces of peelable separate films, one of the separate films is peeled off, the exposed pressure-sensitive adhesive layer is bonded to the retardation plate, and then the other side of the separate film is bonded. This can be done by peeling off the film and bonding the exposed adhesive layer and the linear polarizing plate. The adhesive sheet can be formed, for example, by applying an adhesive to a peelable separate film to form an adhesive layer, and then bonding a peelable separate film from the adhesive layer thereon.

(2nd process)

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

(Third process)

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

(4th process)

An organic EL display panel can be bonded through an adhesive layer exposed by peeling off a separate film from a film laminate having an adhesive layer.

(5th process)

Specific examples of methods for providing through holes in a film laminate having an organic EL display panel include, for example, a method of performing perforation processing using a rotating cutting tool such as a drill. The fifth step can be performed individually or in combination with a film laminate having an organic EL display panel.

Example

Hereinafter, the present invention will be described in more detail through examples. “%” and “part” in the examples are mass% and mass part, unless otherwise specified.

[Measurement of P _EL ]

The sealing layer side of the organic EL display panel (panel replacement) used in each example was bonded to alkali-free glass through an adhesive layer. By using Autograph (Product name (part number): “AGS-50NX”, manufactured by Shimadzu Corporation), one gripping part of the Autograph grips the alkali-free glass, and the other gripping part grips the main body. , P _EL was measured in an environment of a temperature of 23°C and a relative humidity of 55%, with a peeling width of 25 mm, a peeling angle of 180°, and a peeling speed of 300 mm/min.

[Measurement of S _PL ]

The bending strength (S _PL ) was measured using a Gurley stiffness tester (manufactured by Kumagaya Riki Kogyo) based on the Gurley method of JIS L-1085, 1095, and 1913. A sample was produced by cutting a circularly polarizing plate to a width of 25.4 mm and a length of 88.9 mm, and the sample was fixed using a clamp mounted on the movable arm of the device. Afterwards, adjust the position of the sample so that it contacts the upper end of the measurement pendulum, rotate the movable arm at a speed of 2 rpm, and after the pendulum is inclined, the maximum deflection of the sample is determined at the point when the contact point between the sample and the pendulum separates from the inclination angle of the pendulum. The value on the scale mounted on the bottom of the device indicated in the instructions was read. At this time, the weight of the weight required for measurement and the attachment position were appropriately adjusted according to the amount of bending of the sample.

Then the following equation:

Based on this, the bending strength (S _PL ) was calculated.

[Measurement of S _PF ]

S _PF was measured in the same manner as the measurement of S _PL except that a protection film was used instead of a circular polarizer.

[Measurement of F _PF ]

An organic EL display device with a protective film was cut to a width of 25 mm to obtain a measurement sample. Using a high-speed peeling device (manufactured by Imada Seisakusho), the organic EL display panel side of the measurement sample was adhered to the movable stage via an adhesive. Adhesion was measured by holding the protective film of the measurement sample and measuring the force when peeling in the 180° direction at a peeling speed of 18 m/min. Measurements were conducted in an environment with a temperature of 23 ± 2°C and a relative humidity of 50 ± 5%.

[Measurement of thickness]

The thickness of the layer was measured using a contact film thickness measuring device (“MS-5C” manufactured by Nikon Corporation). The thickness of the water-based adhesive layer and the polarizer were measured using a laser microscope ("OLS 3000" manufactured by Olympus Corporation).

[Evaluation of interlayer delamination]

The occurrence of interlayer peeling was confirmed when the protective film was peeled at 18 m/min using a high-speed peeling device (manufactured by Imada Seisakusho Co., Ltd.) equipped with a movable stage. First, samples prepared based on each example were cut to a size of 50 × 150 (mm). Additionally, the movable stage and the organic EL display device side were fixed with double-sided tape (“Nystack” manufactured by Nichiban Co., Ltd.). Next, an adhesive tape (“CT405AP-24” manufactured by Nichiban Co., Ltd., width 24) is bonded to the protective film at the end of the short side (50 mm) side of the sample cut above with a length of 20 mm in the in-plane direction. mm) was attached. Next, using this adhesive tape, the protective film is peeled from the circularly polarizing plate at a length of 10 mm from the short side end, and the adhesive tape is attached to the chuck mounted on the high-speed peeling device so that it is peeled at 180° toward the opposite end. , the movable stage was adjusted. After that, the protective film was peeled using a high-speed peeling device at a peeling speed of 18 m/min toward the opposite short side end. Visual confirmation by reflection of a fluorescent light was performed from both sides of the sample after the test to confirm the occurrence of interlayer peeling. The number of trials was conducted three times while changing the sample.

[Moisture and heat resistance test and observation of color loss]

The circularly polarizing plate produced above was bonded to an alkali-free glass plate using an acrylic adhesive, and was then left for 500 hours in an environment with a temperature of 65°C and a humidity of 90%RH. After that, a polarizing plate related to Cross-Nicol was bonded to the alkali-free glass surface opposite to the tested optical laminated body, observed with an optical microscope, and it was confirmed whether color loss had occurred at the edge. As an optical microscope, “VHX-500” manufactured by Keyence Corporation was used. The results are shown in Table 1. The evaluation criteria are as follows.

No fading: A

Color fading: B

[Bending resistance]

The method for evaluating bending resistance is explained below with reference to FIG. 6. The produced circularly polarizing plate was cut to a size of 10 mm on the short side x 100 mm on the long side using a super cutter so that the long side was in the direction of the absorption axis of the linear polarizer, and was used as a test piece 300. The short side of the test piece was fixed so that the surface on the linear polarizer side was in contact with the two plate jigs 301 and 302 of the bending resistance tester (FIG. 6A). The two plate jigs 301 and 302 were both flat jigs and were arranged to be parallel to each other. For fixation, Kapton film tape (manufactured by Toray DuPont) (303) was used, and both ends of the test piece were fixed in the long side direction with a width of 10 mm, and the inter-jig distance (L1) of the two plate jigs (301, 302) was fixed. was fixed to 53 mm. Next, when the bending radius (R) of the test piece is set to 1.5 mm, the two plate jigs 301 and 302 are moved in the directions indicated by the arrows A1 and A2 (directions approaching each other) to obtain the distance between the jigs (L2). was continuously changed to 2R, and the fixed test piece was bent so that the direction of the absorption axis of the linear polarizer was perpendicular to the bending axis (FIG. 6b). The bending speed was set at 60 rpm, and the number of bending times until cracks or breaks occurred in the film was measured. The results are shown in Table 1. The evaluation criteria are as follows.

Number of bends greater than 25000: A

The number of bends is 5,000 to 25,000 times: B

Number of bends less than 5000: C

[Production of Protective Film (A)]

(Preparation of adhesive composition (1))

Nitrogen gas was introduced into a reaction device equipped with a stirrer, thermometer, reflux cooling, and a nitrogen introduction tube, and the air in the reaction device was replaced with nitrogen gas. After that, 60 parts of solvent (ethyl acetate) were added to the reaction apparatus along with 93 parts of 2-ethylhexyl acrylate, 5.5 parts of 8-hydroxyoctylacrylate, and 1.5 parts of acrylic acid. After that, 0.1 part of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reaction was performed at a temperature of 65°C 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 approximately 500,000 in terms of standard polystyrene as determined by gel permeation chromatography.

To 100 parts of the acrylic polymer contained in the acrylic resin solution (1), 2.0 parts of 1-octylpyridinium dodecylbenzenesulfonate as an antistatic agent was added and stirred, followed by coronate HX (isocyanurate of hexamethylene diisocyanate compound) 1.5 parts (sieve: manufactured by Tosoh Corporation) was added and mixed with stirring to obtain adhesive composition (1).

(Production of protection film (A) with separate film)

After applying the adhesive composition (1) on a 15 ㎛-thick separate film containing a silicone resin-coated polyethylene terephthalate (PET) film, the solvent is removed by drying at 90°C, and the agent has a thickness of 15 ㎛ after drying. 2 An adhesive layer was formed. Thereafter, as a first base film, a polyethylene terephthalate (PET) film with a thickness of 75 μm, on one side of which was subjected to antistatic treatment and antifouling treatment, was used, and the PET film was subjected to antistatic treatment and antifouling treatment. The side opposite to the side was laminated on the second adhesive layer to obtain a protection film (A) with a separate film. The layer structure of the protection film (A) with a separate film was protection film (A) (1st base film/2nd adhesive layer)/separate film.

[Production of Protect Film (B)]

The same procedure as the production of the surface protection film (1) with a separate film, except that a 38 μm thick polyethylene terephthalate (PET) film with antistatic treatment and antifouling treatment on one side was used as the first base film. As a result, a protective film (B) with a separate film was obtained. The layer structure of the protection film 2 with a separate film was protection film (B) (1st base film/2nd adhesive layer)/separate film.

[Production of Protect Film (C)]

A protection film (C) was obtained in the same manner as the protection film D described in the specification (paragraph [0113]) of Japanese Patent Application Laid-Open No. 2018-173550.

[Production of Protect Film (D)]

A protection film (D) was obtained in the same manner as the protection film (C), except that a polyethylene terephthalate (PET) film with a thickness of 75 ㎛ was used without antistatic treatment or antifouling treatment on one side.

[Manufacture Example 1: Production of linear polarizer A]

A polyvinyl alcohol film with an average degree of polymerization of about 2400 and a degree of saponification of 99.9 mol% or more and a thickness of 30 ㎛ was immersed in pure water at 30°C and then immersed in an aqueous solution at 30°C with a mass ratio of iodine:potassium iodine:water of 0.02:2:100. Iodine staining was performed by immersion (hereinafter also referred to as iodine dyeing process). The polyvinyl alcohol film that had gone through the iodine dyeing process was immersed in an aqueous solution of potassium iodide: boric acid: water at a mass ratio of 12:5:100 at 56.5°C to perform boric acid treatment (hereinafter also referred to as boric acid treatment process). The polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8°C and then dried at 65°C to obtain a polarizer (thickness after stretching: 12 μm) in which iodine was adsorbed and oriented in polyvinyl alcohol. At this time, stretching was performed in the iodine dyeing process and boric acid treatment process. The total stretching ratio in this stretching was 5.3 times.

A water-based adhesive was applied to one side of the polarizer, and a triacetylcellulose (TAC) film (thickness: 25 μm) was corona treated and then bonded. Next, a water-based adhesive layer is applied to the surface of the polarizer opposite to the bonded TAC film side, and a triacetylcellulose (TAC) film (thickness: 32 μm) having a hard coat layer is corona treated and bonded to form a straight line. Polarizer A was produced.

[Manufacture Example 2: Production of linear polarizer B]

A water-based adhesive was applied to one side of the polarizer produced in Production Example 1, and a cyclic polyolefin resin (COP) film (thickness: 52 μm) having a hard coat layer was corona treated and then bonded to form linear polarizer B. was produced.

[Manufacture Example 3: Production of linear polarizer C]

(Base film)

As a base film, a triacetylcellulose (TAC) film (manufactured by Konica Minolta Co., Ltd., thickness 25 μm) was prepared.

(Composition for forming an alignment film)

Polymer 1 is a polymer having a photoreactive group containing the following structural units.

From GPC measurement, the molecular weight of polymer 1 obtained was a number average molecular weight of 28200, Mw/Mn 1.82, and the monomer content was 0.5%.

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

(polymerizable liquid crystal compound)

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

Compound (1-6) and compound (1-7) were synthesized by the method described in Lub et al.Recl.Trav.Chim.Pays-Bas, 115, 321-328 (1996).

(Dichromatic pigment)

As the dichroic dye, the azo dye described in the examples of Japanese Patent Application Laid-Open No. 2013-101328 represented by the following formulas (2-1a), (2-1b), and (2-3a) was used.

(Composition for forming a linear polarizing layer)

The composition for forming a linear polarizing layer includes 75 parts by mass of compound (1-6), 25 parts by mass of compound (1-7), and the above formula (2-1a), (2-1b), (2-3a) as a dichroic dye. 2.5 parts by mass each of the azo dyes represented by ), 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure369, manufactured by BASF Japan) as a polymerization initiator, and 1.2 parts by mass of a polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) as a leveling agent was mixed with 400 parts by mass of toluene as a solvent, and the resulting mixture was prepared by stirring at 80°C for 1 hour.

(Composition for protective layer (OC layer))

The composition for the protective layer contains 3 parts by mass of polyvinyl alcohol resin powder (manufactured by Kuraray Corporation, average degree of polymerization 18000, brand name: KL-318) and polyamide epoxy resin (crosslinking agent, Sumika Chemtex) based on 100 parts by mass of water. It was prepared by mixing 1.5 parts by mass of (trade name: SR650 (30)) manufactured by Co., Ltd.

(Production of linear polarizer C)

Corona treatment was performed on the base film. The conditions for corona treatment were an output of 0.3 kW and a processing speed of 3 m/min. Thereafter, the composition for forming an alignment film was applied onto the base film by a bar coat method and dried by heating in a drying oven at 80°C for 1 minute. The obtained dried film was subjected to polarized UV irradiation treatment to form an alignment film. Polarized UV treatment is performed by transmitting light irradiated from a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.) through a wire grid (UIS-27132##, manufactured by Ushio Denki Co., Ltd.) at a wavelength of 365. This was carried out under the condition that the integrated light amount measured at nm was 100 mJ/cm2. The thickness of the alignment film was 100 nm.

On the formed alignment film, the composition for forming a linear polarizing layer was applied by a bar coat method, heated and dried in a drying oven at 120°C for 1 minute, and then cooled to room temperature. Using the UV irradiation device, a linear polarization layer was formed by irradiating the dried film with ultraviolet rays at an accumulated light amount of 1200 mJ/cm2 (based on 365 nm). The thickness of the obtained linearly polarized layer was measured using a laser microscope (OLS 3000 manufactured by Olympus Corporation) and was found to be 1.8 μm. In this way, a laminate containing “base film/alignment film/linear polarization layer” was obtained.

On the formed linear polarizing layer, the composition for a protective layer (OC layer) was applied by a bar coat method to a thickness of 1.0 μm after drying, and dried at a temperature of 80° C. for 3 minutes. In this way, linear polarizing plate C containing “base film/alignment film/linear polarizing layer/protective layer (OC layer)” was obtained.

[Manufacture Example 4: Production of linear polarizer D]

(Base film)

As a base film, a polyethylene terephthalate (PET) film (thickness 100 μm) was prepared.

(Composition for protective layer (HC layer))

2.8 parts by mass of dendrimer acrylate (Miramer SP1106, Miwon) having an 18-functional acrylic group, 6.6 parts by mass of urethane acrylate (Miramer PU-620D, Miwon) having a 6-functional acrylic group, and a photopolymerization initiator (Irgacure-184, BASF) ) 0.5 parts by mass, 0.1 parts by mass of leveling agent (BYK-3530, BYK), and 90 parts by mass of methyl ethyl ketone (MEK) were mixed to prepare a composition for a protective layer (HC layer).

As the composition for forming an alignment film, the composition for forming a linear polarizing layer, and the composition for a protective layer (OC layer), the compositions described in the section above [Linear Polarizing Plate C] were used, respectively.

(Production of linear polarizer D)

The composition for the protective layer (HC layer) was applied to the base film by a bar coat method and dried by heating in a drying oven at 80°C for 3 minutes. The obtained dried film was irradiated with UV light at an exposure dose of 500 mJ/cm2 (based on 365 nm) using a UV irradiation device (SPOT CURE SP-7, manufactured by Ushio Denki Co., Ltd.) to form a protective layer (HC layer). . The thickness of the protective layer (HC layer) was measured using a laser microscope (OLS3000 manufactured by Olympus Corporation) and was 2.0 μm. In this way, a laminate containing “base film/protective layer (HC layer)” was obtained.

Corona treatment was performed once on the protective layer (HC layer) side of the laminate containing the “base film/protective layer (HC layer).” The conditions for corona treatment were an output of 0.3 kW and a processing speed of 3 m/min. Thereafter, the composition for forming an alignment film was applied onto the protective layer (HC layer) by a bar coat method and dried by heating in a drying oven at 80°C for 1 minute. The obtained dried film was subjected to polarized UV irradiation treatment to form a first alignment film. Polarized UV treatment is performed by transmitting light irradiated from a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.) through a wire grid (UIS-27132##, manufactured by Ushio Denki Co., Ltd.) at a wavelength of 365. This was carried out under the condition that the integrated light amount measured at nm was 100 mJ/cm2. The thickness of the alignment film was 100 nm.

On the formed alignment film, the composition for forming a linear polarizing layer was applied by a bar coat method, heated and dried in a drying oven at 120°C for 1 minute, and then cooled to room temperature. Using the UV irradiation device, a linear polarization layer was formed by irradiating the dried film with ultraviolet rays at an accumulated light amount of 1200 mJ/cm2 (based on 365 nm). The thickness of the obtained linearly polarized layer was measured using a laser microscope (OLS 3000 manufactured by Olympus Corporation) and was found to be 1.8 μm. In this way, a laminate containing “base film/protective layer (HC layer)/alignment film/linear polarization layer” was obtained.

On the formed polarizing layer layer, the composition for a protective layer (OC layer) was applied by a bar coat method so that the thickness after drying was 1.0 μm, and dried at a temperature of 80° C. for 3 minutes. In this way, a laminate containing “base film/protective layer (HC layer)/alignment film/linear polarization layer/protective layer (OC layer)” was obtained. Immediately before use, the base film was peeled to obtain a linear polarizing plate D containing “protective layer (HC layer)/alignment film/linear polarizing layer/protective layer (OC layer).”

[Manufacture Example 5: Production of retardation plate]

(Fabrication of 1/4 wavelength retardation layer 1)

A base film containing a polyethylene terephthalate resin (PET) film (thickness 100 ㎛) was prepared. A rubbing treatment was performed on the base film to form an alignment film (1 ㎛ thick). On the alignment film, a composition for forming a liquid crystal layer containing a rod-shaped nematic polymerizable liquid crystal compound (liquid crystal monomer) was applied and solidified by irradiation with ultraviolet rays while maintaining refractive index anisotropy. In this way, a 1/4 wavelength retardation layer with reverse wavelength dispersion as a cured layer of the polymerizable liquid crystal compound with a thickness of 1 μm was formed on the alignment layer of the base film.

(Production of positive C plate)

A base film containing a polyethylene terephthalate resin (PET) film (thickness 38 ㎛) was prepared. The composition for forming a vertical alignment film was applied to one side of the base film to a film thickness of 3 μm, and irradiated with ultraviolet rays of 200 mJ/cm 2 to produce a vertical alignment film. A composition for forming a positive C plate containing a polymerizable liquid crystal compound is applied onto the vertical alignment film, and after drying, the coating film is irradiated with ultraviolet rays (UV) to polymerize the polymerizable liquid crystal compound to form a cured layer of the polymerizable liquid crystal compound. By doing so, a positive C plate was obtained.

(Production of retardation 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. Each corona-treated surface was bonded using the active energy ray-curable adhesive prepared above. Afterwards, from the positive C plate side, using an ultraviolet irradiation device (manufactured by Fusion UV Systems Co., Ltd.), ultraviolet rays are irradiated with an integrated light amount of 400 mJ/cm2 (UV-B) to cure the active energy ray curable adhesive. An adhesive layer was formed. Bonding was performed using a laminator, and the active energy ray-curable adhesive was applied so that the thickness of the adhesive layer after curing was 3 μm. As a result, a top difference layer plate was obtained including the base film, alignment film, 1/4 wavelength retardation layer, active energy ray-curable adhesive layer, positive C plate, vertical alignment film, and base film in this order.

<Example 1>

The 1/4 wavelength retardation layer side of the retardation layer was bonded to the TAC film side of the linear polarizer A through an adhesive layer (thickness: 5 μm) to obtain a circularly polarizing plate. Before joining, corona treatment was performed on each joining surface. Next, protect film C was laminated on the linear polarizer side of the circular polarizer. After that, an adhesive layer was laminated on the side opposite to the protection film side of the circularly polarizing plate, and a film laminate with an adhesive layer was obtained. Next, in order to evaluate interlayer peeling at two levels of adhesion P _EL , organic EL display devices A and B having the following protective films were prepared as follows.

[Organic EL display device A with protective film]

(Linear polarizing layer with diffusion prevention layer)

As a panel replacement for an organic EL display panel, a linear polarizing layer with a diffusion prevention layer was prepared as follows.

(Preparation of water-soluble polymer aqueous solution)

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

In 400 g of dimethyl sulfoxide, 20 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) with a molecular weight of 1000, 0.55 mg of N,N-dimethyl-4-aminopyridine as a nucleophilic agent, and 4.6 g of triethylamine. It was dissolved and the temperature was raised to 60°C while stirring. After that, a solution in which 10.5 g of methacrylic anhydride was dissolved in 50 g of dimethyl sulfoxide was added dropwise over 1 hour, and the reaction was carried out by heating and stirring at a temperature of 60°C for 14 hours. After cooling the obtained reaction solution to room temperature, 481 g of methanol was added to the reaction solution and stirred to completely mix, thereby adjusting the ratio (mass) of the reaction solution to methanol to 1:1. By gradually adding 1500 mL of acetone to this solution, the water-soluble polymer was crystallized by crystallization. The solution containing the obtained white crystals was filtered, washed well with acetone, and then vacuum dried to obtain 20.2 g of water-soluble polymer. 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 components were mixed, and the resulting mixture was stirred at a temperature of 80°C for 1 hour to obtain a composition for forming a photo-alignment layer.

Photo-alignment polymer [polymer represented by the following formula described in Japanese Patent Application Laid-Open No. 2013-33249 (number average molecular weight: about 28200, Mw/Mn: 1.82)]: 2 parts

· Solvent [o-xylene]: 98 parts

(Preparation of first composition)

The first composition was obtained by mixing each of the following components and stirring at a temperature of 80°C for 1 hour. As the dye having absorption anisotropy, an azo dye represented by the following formula described in the examples of Japanese Patent Application Laid-Open No. 2013-101328 was used.

・Polymerizable liquid crystal compound (A1) represented by the following formula: 75 parts

・Polymerizable liquid crystal compound (A2) represented by the following formula: 25 parts

・Dye having absorption anisotropy expressed by the following formula (azo dye 1): 2.5 parts

・Dye having absorption anisotropy expressed by the following formula (azo dye 2): 2.5 parts

・Dye having absorption anisotropy expressed by the following formula (azo dye 3): 2.5 parts

-Polymerization initiator [2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Igacure 369; manufactured by Chiba Specialty Chemicals Co., Ltd.)]: 6 parts

· Leveling agent [polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)]: 1.2 parts

· Solvent [o-xylene]: 250 parts

(Preparation of second composition)

The second composition was obtained by mixing each of the following components and stirring at a temperature of 80°C for 1 hour.

・Polymerizable liquid crystal compound (X1) represented by the following formula: 100 parts

・Polymerizable liquid crystal compound (X2) represented by the following formula: 33 parts

-Polymerization initiator [2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Igacure (registered trademark) 369; manufactured by BASF Japan)]: 8 parts

· Leveling agent [polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)]: 0.1 part

·Reaction additive [LALOMER LR9000; Manufactured by BASF Japan]: 6.7 parts

· Solvent [cyclopentanone]: 546 parts

· Solvent [N-methylpyrrolidone]: 364 parts

(Preparation of composition for forming orientation layer)

A composition for forming an orientation layer was prepared by adding 2-butoxyethanol to SunEver SE-610 (manufactured by Nissan Chemical Industries, Ltd.), a commercially available orientation polymer. The content of solid content relative to the total amount of the composition for forming an orientation layer was 1%, and the content of solvent was 99%. The solid content of the oriented polymer was converted from the nominal concentration of SunEver SE-610.

(Preparation of third composition)

Each of the following components was mixed, stirred at a temperature of 80° for 1 hour, and then cooled to room temperature to obtain a third composition. The content ratio shown below is the content ratio of each component with respect to the total amount of the third composition.

· Polymerizable liquid crystal compound represented by the following formula [LC242; Manufactured by BASF]: 19.2%

·Polymerization initiator [Igacure 907; Manufactured by BASF Japan]: 0.5%

·Leveling agent [manufactured by Big Chemi Japan; BYK361N]: 0.1%

·Reactive additive [Laromer LR-9000; Manufactured by BASF Japan]: 1.1%

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

(Production of linear polarizing layer with diffusion prevention layer)

3% by mass of water-soluble polymer aqueous solution prepared above was applied to the release-treated surface of a release polyethylene terephthalate (PET) film (“FF-50” manufactured by Unichika Co., Ltd., PET film with one-side release treatment, substrate thickness: 50 μm). was applied with a bar coater and dried at a temperature of 100°C for 2 minutes to form a first diffusion prevention layer with a thickness of 2 ㎛ including a film of water-soluble polymer.

After plasma treatment was performed on the surface of the first diffusion prevention layer, the composition for forming a photo-alignment layer prepared above was applied using a bar coater to form a coating film. This coating film was dried at 100°C for 2 minutes to remove the solvent and form a dry film. An orientation regulating force was applied to the dried film by irradiating polarizer external light at an intensity of 20 mJ/cm2 (based on 313 nm), thereby forming a first alignment layer with a thickness of 50 nm.

On the first orientation layer, the first composition prepared above was applied using a bar coater to form a coating film. In addition, the solvent was removed by drying at a temperature of 110°C for 2 minutes, and the polymerizable liquid crystal compound was phase transferred into the liquid phase, and then cooled to room temperature to phase transfer the polymerizable liquid crystal compound into a smectic liquid crystal state. Thereafter, the obtained dry film is irradiated with ultraviolet light at 1000 mJ/cm2 (based on 365 nm) using a high-pressure mercury lamp to polymerize the polymerizable liquid crystal compound contained in the dry film while maintaining the smectic liquid crystal state, thereby reducing the thickness. A first cured layer of 3 μm was formed.

After plasma treatment was performed on the first cured layer, the 3% by mass water-soluble polymer aqueous solution prepared above was applied using a bar coater, and dried at a temperature of 100° C. for 2 minutes to obtain a thickness of 2 including a water-soluble polymer film. A second diffusion prevention layer of ㎛ was formed to obtain a linear polarizing layer A having a diffusion prevention layer. The layer structure of the linear polarizing layer A with a diffusion prevention layer was release PET film/first diffusion prevention layer/linear polarization layer (first alignment layer/first cured layer)/second diffusion prevention layer. At this time, the release PET film corresponds to the main body of the organic EL display panel, and the area from the first diffusion prevention layer to the second diffusion prevention layer corresponds to the sealing layer. The adhesion (P _EL ) between the release PET film (main body) and the first diffusion prevention layer to the second diffusion prevention layer (sealing layer) was 0.03 [N/25 mm]. Additionally, in the measurement of adhesion (P _EL ), no separation occurred between the first diffusion prevention layer and the second diffusion prevention layer.

A second diffusion prevention layer side (sealing layer side) of a linear polarizing layer (a replacement for an organic EL display panel) having a diffusion prevention layer, and a film laminate having the adhesive layer obtained above (the linear polarizing plate is A, and the protection film is C). ) was bonded to an adhesive layer to produce an organic EL display device A with a protection film.

[Organic EL display device B with protective film]

(Production of sealing layer with base layer)

As a panel replacement for an organic EL display panel, a sealing layer having a base layer was produced as follows. Corona treatment was performed on the surface opposite to the release-treated side of a release polyethylene terephthalate (PET) film (“FF-50” manufactured by Unichika Co., Ltd., PET film with one-side release treatment, substrate thickness: 50 μm). . On this corona-treated surface, the composition for forming a photo-alignment layer prepared above was applied using a bar coater, dried at 120°C for 2 minutes, and cooled to room temperature to form a dry film. The dried film was irradiated with polarized ultraviolet light at an intensity of 100 mJ/cm2 (based on 313 nm) to form a second alignment layer with a thickness of 100 nm.

On the second orientation layer, the second composition prepared above was applied using a bar coater to form a coating film. Additionally, after drying by heating at 120°C for 2 minutes, it was cooled to room temperature to obtain a dry film. Thereafter, the dried film is irradiated with ultraviolet rays at an exposure amount of 1000 mJ/cm2 (based on 365 nm) using an ultraviolet irradiation device, so that the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the surface of the first retardation layer. A second cured layer with a thickness of 2 μm was formed, thereby obtaining a first phase difference layer having a base layer. The layer structure of the first retardation layer having a base material layer was release PET film/1st retardation layer (2nd alignment layer/2nd cured layer). At this time, the release PET film corresponds to the main body portion of the organic EL display panel, and the first phase difference layer (second alignment layer/second cured layer) corresponds to the sealing layer. The adhesion (P _EL ) between the release PET film (main body) and the first phase difference layer (second orientation layer/second cured layer) (sealing layer) was 0.06 [N/25 mm]. In addition, in the measurement of adhesion (P _EL ), no peeling occurred within the first phase difference layer (2nd alignment layer/2nd cured layer).

An organic EL display device having a protection film by bonding the sealing layer side of the sealing layer having a base layer and the adhesive layer of the film laminate having the adhesive layer obtained above (the linear polarizing plate is A and the protection film is C). B was produced.

After providing a through hole in the organic EL display devices A and B with a protection film using a drill, the protection film was peeled off, and interlayer peeling was evaluated. The results are shown in Table 1.

<Examples 2 to 14>

Interlayer peeling was evaluated at two levels of adhesion (P _EL ) in the same manner as in Example 1, except that the protective film and linear polarizing plate shown in Table 1 were used. The results are shown in Table 1.

In addition, the evaluation result is evaluated as evaluation A when peeling is not recognized in all three tests in the evaluation of interlayer peeling,

P _EL = 0.03 N/25 mm Linear polarizing layer with diffusion prevention layer A [Panel replacement for organic EL display panel] When peeling is recognized in one sheet and peeling is not recognized in all remaining panel replacements, evaluation B And,

P _EL = 0.03 N/25 mm Linear polarizing layer with a diffusion prevention layer A (panel replacement for organic EL display panel) is evaluated when peeling is recognized in all three sheets and peeling is not recognized in all remaining similar panels. Let it be C,

Linear polarizing layer A [panel replacement for organic EL display panel] having a diffusion prevention layer of P _EL =0.03 N/25 mm, and a sealing layer [substitute for organic EL display panel] having a base layer having P _EL =0.06 N/25 mm When the occurrence of peeling is recognized, it is given an evaluation of D,

When peeling was recognized in all organic EL display panel replacement products, an evaluation was made of E.

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

Claims (5)

An organic EL display device having a protection film and an organic EL display device,
When viewed in plan, it has a through hole,
The protective film is laminated in a peelable manner on the viewing side of the organic EL display device,
The organic EL display device includes an organic EL display panel and a circularly polarizing plate laminated on a viewing side of the organic EL display panel through an adhesive layer,
The organic EL display panel includes a main body portion and a sealing layer laminated on a viewing side of the main body portion,
The adhesion between the main body and the sealing layer is P _EL [N/25 mm], the bending strength of the circular polarizer is S _PL [N m], the bending strength of the protection film is S PF [N m], and the bending strength of the protective film is S _PF [N m]. When the peeling force when peeling the protect film from the circularly polarizing plate at a peeling speed of 18 m/min is set to F _PF [N/25 mm], the following equation:
(1) P _EL ≤0.10[N/25 ㎜]
(2) 0.10[25 ㎜/N]≤S _PL /(S _PF ×F _PF )
An organic EL display device having a protection film that satisfies the above. The organic EL display device according to claim 1, wherein the circularly polarizing plate is a laminate of a liquid crystal curing polarizer layer and a liquid crystal curing retardation layer. The organic EL display device according to claim 1, wherein the diameter of the through hole is 1 mm or more. The organic EL display device according to claim 2, wherein the diameter of the through hole is 1 mm or more. The organic EL display device according to any one of claims 1 to 4, wherein the thickness of the circularly polarizing plate is 120 μm or less.