JP6547481B2 - Organic electroluminescent laminate - Google Patents

Description

The present invention relates to an organic electroluminescent laminate.

In recent years, an optical film used for organic electroluminescence may have excellent hardness and may be required to have excellent durable folding performance without causing cracks even when the optical film is repeatedly folded.

However, since the hardness and the folding performance are usually in a trade-off relationship, when the hardness is improved in the conventional optical film, the durable folding performance is reduced, and the hardness is reduced when the durable folding performance is improved. Therefore, these performances could not be made excellent simultaneously.

In organic electroluminescence, a glass substrate is often used. However, glass is high in hardness but is broken when folded and can not be provided with folding performance, and since glass is a material with a large specific gravity, it is necessary to make it thin to achieve weight reduction, When the glass is made thinner, there is a problem that the strength is reduced and the glass is easily broken.

Further, for example, in Patent Document 1, as an optical film having hardness and flexibility, two hard coat layers having different Vickers hardness are formed on one surface of a substrate film such as a cellulose acylate film or a polyester film. An optical film provided is disclosed.
However, although such an optical film has excellent hardness, the base film may be broken or a mark of folding may be caused by repeated folding, and in such a case that the durable folding performance required in recent years is satisfied. It was not.

Moreover, although it is examined using a polyimide film as a base film in an optical film from having the outstanding mechanical strength, a polyimide film generally has low transparency and it is used as an optical film. Was not suitable.
Furthermore, even if it uses a polyimide film as a base film, it was difficult to make compatible the outstanding durable folding performance and hardness which were requested | required in recent years.

JP, 2014-186210, A

An object of the present invention is to provide a laminate for organic electroluminescence having excellent hardness, transparency, and durable folding performance in view of the above-mentioned present situation.

The present invention is a laminate for organic electroluminescence in which an optical laminate is laminated on one surface of the organic electroluminescence layer, and a test in which the entire surface of the organic electroluminescence laminate is folded 180 ° at intervals of 20 mm It is a laminate for organic electroluminescence characterized in that no cracking or breakage occurs when repeated 100,000 times.

In the laminate for organic electroluminescence of the present invention, in the optical laminate, the substrate film is preferably a polyimide film or an aramid film.
Moreover, as for an optical laminated body, it is preferable that the thickness of a base film is 10-55 micrometers.
In addition, the optical laminate is provided on the first hard coat layer provided on the side opposite to the organic electroluminescent layer of the base film, and on the side opposite to the base film of the first hard coat layer. It is preferable to have a second hard coat layer.
Further, the second hard coat layer contains a cured product of a polyfunctional (meth) acrylate monomer as a resin component, and the first hard coat layer contains a cured product of a polyfunctional (meth) acrylate as a resin component, It is preferable to contain the silica particle disperse | distributed in the said resin component, and it is preferable that the said silica particle is a reactive silica particle.
In addition, the optical laminate preferably further includes a cured layer of a monofunctional monomer.

In the organic electroluminescent layer, the substrate is preferably a polyimide film, an aramid film, a polyester film, a polyethylene naphthalate film, a cycloolefin film or an acrylic film.
Hereinafter, the present invention will be described in detail.

The laminate for organic electroluminescence of the present invention (hereinafter, electroluminescence is also simply referred to as organic EL) has a structure in which an optical laminate is laminated on one surface of an organic EL layer.
In the optical laminate, the substrate film is preferably a polyimide film or an aramid film.
Here, the polyimide film and the aramid film are generally colored (yellow) because they have an aromatic ring in the molecule, but when used for an optical film application, the skeleton in the molecule is changed Is a film called “transparent polyimide” or “transparent aramid” with enhanced transparency. On the other hand, it is preferable to use the colored conventional polyimide film etc. for electronic materials, such as a printer and an electronic circuit, from the surface of heat resistance and flexibility.
A laminate for an organic EL using a substrate film made of these materials does not have cracks or fractures in the durable folding test described later, and has not only the excellent durable folding performance required in recent years, but also excellent hardness. And transparency.
Moreover, a polyimide film and an aramid film are excellent also in heat resistance, and by baking, it can also provide the further outstanding hardness and transparency.

Here, in the laminate for an organic EL of the present invention, the above-mentioned excellent hardness means the pencil hardness test (750 g load) defined in JIS K5600-5-4 (1999) of the hard coat layer in the optical laminate to be described later. The hardness measured under the conditions means 5H or more, preferably 6H or more, and more preferably 7H or more.
Further, in the laminate for an organic EL of the present invention, the above-mentioned excellent transparency means the total light transmittance when the hard coat layer described later does not have an uneven shape on the surface opposite to the substrate film side. Is 85% or more, and the total light transmittance is preferably 90% or more.
On the other hand, when the hard coat layer described later has an uneven shape on the surface opposite to the substrate film side, it means that the total light transmittance is 80% or more, and the total light transmittance is 85% or more Is preferred.

As said polyimide film, the compound which has a structure represented by a following formula is mentioned, for example.
In the following formulas, n is a repeating unit and represents an integer of 2 or more.

The above-mentioned aramid film generally has a skeleton represented by the following formulas (18) and (19), and as the above-mentioned aramid film, for example, a compound represented by the following formula (20) Can be mentioned.
In the following formulas, n is a repeating unit and represents an integer of 2 or more.

A commercially available thing may be used for the polyimide film or aramid film represented by said Formula (1)-(17) and (20).
Examples of commercially available products of the transparent polyimide film include neoprim manufactured by Mitsubishi Gas Chemical Co., Ltd., and examples of commercially available products of the transparent aramid film include Miktron manufactured by Toray Industries, Inc.
Moreover, you may use what was synthesize | combined by the well-known method as the polyimide film or aramid film represented by said Formula (1)-(17) and (20).
For example, the synthesis method of the polyimide film represented by the said Formula (1) is described in Unexamined-Japanese-Patent No. 2009-132091, and, specifically, following formula (21)

Reacting 4,4'-hexafluoropropylidenebisphthalic acid dianhydride (6FPA) represented by and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFDB) It can be obtained by

The weight average molecular weight of the polyimide film or aramid film is preferably in the range of 3,000 to 500,000, more preferably in the range of 5,000 to 300,000, and still more preferably in the range of 10,000 to 200,000. . When the weight average molecular weight is less than 3,000, sufficient strength may not be obtained, and when it exceeds 500,000, the viscosity increases and the solubility decreases, so a film having a smooth surface and a uniform film thickness is obtained. I can not do it.
In addition, in this specification, a weight average molecular weight is the polystyrene conversion value measured by gel permeation chromatography (GPC).

Among the above-mentioned polyimide films or aramid films, polyimide films or aramid films having a structure in which intra-molecular or inter-molecular charge transfer is unlikely to occur are preferred because they have excellent transparency. And fluorinated polyimide films such as the above formulas (9) to (12), and aramid films having halogen groups such as the above formula (20) and the like.
In addition, fluorinated polyimide films such as the above formulas (1) to (8) have high heat resistance because they have a fluorinated structure, and are not colored by heat during polyimide film production. So it has excellent transparency.
The base film has a hardness of 5 H or more, which is measured under the condition of a pencil hardness test (750 g load) defined in JIS K 5600-5-4 (1999) of the hard coat layer described later. It is preferable to use an aramid film having a fluorinated polyimide film such as (1) to (8) or a halogen group such as the above formula (20). Among them, it is more preferable to use a polyimide film represented by the above-mentioned formula (1) because it can impart extremely excellent hardness of 7 H or more to the above-mentioned pencil hardness.

It is preferable that the said base film is 10-55 micrometers in thickness. When the thickness of the substrate film is less than 10 μm, the curl of the laminate for an organic EL of the present invention may be large, and the hardness may be insufficient, and the pencil hardness described later may not be 4H or more. When the laminate for an organic EL of the present invention is produced by Roll to Roll, wrinkles are likely to occur, which may cause deterioration in the appearance. On the other hand, if the thickness of the substrate film exceeds 55 μm, the folding performance of the laminate for an organic EL of the present invention may be insufficient, and the requirements for the durable folding test described later may not be satisfied. The laminate for EL becomes heavy, which is not preferable in terms of weight reduction.

In the laminate for an organic EL of the present invention, no cracking or breakage occurs when the test of folding the entire surface of the laminate for an organic EL at 180 ° with a distance of 20 mm is repeated 100,000 times.
In the laminate for an organic EL of the present invention, it is preferable that no cracking or breakage occurs when the test of folding the entire surface of the laminate for an organic EL at 180 ° is repeated 100,000 times at an interval of 15 mm; It is more preferable that a crack or a fracture does not arise when the test which folds the whole surface of the above-mentioned layered product for organic EL by 180 degrees is repeated 100,000 times.
FIG. 1 is a cross-sectional view schematically showing a test in which the entire surface of the laminate for an organic EL of the present invention is folded 180 ° at intervals of 520 mm (hereinafter, also referred to as a durable folding test). In the present invention, the distance of 520 mm means that the distance between the facing organic EL laminates is 520 mm.
As shown in FIG. 1 (a), in the durable folding test, first, one side of the laminate 10 for an organic EL of the present invention and the other side facing the one side are made parallel to each other. It fixes to the upper fixed part 11 and the lower fixed part 12 which were arrange | positioned, respectively. In addition, although the laminated body for organic EL of this invention may be arbitrary shapes, it is preferable that the laminated body 10 for organic EL in this invention in the said durable folding test is rectangular.
Further, as shown in FIG. 1, the upper fixing portion 11 is fixed, and the lower fixing portion 12 is movable left and right while maintaining the parallel with the upper fixing portion 11.

Next, as shown in FIG. 1 (b), the lower fixed portion 12 is moved leftward to move the bent portion of the test piece 10 to the vicinity of the other side fixed to the lower fixed portion 12, Furthermore, as shown in FIG. 1C, by moving the lower fixing portion 12 to the right, the bent portion of the test piece 10 is moved to the vicinity of one side fixed to the upper fixing portion 11.
By moving the lower fixing portion 12 as shown in FIGS. 1 (a) to 1 (c), the entire surface of the laminate for an organic EL of the present invention can be folded 180 °.
The laminate for an organic EL according to the present invention is cracked or broken in the test piece when the laminate 10 for an organic EL is subjected to the folding test represented in FIGS. 1 (a) to 1 (c) described above 100,000 times. Does not occur. If cracking or breakage occurs in the laminate 10 for an organic EL of the present invention within 100,000 times, the durable folding performance of the laminate for an organic EL of the present invention becomes insufficient. In the present invention, it is preferable that no cracking or breakage occurs when the above durable folding test is performed 150,000 times on the laminate 10 for an organic EL of the present invention.
Moreover, although the laminated body 10 for organic EL of this invention may be a thing which a crack or a fracture does not produce when the said durable folding test is done with respect to single side | surface, the said durable folding test is made with respect to both sides. Preferably, no cracking or breakage occurs when done.
In the present invention, even if the above-described laminate 10 for an organic EL according to the present invention is rotated 90 ° and subjected to the same endurance folding test, no cracking or breakage similarly occurs.

It is preferable that the laminated body for organic EL of this invention has interference fringe prevention performance.
The laminate for an organic EL according to the present invention has folding performance, and thus has a new problem of interference fringes such as interference fringes being noticeable in the folding part or movement of the interference fringes by folding.
The laminate for organic EL of the present invention determines the spectral reflectance of the laminate for organic EL in a wavelength range of 400 nm to 700 nm, and the standard deviation of the spectral reflectance in an arbitrary 50 nm range is less than 0.045. Is preferred.
The standard deviation of the spectral reflectance can be determined by the following procedure.
First, the reflectance in the wavelength range of 380 nm to 780 nm of the laminate for an organic EL according to the present invention is measured by a five-degree reflectometry using a spectrophotometer. Specifically, light having an incident angle of 5 degrees is irradiated to the surface of the laminate for an organic EL of the present invention on which the hard coat layer is formed, and the positive electrode reflected on the laminate for an organic EL of the present invention The reflected light in the reflection direction is received, and the reflectance in the wavelength range of 380 nm to 780 nm is measured.
Next, an approximate value is obtained with a second-order polynomial for the wavelength range of 400 to 700 nm of the measurement data.
Finally, for any 50 nm range, the standard deviation is calculated from the difference between the measured value and the approximation with a quadratic polynomial.
In addition, the said spectral reflectance used the spectral reflectance measured by the spectrophotometer (MPC3100, Shimadzu Corp. make).

In the laminate for an organic EL of the present invention, the standard deviation of the spectral reflectance in an arbitrary range of 50 nm is less than 0.045 in the visible light range of wavelengths 400 nm to 700 nm.
The laminate for an organic EL of the present invention satisfying the requirements of the standard deviation of the spectral reflectance described above has extremely excellent interference fringe prevention performance, no interference fringes are generated in the folded portion, and movement caused by folding is achieved. No interference fringes are observed either.
In the laminate for organic EL of the present invention, the standard deviation of the spectral reflectance in an arbitrary range of 50 nm is preferably less than 0.035 and less than 0.025 in the visible light region of wavelengths 400 nm to 700 nm. Is more preferred.
In the laminate for an organic EL according to the present invention, the standard deviation in the range of 50 nm having the largest standard deviation in the range of wavelengths 400 to 700 nm is more preferably less than 0.045, and less than 0.035. It is especially preferred that there be less than 0.025.

In the laminate for an organic EL of the present invention, the optical laminate preferably further includes a cured layer of a monofunctional monomer.
The cured layer of the monofunctional monomer is preferably provided on the side opposite to the organic EL layer of the base film.
In addition, the cured layer of the monofunctional monomer may be provided between the base film and the first hard coat layer described later, and the cured layer of the first hard coat layer and the second hard coat layer described later Although it may be interposed, it is more preferable to have it between the above-mentioned base film and the first hard coat layer described later, from the viewpoint of imparting extremely excellent interference fringe prevention properties.
The cured layer of the monofunctional monomer is a layer for imparting the above-described interference fringe prevention performance.
In the laminate for organic EL of the present invention, in the optical laminate, when forming the cured layer of the monofunctional monomer, the monofunctional monomer component in the composition for the cured layer of the monofunctional monomer described later is the above-described group By dissolving the material film or the like, the refractive index of the dissolved portion of the resin base material or the like changes stepwise, and interface reflection can be suppressed, so that extremely excellent interference fringe prevention performance can be imparted. .

The thickness of the cured layer of the monofunctional monomer is preferably 0.5 to 8 μm. If it is less than 0.5 μm, the above-mentioned interference fringe prevention performance may not be sufficiently imparted, and if it exceeds 8 μm, sufficient pencil hardness may not be imparted.
A more preferable range of the thickness of the cured layer of the monofunctional monomer is 1 to 5 μm, and more preferably 1 to 3 μm.
The thickness of the hard coat layer can be measured by cross-sectional microscope observation.

As a monofunctional monomer used for the cured layer of the said monofunctional monomer, ionizing radiation curable resin is mentioned, for example, Especially, a monofunctional acrylic monomer is used suitably.
The monofunctional acrylic monomer is at least one selected from the group consisting of acryloyl morpholine, N-acryloyloxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate. Among them, even when a polyimide film or the like excellent in solvent resistance is used as a resin substrate, the film can be suitably dissolved, and extremely excellent interference fringe prevention performance is imparted. It is preferable that it is acryloyl morpholine from what can be done.

The cured layer of the monofunctional monomer is, for example, a composition for a cured layer of a monofunctional monomer containing the above-described monofunctional monomer and a solvent, which is coated on the surface of the base film, and the formed coating is dried. It can be formed by post curing.
As a solvent in the composition for cured layers of the said monofunctional monomer, the solvent used by the composition for hard-coat layers mentioned later can be used suitably.

The composition for the cured layer of the monofunctional monomer is, similarly to the composition for the hard coat layer described later, a photopolymerization initiator, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, a coloring Inhibitors, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers and the like may be added.

In the laminate for an organic EL according to the present invention, the optical laminate comprises a first hard coat layer provided on the side opposite to the organic EL layer of the base film, and the base film side of the first hard coat layer. And the second hard coat layer provided on the opposite side.
Hereinafter, both the first hard coat layer and the second hard coat layer are also simply referred to as “hard coat layer” unless it is necessary to distinguish them.

The first hard coat layer is a layer for imparting hardness, and the Martens hardness at the center of the cross section is preferably 500 MPa or more and less than 1000 MPa.
By setting the Martens hardness of the first hard coat layer in the above range, the hardness of a pencil hardness test (750 g load) defined in JIS K 5600-5-4 (1999) of the hard coat layer is 4 H or more. In addition, sufficient durability folding performance can be imparted to the laminate for an organic EL of the present invention. The more preferable lower limit of the Martens hardness at the center of the cross section of the first hard coat layer is 600 MPa, and the more preferable upper limit is 950 MPa.

The second hard coat layer is a layer for imparting the above-described durability and scratch resistance, and the Martens hardness at the center of the cross section is preferably 350 MPa or more and 600 MPa or less. By setting the Martens hardness of the second hard coat layer to the above range, it has sufficient endurance folding performance, and the surface of the hard coat layer while applying a load of 1 kg / cm ² with # 0000 steel wool. It is possible to impart extremely excellent scratch resistance such as no scratching in a steel wool test in which the surface is rubbed back and forth 3500 times. The more preferable lower limit of the Martens hardness at the center of the cross section of the second hard coat layer is 375 MPa, and the more preferable upper limit is 575 MPa.
In the optical layered body, the Martens hardness of the first hard coat layer is preferably larger than the Martens hardness of the second hard coat layer. By having such a relationship of Martens hardness, the pencil hardness of the laminate for an organic EL of the present invention is particularly good. This is because when the laminate for an organic EL of the present invention is subjected to a pencil hardness test and a load is applied to a pencil, deformation of the laminate for an organic EL of the present invention is suppressed and deformation of a scratch or dent is caused. It is because it decreases. Also, it has sufficient endurance folding performance, and no scratch is generated in the steel wool test in which the surface of the hard coat layer is subjected to 3500 frictions while applying a load of 1 kg / cm ² with # 0000 steel wool. It is possible to impart extremely excellent scratch resistance.
As a method of making the Martens hardness of the first hard coat layer larger than the Martens hardness of the second hard coat layer, for example, control is performed so that the content of the silica fine particles described later is contained more on the first hard coat layer side. And the like.
In the laminate for organic EL of the present invention, the hard coat layer may have a single structure, in which case the silica fine particles described later in the hard coat layer are unevenly distributed on the substrate film side, that is, the above The proportion of the silica fine particles in the hard coat layer is preferably inclined so as to be larger on the side of the base film and to decrease toward the side opposite to the side of the base film.
In addition, in this specification, "Martens hardness" is hardness when an indenter is indented 500 nm by the hardness measurement by a nanoindentation method.
In addition, in this specification, the measurement of the Martens hardness by the said nanoindentation method was performed using "TI950 TriboIndenter" by HYSITRON (Hyditron) company. That is, a Berkovich indenter (triangular pyramid) is pushed 500 nm from the surface of the hard coat layer of the laminate for an organic EL according to the present invention as the above indenter, held constant for relaxation of residual stress, and then unloaded and relaxed. The Martens hardness is calculated by P _max / A using the max load (P _max (μN) and the depression area (A (nm ² ) at a depth of 500 nm).

The first hard coat layer preferably contains a cured product of a polyfunctional (meth) acrylate monomer as a resin component, and preferably contains silica fine particles dispersed in the resin component.
Examples of the polyfunctional (meth) acrylate monomers include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and pentaerythritol triol. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) Acrylate, tetrapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin Tetra (meth) acrylate, adamantyl di (meth) acrylate, isoboronyl di (meth) acrylate, dicyclopentadi (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and PO , EO, caprolactone and the like.
Among them, those having 3 to 6 functional groups are preferable because they can suitably satisfy the above-mentioned martens hardness, and, for example, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA) And dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate and the like.
In the present specification, (meth) acrylate means acrylate and methacrylate.

The silica fine particles are preferably reactive silica fine particles. The reactive silica fine particles are silica fine particles capable of forming a crosslinked structure with the polyfunctional (meth) acrylate monomer, and the first hard coat layer contains the reactive silica fine particles. Hardness can be sufficiently increased.

The above-mentioned reactive silica fine particles preferably have a reactive functional group on the surface, and as the reactive functional group, for example, a polymerizable unsaturated group is suitably used, and more preferably a photocurable unsaturated group And particularly preferably ionizing radiation curable unsaturated groups. As a specific example of the said reactive functional group, ethylenic unsaturated bonds, such as a (meth) acryloyl group, a vinyl group, an allyl group, an epoxy group, etc. are mentioned, for example.

The reactive silica fine particles are not particularly limited, and conventionally known ones can be used, and examples thereof include reactive silica fine particles described in JP-A-2008-165040. Moreover, as a commercial item of the said reactive silica particle, For example, Nissan Chemical Industries, Ltd. make; MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, JGC Catalysts Chemical Corporation make; V8802, V8803 etc. are mentioned. .

Further, the above-mentioned silica fine particles may be spherical silica fine particles, but it is preferable that they are modified silica fine particles. Spherical silica microparticles and atypical silica microparticles may be mixed.
In the present specification, the atypical silica fine particles mean silica fine particles having a shape of potato-like random unevenness on the surface.
The surface area of the atypical silica fine particles is larger than that of the spherical silica fine particles, and by containing such atypical silica fine particles, the contact area with the polyfunctional (meth) acrylate or the like becomes large, and the hard coat is produced. The hardness of the layer (pencil hardness) can be made better.
It can be confirmed by observing the cross section of the first hard coat layer with an electron microscope whether it is the above-mentioned modified silica fine particle or not.

When the above-mentioned silica particles are modified silica particles, the average particle diameter of the modified silica particles is preferably 5 to 200 nm. If it is less than 5 nm, it may be difficult to produce the fine particles themselves, the fine particles may be aggregated, and it may be extremely difficult to form a different shape, and furthermore, the ink before the application may be used. At the stage, the dispersibility of the atypical silica fine particles may be poor and may cause aggregation. On the other hand, when the average particle diameter of the modified silica fine particles exceeds 200 nm, large irregularities may be formed in the hard coat layer, and problems such as an increase in haze may occur.
The average particle diameter of the atypical silica fine particles is the average of the maximum value (long diameter) and the minimum value (short diameter) of the distance between two points of the outer circumference of the atypical silica fine particles which appeared in cross-sectional microscopic observation of the hardcoat layer. It is a value.

The hardness (martens hardness) of the first hard coat layer can be controlled by controlling the size and amount of the silica fine particles, and as a result, the first hard coat layer and the second hard coat layer can be formed. it can.
For example, when forming the said 1st hard-coat layer, it is preferable that the said silica particle is 5-200 nm in diameter, and it is 25-60 mass parts with respect to 100 mass parts of said resin components.

Moreover, it is preferable that the said 2nd hard-coat layer contains the hardened | cured material of polyfunctional (meth) acrylate as a resin component.
As said polyfunctional (meth) acrylate, the thing similar to what was mentioned above is mentioned.
Moreover, in addition to the said polyfunctional (meth) acrylate as a resin component, the said 2nd hard-coat layer may contain polyfunctional urethane (meth) acrylate and / or polyfunctional epoxy (meth) acrylate etc.
Furthermore, the second hard coat layer may contain the silica fine particles described above. Although it does not specifically limit as content of the said silica particle in the said 2nd hard-coat layer, For example, it is preferable that it is 0-20 mass% in the said 2nd hard-coat layer.

The hard coat layer may contain any material other than the above-described materials, as long as the above-described martens hardness is satisfied, in any of the first hard coat layer and the second hard coat layer. For example, as a material of the resin component, a polymerizable monomer, a polymerizable oligomer or the like which forms a cured product by irradiation of ionizing radiation may be included.
Examples of the polymerizable monomer or polymerizable oligomer include (meth) acrylate monomers having a radically polymerizable unsaturated group in the molecule, and (meth) acrylate oligomers having a radically polymerizable unsaturated group in the molecule. Be
As a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule or a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule, for example, urethane (meth) acrylate, polyester (meta) And monomers) or oligomers such as acrylates, epoxy (meth) acrylates, melamine (meth) acrylates, polyfluoroalkyl (meth) acrylates, silicone (meth) acrylates and the like. These polymerizable monomers or polymerizable oligomers may be used alone or in combination of two or more. Among them, urethane (meth) acrylates having a multifunctional (six or more functional) and a weight average molecular weight of 1000 to 10,000 are preferable.

In addition, a monofunctional (meth) acrylate monomer may be further contained as a material which comprises the said hard-coat for hardness adjustment of the viscosity of a composition, adhesiveness improvement, etc.
Examples of the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxy polyethylene glycol (meth) acrylate, isostearyl (meth) acrylate, 2-acryloyloxyethyl succinate, acryloyl morpholine, N Acryloyloxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, adamantyl acrylate and the like.

From the viewpoint of improving the hardness of the hard coat layer, the weight average molecular weight of the polymerizable monomer is preferably less than 1000, and more preferably 200 to 800.
The weight average molecular weight of the polymerizable oligomer is preferably 1,000 to 20,000, more preferably 1,000 to 10,000, and still more preferably 2,000 to 7,000.
In addition, in this specification, the weight average molecular weight of the said polymerizable monomer and a polymerizable oligomer is a weight average molecular weight of polystyrene conversion measured by GPC method.

The hard coat layer may contain an ultraviolet absorber (UVA).
The laminate for an organic EL of the present invention is particularly suitably used for mobile terminals such as foldable smart phones and tablet terminals as described later, but such mobile terminals are often used outdoors, Therefore, there is a problem that the polarizer disposed below the laminate for an organic EL of the present invention is easily deteriorated by being exposed to ultraviolet light.
However, since the hard coat layer is disposed on the display screen side of the polarizer, when the hard coat layer contains an ultraviolet absorber, the polarizer is preferably deteriorated due to exposure to ultraviolet rays. It can be prevented.
In addition, the said ultraviolet absorber (UVA) may be contained in the base film in the said optical laminated body. In this case, the ultraviolet absorber (UVA) may not be contained in the hard coat layer.

Examples of the UV absorber include triazine UV absorbers, benzophenone UV absorbers, and benzotriazole UV absorbers.

Examples of the triazine-based ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy) phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, for example. 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyl) Oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, and 2- [4-[(2-hydroxy-3- (2) ' -Ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.
Moreover, as a triazine type ultraviolet absorber marketed, TINUVIN460, TINUVIN477 (all are BASF Corporation make), LA-46 (ADEKA company make) etc. are mentioned, for example.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate salt, sodium hydroxymethoxybenzophenone sulfonate and the like can be mentioned.
Moreover, as a benzophenone series ultraviolet absorber marketed, CHMASSORB81 / FL (made by BASF Corporation) etc. are mentioned, for example.

Examples of the benzotriazole-based ultraviolet absorber include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, and the like. -(2H-benzotriazol-2-yl) -6- (linear and branched dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl- 6- (tert-Butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert -Butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3') — (3 ′ ′, 4 ′ ′, 5 ′ ′, 6 ′ ′-tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetra) Methyl butyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, etc. It can be mentioned.
Moreover, as a benzotriazole type ultraviolet-ray absorber marketed, for example, KEMISORB71D, KEMISORB79 (all are made by Chemi-Pro Chemical Co., Ltd.), JF-80, JAST-500 (all are made by Johoku Chemical Co., Ltd.), ULS-1933D (Made by one company), RUVA-93 (made by Otsuka Chemical Co., Ltd.), etc. are mentioned.

Among the above-mentioned UV absorbers, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferably used.
The ultraviolet absorber preferably has a high solubility with the resin component constituting the hard coat layer, and preferably has a low bleed out after the above-mentioned endurance folding test.
The UV absorber is preferably polymerized or oligomerized.
The UV absorber is preferably a benzotriazole, triazine, a polymer or an oligomer having a benzophenone skeleton, and more specifically, an arbitrary ratio of (meth) acrylate having a benzotriazole or benzophenone skeleton and methyl methacrylate (MMA) It is preferable that the polymer be thermally copolymerized.
The UVA can also play a role of protecting the organic EL layer from ultraviolet light.

Although it does not specifically limit as content of the said ultraviolet absorber, It is preferable that it is 1 to 6 mass parts with respect to 100 mass parts of resin solid content of the said hard-coat layer. When the amount is less than 1 part by mass, the above-mentioned effect of containing the ultraviolet absorber in the hard coat layer may not be sufficiently obtained. When the amount is more than 6 parts by mass, the hard coat layer significantly colorizes and strength decreases. May occur. The more preferable lower limit of the content of the ultraviolet absorber is 2 parts by mass, and the more preferable upper limit is 5 parts by mass.

The layer thickness of the hard coat layer is preferably 2.0 to 5.0 μm in the case of the first hard coat layer, and 0.5 to 4.0 μm in the case of the second hard coat layer. Is preferred. If the thickness of the layer is less than the lower limit, the hardness of the hard coat layer may be significantly reduced. If the thickness of the layer exceeds the upper limit, the coating of the coating solution for forming the hard coat layer becomes difficult. Moreover, the processability (especially chipping resistance) resulting from having thickness too thick may deteriorate.
The lower limit of the layer thickness of the first hard coat layer is preferably 2.5 μm, more preferably 4.5 μm, and the lower limit of the layer thickness of the second hard coat layer is preferably 1.0 μm, more preferably It is 3.5 μm.
In addition, the layer thickness of the said hard-coat layer is an average value of the thickness of ten arbitrary places obtained by measuring by the electron microscope (SEM, TEM, STEM) observation of a cross section.

In the optical laminate, in the laminate for an organic EL of the present invention having a hard coat layer, the transmittance of light with a wavelength of 380 nm is preferably 10% or less, more preferably 8% or less. When the transmittance exceeds 10%, when the laminate for an organic EL of the present invention is used for a mobile terminal, the polarizer may be exposed to ultraviolet rays and easily deteriorated. A more preferable upper limit of the light transmittance at a wavelength of 380 nm of the hard coat layer is 5%.
Further, the hard coat layer preferably has a haze of 2.5% or less. When it exceeds 2.5%, when the laminate for an organic EL of the present invention is used for a mobile terminal, there is a possibility that the whitening of the display screen becomes a problem. The more preferable upper limit of the said haze is 1.5%, and a still more preferable upper limit is 1.0%.
Moreover, the said transmittance | permeability and haze can be measured according to JISK-7361 using a haze meter (the Murakami Color Research Laboratory make, product number; HM-150).
In addition, the haze of the whole laminated body for organic EL of this invention becomes the sum total of the haze of the said hard-coat layer, and the haze of the said base film, and when the haze of the said base film is higher than 1%, the organic of this invention The overall haze of the EL laminate is higher than 1%.

The hard coat layer may optionally contain, for example, a lubricant, a plasticizer, a filler, an antistatic agent, an antiblocking agent, a crosslinking agent, a light stabilizer, an antioxidant, a colorant such as a dye or a pigment, and the like. The component of (a) may be contained.

Moreover, the said optical laminated body is another hard-coat layer (following, back surface hard) on the opposite side in which the above-mentioned hard-coat layer (1st hard-coat layer and 2nd hard-coat layer) of the said base film was provided. The coat layer may also be formed. As said back surface hard-coat layer, the layer similar to the hard-coat layer mentioned above is mentioned, for example.
Moreover, it is preferable to have a back surface hard-coat layer (1) and / or a back surface hard-coat layer (2) as said back surface hard-coat layer.
Examples of the back surface hard coat layer (1) and the back surface hard coat layer (2) include layers having the same composition and thickness as the first hard coat layer described above or the second hard coat layer described above.
That is, when the optical laminate has the back hard coat layer, a structure having the back hard coat layer (1) similar to the first hard coat layer described above as the back hard coat layer, the second hard A structure having a back surface hard coat layer (1) similar to the coat layer, a back surface hard coat layer (1) similar to the first hard coat layer described above, and a back surface hard coat layer similar to the second hard coat layer described above (2 And a back surface hard coat layer (1) similar to the second hard coat layer described above and a back surface hard coat layer similar to the first hard coat layer described above (2). And the structure laminated in this order from the base film side.
In addition, since the said back surface hard-coat layer is arrange | positioned on the outermost surface side and the opposite side, the antifouling performance mentioned later is unnecessary.

Moreover, it is preferable that the laminated body for organic EL of this invention has antifouling performance. Such antifouling performance can be obtained, for example, by incorporating an antifouling agent in the hard coat layer of the optical laminate.
The hard coat layer containing the antifouling agent preferably has a contact angle of 100 ° or more with respect to water on the surface, and in the laminate for an organic EL of the present invention immediately after production, the water on the surface of the hard coat layer is The contact angle to the surface is more preferably 105 ° or more, and a steel wool resistance test in which the surface of the second hard coat layer is rubbed back and forth 3500 times under a load of 1 kg / cm ² with # 0000 steel wool The contact angle to water of the surface of the hard coat layer after the treatment is preferably 90 ° or more, more preferably 103 ° or more.

The antifouling agent is preferably contained unevenly on the outermost surface side of the hard coat layer. When the antifouling agent is uniformly contained in the hard coat layer, the addition amount needs to be increased in order to provide sufficient antifouling performance, which may lead to a decrease in the film strength of the hard coat layer. In addition, when the said hard-coat layer has the 1st hard-coat layer and 2nd hard-coat layer which were mentioned above, the said antifouling agent is unevenly distributed in the outermost surface side of the 2nd hard-coat layer arrange | positioned at outermost surface side. Preferably, it is included.
As a method of unevenly distributing the antifouling agent on the outermost surface side of the hard coat layer, for example, at the time of forming the hard coat layer, the coating film formed using the composition for hard coat layer described later is dried and cured Before the mixture is heated, the coating film is heated to lower the viscosity of the resin component contained in the coating film to increase the flowability, and the antifouling agent is unevenly distributed on the outermost surface side. By selecting and using a stain, the antifouling agent is floated on the surface of the coating without applying heat when the coating is dried, and then the coating is cured to make the antifouling agent on the outermost surface side. There is a method of making it unevenly distributed.

The antifouling agent is not particularly limited, and examples thereof include silicone-containing antifouling agents, fluorine-containing antifouling agents, silicone-containing and fluorine-containing antifouling agents, and each may be used alone. You may mix and use. Moreover, as said antifouling agent, an acrylic antifouling agent may be sufficient.
The content of the antifouling agent is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the above-described resin material. If the amount is less than 0.01 parts by weight, the hard coat layer may not be provided with sufficient antifouling performance, and since the slipperiness is poor, scratches may occur even in a steel wool resistance test. On the other hand, if it exceeds 3.0 parts by weight, the hardness of the hard coat layer may be lowered, and the antifouling agent itself becomes ball-like (micellar), and the resin component of the hard coat layer and the antifouling agent In some cases, phase separation (sea-island state) may occur finely, which may result in whitening.
The antifouling agent preferably has a weight average molecular weight of 20,000 or less, and a compound having preferably 1 or more, more preferably 2 or more reactive functional groups in order to improve the durability of the antifouling performance. It is. Among them, excellent scratch resistance can be imparted by using an antifouling agent having two or more reactive functional groups.
When the antifouling agent does not have a reactive functional group, the antifouling agent is transferred to the back surface when stacked, even when the laminate for an organic EL of the present invention has a roll shape or a sheet shape. If other members are stuck or painted on the back surface, the other members may peel off, and may be easily peeled off by performing a plurality of folding tests.
In addition, the said weight average molecular weight can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC).

Furthermore, the antifouling agent having the reactive functional group has good performance persistence (durability) of antifouling performance, and among them, the hard coat layer containing the above-mentioned fluorine-containing antifouling agent is accompanied by fingerprints It is difficult (not noticeable) and the wiping property is also good. Furthermore, since the surface tension at the time of coating of the composition for forming a hard coat layer can be lowered, the leveling property is good and the appearance of the hard coat layer to be formed becomes good.
Moreover, the hard-coat layer containing the said silicone-containing type antifouling agent has good slipperiness, and steel wool resistance is favorable.
The laminate for an organic EL of the present invention, which contains such a silicone-containing antifouling agent in the hard coat layer, improves sliding when contacted with a finger, a pen or the like, and hence the touch feeling is improved. In addition, fingerprints are also less likely to be attached to the above-mentioned hard coat layer (not noticeable), and the wiping performance is also improved. Furthermore, since the surface tension at the time of application of the composition (composition for hard coat layer) at the time of forming the above-mentioned hard coat layer can be lowered, leveling property is good and appearance of the hard coat layer to be formed is good. It becomes a thing.
Moreover, as an antifouling agent which has the said reactive functional group, it is available as a commercial item, As a commercial item except the above, as a silicone containing antifouling agent, for example, SUA1900L10 (Shin-Nakamura Chemical Co., Ltd.) Made), SUA1900L6 (made by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (made by Daicel-Cytec Co., Ltd.), UT3971 (made by Nippon Gosei Co., Ltd.) -164E, X22-174BX, X22-2426, KBM 503. KBM5103 (Shin-Etsu Chemical Co., Ltd.), TEGO-RAD 2250, TEGO-RAD 2300. TEGO-RAD 2200 N, TEGO-RAD 2010, TEGO-RAD 2500, TEGO-RAD 2600, TEGO-RAD 2700 (manufactured by Evonik Japan), Megafuck RS 854 (manufactured by DIC), and the like.
As the fluorine-containing antifouling agent, for example, Optool DAC, Optool DSX (manufactured by Daikin Industries, Ltd.), Megafuck RS71, Megafuck RS74 (manufactured by DIC), LINC152EPA, LINC151EPA, LINC182UA (manufactured by Kyoeisha Chemical Co., Ltd.), For example, there are 650A, aftergent 601 AD, aftergent 602, and the like.
Moreover, as a fluorine-containing and silicone-containing antifouling agent having a reactive functional group, for example, Megafac RS 851, Megacac RS 852, Megacac RS 853, Megacac RS 854 (manufactured by DIC), Opstar TU 2225, Opstar TU 22 22 (Manufactured by JSR Corporation), X71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

In the above-mentioned optical layered product, in order to improve the coatability of the composition at the time of formation of the first hard coat layer, the first hard coat layer contains a surfactant (leveling agent) as required. It may be
When the addition amount of the above-mentioned leveling agent is too large, bubbles are generated in the coating when forming the first hard coat layer and become defects, or when the second hard coat layer is laminated, the second hard The coat layer may be repelled or the adhesion may be deteriorated.
In addition, when the coating film when forming the first hard coat layer is also nonuniform or has unevenness, defects or the like, cracking or breakage may occur in the above-mentioned endurance folding test.

The hard coat layer can be formed, for example, using a composition for a hard coat layer obtained by adding the above-mentioned resin component, reactive silica fine particles, an ultraviolet absorber, and other components.
The composition for a hard coat layer may contain a solvent, if necessary.

Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (eg, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol, ester (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA), aliphatic Hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), (Eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), carbonate (dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate) and the like. These solvents may be used alone or in combination of two or more.
Among them, as the solvent, a resin component such as the above-mentioned polymerizable monomer and / or polymerizable oligomer, and other additives can be dissolved or dispersed, and the composition for the hard coat layer can be suitably coated. Preferred are methyl isobutyl ketone and methyl ethyl ketone.

The composition for a hard coat layer preferably has a total solid content of 25 to 55%. If it is less than 25%, residual solvent may remain or whitening may occur. If it exceeds 55%, the viscosity of the composition for hard coat layer may be increased, the coatability may be reduced, and unevenness or streaks may appear on the surface. The solid content is more preferably 30 to 50%.

As a method of producing the above-mentioned optical layered product using the above-mentioned composition for hard court layers, composition for hard court layers is applied, for example on one side of the above-mentioned base film, and a coating layer is formed, There is a method of drying and curing the coated layer.

As a method of apply | coating the said composition for hard-coat layers on one side of the said base film, and forming an application layer, a spin coat method, a dip method, a spray method, the die coating method, the bar-coat method, a roll, for example Various known methods such as coater method, meniscus coater method, flexographic printing method, screen printing method, bead coater method can be mentioned.

Although it does not specifically limit as a drying method of the said coating film, Generally, it is good to dry at 30-120 degreeC for 10 to 120 second.
In addition, as a method of curing the coating film, a known method may be appropriately selected according to the composition of the composition for the hard coat layer and the like. For example, if the composition for the hard coat layer is of the ultraviolet ray curing type, it may be cured by irradiating the coating layer with ultraviolet rays.

In the case where the hard coat layer has the above-described first hard coat layer and the second hard coat layer, the composition for the first hard coat layer prepared to form the first hard coat layer is the above-mentioned group. The coated film formed on the material film is dried and then half cured. The adhesion of the first hard coat layer and the second hard coat layer becomes extremely excellent by forming a second hard coat layer described later in a state where the above-mentioned coating film is not completely cured and half cured. . As a method of carrying out the half curing of the said coating film, the method of irradiating an ultraviolet-ray to 100 mJ / cm < ² > or less etc. is mentioned to the dried said coating film, for example.
The coating film formed by applying the composition for the second hard coating layer prepared to form the second hard coating layer on the above half cured first hard coating layer is dried and then the coating film is obtained. By completely curing, a second hard coat layer can be formed on the first hard coat layer. In addition, the steel wool resistance of the surface of the said hard-coat layer (2nd hard-coat layer) becomes excellent by fully curing the coating film using the said composition for 2nd hard-coat layers. As a method of completely curing the coating film of the composition for the second hard coat layer, for example, the coating film is subjected to a nitrogen atmosphere (oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less) And curing by ultraviolet irradiation. The steel wool resistance can also be improved by increasing the degree of crosslinking (reaction rate) of the side opposite to the first hard coat layer side of the second hard coat layer, which is the outermost surface.
In addition, when forming a 1st hard-coat layer and a 2nd hard-coat layer by the method mentioned above, in order to obtain the hard-coat layer (a 1st hard-coat layer and a 2nd hard-coat layer) hardened enough, ultraviolet irradiation is carried out The amount is preferably 150 mJ / cm ² or more in total.

In the present invention, the hard coat layer may be formed by using a conventionally known thermosetting sol gel method.
In addition, the sol-gel method of the above-mentioned thermosetting system generally hydrolyzes an alkoxysilane compound having an epoxy group to form a gel which has lost fluidity by a polycondensation reaction, and this gel is heated to form an oxide. In general, for example, a method of obtaining an oxide by hydrolyzing an alkoxysilane compound and causing a polycondensation reaction, or heating an alkoxysilane compound having an isocyanate group to polycondensation is known. Alternatively, the method may be a method of obtaining an oxide, or a method of mixing an alkoxysilane compound and a compound having an isocyanate group in an arbitrary ratio to cause hydrolysis and a polycondensation reaction.
The alkoxysilane compound having an epoxy group is not particularly limited as long as it has at least one epoxy group and at least one hydrolyzable silicon group in the molecule, and examples thereof include γ-glycidoxypropyltrimethoxysilane, γ And glycidoxypropyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

The hydrolyzate of the alkoxysilane compound having an epoxy group can be obtained by dissolving the alkoxysilane compound having an epoxy group in a suitable solvent and performing hydrolysis. As the solvent to be used, for example, alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, Or the mixture of these is mentioned. Among them, methyl ethyl ketone is preferred in that it has a suitable drying rate to form a film.

In the case of carrying out the above-mentioned hydrolysis, a catalyst may be used if necessary. The catalyst to be used is not particularly limited, and known acid catalysts or base catalysts can be used.
Examples of the acid catalyst include organic acids such as acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, malonic acid, maleic acid, toluenesulfonic acid, oxalic acid and the like Inorganic acids such as hydrochloric acid, nitric acid and halogenated silanes; acidic sol-like fillers such as acidic colloidal silica and thiania sol, and the like. These may be used alone or in combination of two or more.
Examples of the base catalyst include aqueous solutions of hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide, aqueous ammonia, aqueous solutions of amines, and the like. Among them, the use of hydrochloric acid or acetic acid, which has high catalytic reaction efficiency, is preferable.

The alkoxysilane compound is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane and methyltriethoxysilane. Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldisilane Ethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxy Trimethoxysilane, .gamma.-chloropropyl trimethoxy silane, .gamma.-mercaptopropyltrimethoxysilane, and the like.
Two or more of these may be used in combination.

Moreover, it does not specifically limit as an alkoxysilane compound which has the said isocyanate group, For example, 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane, 2-isocyanate ethyl tri n-propoxysilane etc. are mentioned.

Moreover, the compound which has the said isocyanate group is not specifically limited, For example, tolylene diisocyanate (TDI), 3,3'- tolylene-4,4'-isocyanate, diphenylmethane 4,4'-diisocyanate (MDI), triphenyl Methane p, p ′, p ′ ′-triisocyanate (TM), 2,4-tolylene dimer (TT), naphthalene-1,5-diisocyanate, tris (4-phenylisocyanate) thiophosphate, crude (MDI) ), TDI trimer, dicyclohexamethane 4,4′-diisocyanate (HMDI), hydrogenated TDI (HTDI), metaxylylene diisocyanate (XDI), hexahydrometaxylylene diisocyanate (HXDI), hexamethylene diisocyanate, Trimethylpropane 1-Methyl-2-isocyano-4-Kababamate, polymethylene polyphenyl isocyanate, 3,3'-dimethoxy 4,4'-diphenyl diisocyanate, diphenyl ether 2,4,1'-triisocyanate, m-xylylene diisocyanate (MXDI And polymethylene polyphenyl isocyanate (PAPI).

The hard coat layer may or may not have a concavo-convex shape on the surface opposite to the base film, but it has visibility for preventing reflection by external light and glare on the screen. From the viewpoint of improvement, it is preferable to have an uneven shape on the surface opposite to the base film side.
In the hard coat layer having the concavo-convex shape, the first hard coat layer may have a concavo-convex shape on the surface opposite to the base film, or the opposite side to the base film of the second hard coat layer It may have a concavo-convex shape on the surface of.
In the concavo-convex shape of the hard coat layer, an average spacing of concavities and convexities on the surface opposite to the base film of the hard coat layer is Sm, an average inclination angle of concavities and convexities is θa, and arithmetic mean roughness of concavities and convexities is Ra. It is preferable that the following formula be satisfied.
30 μm <Sm <90 μm,
2 <θa <15,
0.5 μm <Ra <1.5 μm
The above Sm, θa and Ra are values obtained by a method in accordance with JIS B 0601-1994, and can be obtained by measurement using, for example, a surface roughness measuring device: SE-3400 / Kosaka Lab.

In the concavo-convex shape of the hard coat layer, an average spacing of concavities and convexities on the surface opposite to the base film of the hard coat layer is Sm, an average inclination angle of concavities and convexities is θa, and arithmetic mean roughness of concavities and convexities is Ra. It is preferable that the following formula be satisfied.
Sm: preferably 30 μm <Sm <600 μm,
More preferably, 30 μm <Sm <90 μm
θa: preferably 0.1 <θa <1.2,
More preferably, 0.1 <θa <0.5
Ra: preferably 0.02 μm <Ra <1.0 μm,
More preferably, 0.02 μm <Ra <0.20 μm
The above Sm, θa and Ra are values obtained by a method in accordance with JIS B 0601-1994, and can be obtained by measurement using, for example, a surface roughness measuring device: SE-3400 / Kosaka Lab.

The uneven shape of the surface of the hard coat layer opposite to the base film side is formed of a composition containing an antiglare agent, formed by phase separation of resin, or formed by embossing. Good.
Especially, it is preferable that the uneven | corrugated shape of the surface on the opposite side to the said base film side of the said hard-coat layer is formed with the composition for hard-coat layers containing an anti-glare agent.
The antiglare agent is a fine particle, and the shape is not particularly limited, such as a spherical shape, an elliptical shape, and an irregular shape. In addition, inorganic or organic fine particles can be used as the above-mentioned antiglare agent, and transparent fine particles are preferable.
A plastic bead can be mentioned as a specific example of organic type particulates. As plastic beads, polystyrene beads (refractive index 1.60), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49 to 1.53), acrylic-styrene copolymer beads (refractive index 1) .54 to 1.58), benzoguanamine-formaldehyde condensate beads (refractive index 1.66), melamine-formaldehyde condensate (refractive index 1.66), polycarbonate beads (refractive index 1.57), polyethylene beads (refractive index 1.50), etc. It is preferable that the said plastic bead has a hydrophobic group on the surface, for example, a polystyrene bead can be mentioned.
As inorganic type microparticles | fine-particles, the inorganic silica beads etc. which had a specific shape, such as amorphous silica and spherical shape, can be mentioned.
Among them, it is preferable to use acrylic-styrene copolymer beads and / or amorphous silica as the above-mentioned antiglare agent.

The average particle diameter of the antiglare agent is preferably 1 to 10 μm, and more preferably 3 to 8 μm. The above-mentioned average particle diameter is a value obtained by measurement with a laser diffraction / scattering particle size distribution measuring apparatus in the state of a 5% by mass dispersion of toluene.
The content of the antiglare agent is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the binder resin solid content.

Moreover, it is preferable that the hard-coat layer which has the uneven | corrugated shape of the surface on the opposite side to the said base film side is what contains an internal scattering particle | grain further. The internal scattering particles can impart internal haze and suppress surface glaring (scintillation) and the like.
Examples of the internal scattering particles include organic particles having a relatively large difference in refractive index with the binder resin constituting the hard coat layer, and examples thereof include acrylic-styrene copolymer beads (refractive index 1.54 to 1. 58), melamine beads (refractive index 1.57), polystyrene beads (refractive index 1.60), polyvinyl chloride beads (refractive index 1.60), benzoguanamine-formaldehyde condensate beads (refractive index 1.66), melamine -Plastic beads such as formaldehyde condensate (refractive index 1.66) can be mentioned.
These particles may be used in combination of the property as the above-mentioned antiglare agent and the property as an internal scattering particle.

The average particle diameter of the internal scattering particles is preferably 0.5 to 10 μm, and more preferably 1 to 8 μm. The above-mentioned average particle diameter is a value obtained by measurement with a laser diffraction / scattering particle size distribution measuring apparatus in the state of a 5% by mass dispersion of toluene.
It is preferable that it is 0.1-40 mass% with respect to 100 mass parts of binder resin solid content, and, as for the addition amount of the said internal scattering particle, it is more preferable that it is 1-30 mass%.

As a binder resin of the hard-coat layer which has the uneven | corrugated shape on the surface on the opposite side to the said base film side, the thing similar to the binder resin which can be used for the hard-coat layer mentioned above can be mentioned.

The hard coat layer having a concavo-convex shape on the surface opposite to the base film side may further contain other components as necessary to the extent that the effect of the present invention is not impaired. As said other component, the thing similar to the other component which can be used for the hard-coat layer mentioned above can be mentioned.

The hard coat layer having an uneven shape on the surface opposite to the base film side may be formed by a known method. For example, a binder resin, an antiglare agent and other components may be mixed and dispersed with a solvent to prepare a composition for a hard coat layer, and the composition may be formed by a known method. The method of preparing the composition for the hard coat layer and the method of forming the hard coat layer using the same are the same as the method of preparing the composition for the hard coat layer described above and the method of forming the hard coat layer. Each method can be mentioned.

It is preferable that the layer thickness of the hard-coat layer which has the uneven | corrugated shape of the surface on the opposite side to the said base film side is 1-10 micrometers. If the thickness is less than 1 μm, the antiglare property may not be suitably provided. If it exceeds 10 μm, curls and cracks may occur.
The layer thickness is a value obtained by measuring the cross section of the optical laminate with an electron microscope (SEM, TEM, STEM).

It is preferable that the above-mentioned optical layered product further has a conductive layer.
The conductive layer preferably contains, for example, a conductive fibrous filler as a conductive agent.

The conductive fibrous filler preferably has a fiber diameter of 200 nm or less and a fiber length of 1 μm or more.
When the fiber diameter exceeds 200 nm, the haze value of the conductive layer to be produced may be high or the light transmission performance may be insufficient. The preferable lower limit of the fiber diameter of the conductive fibrous filler is 10 nm from the viewpoint of the conductivity of the conductive layer, and the more preferable range of the fiber diameter is 10 to 180 nm.
Moreover, when the fiber length of the said conductive fibrous filler is less than 1 micrometer, the conductive layer which has sufficient conductive performance may not be formed, aggregation may generate | occur | produce and a raise of a haze value, or the fall of light transmission performance. The upper limit of the fiber length is preferably 500 μm, the more preferable range of the fiber length is 3 to 300 μm, and the more preferable range is 10 to 30 μm.
The fiber diameter and the fiber length of the conductive fibrous filler may be, for example, an electron microscope such as SEM, STEM, or TEM, and the fiber diameter and the fiber length of the conductive fibrous filler may be 1,000 to 500,000 times. It can be determined as an average of 10 measured points.

The conductive fibrous filler is preferably at least one selected from the group consisting of conductive carbon fibers, metal fibers, and metal-coated synthetic fibers, for example.
Examples of the conductive carbon fiber include vapor grown carbon fiber (VGCF), carbon nanotube, wire cup, wire wall and the like. These conductive carbon fibers may be used alone or in combination of two or more.

As the metal fiber, for example, a fiber produced by a wire drawing method or a cutting method in which stainless steel, iron, gold, silver, aluminum, nickel, titanium and the like are thin and elongated can be used. Such metal fibers can be used alone or in combination of two or more. Among these metal fibers, metal fibers using silver are preferable because of excellent conductivity.

Examples of the metal-coated synthetic fibers include fibers obtained by coating acrylic fibers with gold, silver, aluminum, nickel, titanium and the like. Such metal-coated synthetic fibers can be used alone or in combination of two or more. Among these metal-coated synthetic fibers, metal-coated synthetic fibers using silver are preferable because of excellent conductivity.

The content of the conductive fibrous filler in the conductive layer is, for example, preferably 20 to 3000 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer. If the amount is less than 20 parts by mass, a conductive layer having sufficient conductive performance may not be formed. If the amount is more than 3000 parts by mass, the haze of the conductive laminate of the present invention is increased or the light transmission performance is insufficient. It may be In addition, when the amount of binder resin entering the contact points of the conductive fibrous filler is increased, the conductivity of the conductive layer may be deteriorated, and a target resistance value may not be obtained in the conductive laminate of the present invention. The more preferable lower limit of the content of the conductive fibrous filler is 50 parts by mass, and the more preferable upper limit is 1000 parts by mass.
In addition, it does not specifically limit as a resin component of the said conductive layer, A conventionally well-known material is mentioned.

Moreover, as other conductive agents other than the above-mentioned conductive fibrous filler, for example, quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as first to third amino groups, sulfonic acid Anionic compound having an anionic group such as base, sulfate ester base, phosphate ester base, phosphonate base, amphoteric compound such as amino acid type and amino sulfate ester type, nonionic compound such as amino alcohol type, glycerin type and polyethylene glycol type Compounds, organometallic compounds such as alkoxides of tin and titanium, metal chelate compounds such as acetylacetonate salts thereof, and the like, compounds obtained by polymerizing the compounds listed above, and tertiary amino groups , A quaternary ammonium group or a metal chelate moiety, and Polymerizable monomer or oligomer by line, or have a polymerizable polymerizable functional groups by ionizing radiation, and the polymerizable compound of the organic metal compounds, such as coupling agents.
The content of the other conductive agent is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer. When the amount is less than 1 part by mass, a conductive layer having sufficient conductive performance may not be formed. When the amount is more than 50 parts by mass, the haze of the conductive laminate of the present invention is increased or the light transmission performance is insufficient. It may be

Furthermore, as the conductive agent, for example, conductive fine particles can also be used.
As a specific example of the said electroconductive fine particles, what consists of metal oxides can be mentioned. As such a metal oxide, for example, ZnO (refractive index 1.90, hereinafter, the numerical value in parentheses represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₃ (1.71) , SnO ₂ (1.997), indium tin oxide (1.95), often abbreviated as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (Abbreviation: ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), etc. can be mentioned. The average particle diameter of the conductive fine particles is preferably 0.1 nm to 0.1 μm. By being in such a range, when the conductive fine particles are dispersed in the raw material of the resin component constituting the conductive layer, a composition capable of forming a highly transparent film having little haze and good total light transmittance. The thing is obtained.
The content of the conductive fine particles is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer. When the amount is less than 10 parts by mass, a conductive layer having sufficient conductive performance may not be formed. When the amount exceeds 400 parts by mass, the haze of the conductive laminate of the present invention may be increased or the light transmission performance may be insufficient. It may be

Examples of the conductive agent include aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroconjugated conjugated polyaniline, and mixed conjugated poly (Phenylene vinylene), a multi-chain type conjugated system which is a conjugated system having a plurality of conjugated chains in the molecule, a conductive complex which is a polymer in which the aforementioned conjugated polymer chain is grafted or block-conjugated to a saturated polymer, etc. And a high molecular weight conductive agent can be used.

The conductive layer may contain refractive index adjusting particles.
Examples of the refractive index adjusting particles include high refractive index fine particles and low refractive index fine particles.
The above-mentioned high refractive index fine particles are not particularly limited, and examples thereof include aromatic polyimides, epoxy resins, (meth) acrylic resins (acrylates and methacrylate compounds), polyester resins, urethane resins, and other resin materials such as aromatic rings and sulfur. Examples thereof include fine particles of a resin having a high refractive index containing an atom or a bromine atom, a material having a high refractive index such as a precursor thereof, metal oxide fine particles, metal alkoxide fine particles, and the like.
The low refractive index fine particles are not particularly limited, and for example, a resin having a low refractive index in which a resin material such as an epoxy resin, (meth) acrylic resin, polyester resin and urethane resin contains a fluorine atom, and a precursor thereof Examples include fine particles made of a material having a low refractive index, or magnesium fluoride fine particles, and hollow or porous fine particles (organic or inorganic).

As the organic EL layer, conventionally known ones can be used.
In the laminate for organic EL of the present invention, the substrate used for the organic EL layer is preferably a polyimide film, an aramid film, a polyester film, a polyethylene naphthalate film, a cycloolefin film or an acrylic film.

In the organic EL laminate of the present invention, a known touch panel, retardation film or the like may be laminated between the organic EL layer and the optical laminate.
In the laminate for organic EL of the present invention, the substrate used for the touch panel is preferably a polyimide film, an aramid film, a polyester film, a polyethylene naphthalate film, a cycloolefin film or an acrylic film.

The laminate for an organic EL according to the present invention has the above-mentioned constitution and does not cause cracking or breakage in the endurance folding test, so it has extremely excellent folding properties, and further, excellent hardness and transparency. Have.
Such a laminate for an organic EL of the present invention can not only be used as a surface protection film of an image display device such as a liquid crystal display device, but also a curved display, a surface protection film of a product having a curved surface, and the surface of a foldable member It can be used as a protective film.
Among them, the laminate for an organic EL of the present invention is suitably used as a surface protective film of a foldable member because it has extremely excellent foldability.
Moreover, since the laminated body for organic EL of this invention is a member used as applications, such as a foldable smart phone and a foldable tablet, it is preferable that it is what has antibacterial property. It does not specifically limit as method to provide the said antimicrobial property, A conventionally well-known method is mentioned.
Moreover, it is preferable that the laminated body for organic EL of this invention has the blue light cut property by the conventionally well-known method. In addition, the said blue light means the light of wavelength 385-495 nm.

The foldable member is not particularly limited as long as it is a member having a foldable structure, and examples thereof include foldable smartphones, foldable touch panels, tablets, foldable (electronic) albums, and the like.
The folding point in the member having the structure to be folded may be one or more. The direction of folding can also be arbitrarily determined as needed.

Since the laminate for an organic EL of the present invention has the above-described structure, it has excellent hardness, transparency and durable folding performance.
Therefore, the laminate for an organic EL of the present invention can be suitably used as a curved display, a surface protection film of a product having a curved surface, or a surface protection film of a foldable member.

It is a sectional view showing an endurance fold test typically.

The present invention will be described in more detail by way of the following Examples and Comparative Examples, but the present invention is not limited to only these Examples and Comparative Examples.
In the following description, "part" or "%" is on a mass basis unless otherwise noted.

Example 1
A polyimide film represented by the above formula (1) having a thickness of 30 μm is prepared as a base film, and composition 1 for hard coat layer of the following composition is coated on one surface of the base film, and coated. A film was formed.
Next, the formed coating film is heated at 70 ° for 1 minute to evaporate the solvent in the coating film, and the ultraviolet light is exposed to the air using an ultraviolet irradiation device (Fusion UV System Japan Ltd., light source H bulb). The coated film was half-cured by irradiation so that the integrated light amount would be 100 mJ / cm ² to form a first hard coat layer with a thickness of 3 μm.
Subsequently, on the first hard coat layer, composition A for hard coat layer having the following composition was applied to form a coating film. Next, the formed coating film is heated at 70 ° for 1 minute to evaporate the solvent in the coating film, and the ultraviolet light is irradiated with oxygen using an ultraviolet irradiation device (Fusion UV System Japan Ltd., light source H bulb) Was irradiated so that the integrated light amount would be 200 mJ / cm ² under 200 ppm or less to completely cure the coating film, to form a second hard coat layer having a thickness of 2 μm, thereby manufacturing an optical laminate. .

(Composition for hard coat layer 1)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 25 parts by mass Dipentaerythritol EO modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass atypical silica fine particles (Average particle size: 25 nm, manufactured by JGC Catalysts & Chemical Co., Ltd.) 50 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the first hard coat layer obtained was 830 MPa.

(Composition A for Hard Coat Layer)
Urethane acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.) 25 parts by mass A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 50 parts by mass multifunctional acrylate polymer (Akrit 8KX-012C, Taisei Fine Chemical Co., Ltd.) 25 parts by mass (solid conversion)
Antifouling agent (BYKUV 3500, manufactured by BIC-Chemie) 1.5 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the second hard coat layer obtained was 500 MPa.

(Example 2)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the second hard coat layer was 4 μm.

(Example 3)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was 5 μm.

(Example 4)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the second hard coat layer was set to 0.75 μm.

(Example 5)
An optical laminate was manufactured in the same manner as Example 1, except that the thickness of the first hard coat layer was 2 μm.

(Example 6)
It is carried out except using the composition 2 for hard-coat layers of the following composition instead of the composition 1 for hard-coat layers, and replacing with the composition A for hard-coat layers and using the composition B for hard-coat layers of the following compositions. The first hard coat layer and the second hard coat layer were formed in the same manner as in Example 1 to produce an optical laminate.

(Composition for hard coat layer 2)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 25 parts by mass, hexafunctional acrylate (MF001, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 25 parts by mass, irregular silica fine particles (average particle diameter 25 nm, JGC Catalysis Chemical Industries, Ltd. 50 parts by mass (solid conversion)
Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the first hard coat layer obtained was 890 MPa.

(Composition B for hard coat layer)
Urethane acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.) 50 parts by mass A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 50 parts by mass Antifouling agent (BYKUV 3500, manufactured by Bick Chemie) 5 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the second hard coat layer obtained was 600 MPa.

(Example 7)
It is carried out except using the composition 3 for hard-coat layers of the following composition instead of the composition 1 for hard-coat layers, and using the composition C for hard-coat layers of the following compositions instead of the composition A for hard-coat layers. The first hard coat layer and the second hard coat layer were formed in the same manner as in Example 1 to produce an optical laminate.

(Composition for hard coat layer 3)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 35 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass of atypical silica fine particles (Average particle size: 25 nm, manufactured by JGC Catalysts & Chemical Co., Ltd.) 30 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the first hard coat layer obtained was 620 MPa.

(Composition for hard coat layer C)
Urethane acrylate (KRM 8452, manufactured by Daicel Ornex) 100 parts by mass Antifoulant (TEGO-RAD 2600, manufactured by Evonik Japan)
1.5 parts by mass (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the second hard coat layer obtained was 420 MPa.

(Example 8)
It is carried out except using the composition 4 for hard-coat layers of the following composition instead of the composition 1 for hard-coat layers, and using the composition D for hard-coat layers of the following composition instead of the composition A for hard-coat layers. The first hard coat layer and the second hard coat layer were formed in the same manner as in Example 1 to produce an optical laminate.

(Composition for hard coat layer 4)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 25 parts by mass, hexafunctional acrylate (MF001, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 10 parts by mass, multifunctional acrylate polymer (PVEEA, AX-4) -HC, manufactured by Nippon Shokubai Co., Ltd.)
15 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Atypical silica fine particles (average particle diameter 25 nm, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 50 parts by mass (solid conversion)
Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the first hard coat layer obtained was 800 MPa.

(Composition for hard coat layer D)
Urethane acrylate (UV7600B, manufactured by Nippon Gohsei Chemical Co., Ltd.) 50 parts by mass Pentaerythritol triacrylate (M306, manufactured by Toagosei Co., Ltd.) 50 parts by mass Antifouling agent (X71-1203M) (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass (solid Conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the second hard coat layer obtained was 600 MPa.

(Example 9)
It is carried out except using the composition 5 for hard-coat layers of the following composition instead of the composition 1 for hard-coat layers, and using the composition E for hard-coat layers of the following composition instead of the composition A for hard-coat layers. The first hard coat layer and the second hard coat layer were formed in the same manner as in Example 1 to produce an optical laminate.

(Composition for hard coat layer 5)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 25 parts by mass Dipentaerythritol EO modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass of solid silica Fine particles (average particle size 12 nm, MIBKSD, manufactured by Nissan Chemical Industries, Ltd.)
50 parts by mass (solid conversion)
Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the obtained first hard coat layer was 730 MPa.
The solid silica fine particles were spherical solid silica fine particles.

(Composition for Hard Coat Layer E)
Urethane acrylate (UV7600B, manufactured by Nippon Gosei Co., Ltd.) 45 parts by mass Pentaerythritol triacrylate (M306, manufactured by Toagosei Co., Ltd.) 45 parts by mass Solid silica fine particles (average particle diameter 12 nm, MIBKSD, manufactured by Nissan Chemical Industries, Ltd.) 10 parts by mass antifouling Agent (Optool DAC, manufactured by Daikin Industries, Ltd.) 0.5 parts by mass (solid conversion)
Photopolymerization initiator (Irg 184) 4 parts by weight Solvent (MIBK) 150 parts by mass The Martens hardness of the second hard coat layer obtained was 500 MPa.

(Example 10)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the base film was 50 μm.

(Example 11)
An optical laminate was manufactured in the same manner as Example 1, except that the thickness of the first hard coat layer was 5 μm and the thickness of the second hard coat layer was 4 μm.

(Example 12)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the substrate film was changed to 20 μm.

(Example 13)
The substrate film is the same as in Example 1 except that the polyimide film represented by the above formula (2) of 30 μm in thickness is used instead of the polyimide film represented by the above formula (1) of 30 μm in thickness. The optical laminate was manufactured.

(Example 14)
The substrate film is the same as in Example 1 except that a polyimide film represented by the above formula (3) with a thickness of 30 μm is used instead of the polyimide film represented by the above formula (1) with a thickness of 30 μm. The optical laminate was manufactured.

(Example 15)
The substrate film is the same as Example 1, except that the polyimide film represented by the above formula (1) of 30 μm in thickness is used instead of the polyimide film represented by the above formula (1) of 30 μm in thickness. The optical laminate was manufactured.

(Example 16)
The substrate film is the same as in Example 1 except that a polyimide film represented by the above formula (9) with a thickness of 30 μm is used instead of the polyimide film represented by the above formula (1) with a thickness of 30 μm. The optical laminate was manufactured.

(Example 17)
As a substrate film, an aramid film (product name: Miktron, manufactured by Toray Industries, Inc.) represented by the above formula (20) with a thickness of 30 μm is substituted for the polyimide film represented by the above formula (1) with a thickness of 30 μm An optical laminate was produced in the same manner as in Example 1 except that it was used.

(Comparative example 1)
Example 1 was repeated except that a 25 μm thick triacetyl cellulose film (TAC, manufactured by Fujifilm Corporation) was used instead of the 30 μm thick polyimide film represented by the above formula (1) as the base film. An optical laminate was produced in the same manner.

(Comparative example 2)
The same as Example 1, except that a 50 μm thick polyethylene terephthalate film (PET film, manufactured by Toray Industries, Inc.) was used instead of the 30 μm thick polyimide film represented by the above formula (1) as the base film. The optical laminate was manufactured.

(Comparative example 3)
Example 1 was repeated except that as the substrate film, a 30 μm thick polyethylene naphthalate film (PEN film, manufactured by Teijin Limited) was used instead of the 30 μm thick polyimide film represented by the above formula (1). An optical laminate was produced in the same manner.

(Comparative example 4)
The same as Example 1, except that a 25 μm-thick cycloolefin film (COP, manufactured by Nippon Zeon Co., Ltd.) was used instead of the 30 μm-thick polyimide film represented by the above formula (1) as the base film. The optical laminate was manufactured.

(Comparative example 5)
The curing condition of the first hard coat layer is that the integrated light quantity is 200 mJ / cm ² under the condition that the oxygen concentration is 200 ppm or less by using an ultraviolet irradiation device (light source H bulb manufactured by Fusion UV System Japan Co., Ltd.) An optical laminate was produced in the same manner as in Example 1 except that the coating was cured by irradiation as described above.

(Reference Example 1)
An optical laminate was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was 10 μm.

(Reference Example 2)
An optical laminate was produced in the same manner as in Example 1 except that the second hard coat layer was not provided.

(Reference Example 3)
An optical laminate was manufactured in the same manner as Example 1, except that the thickness of the first hard coat layer was 2 μm and the thickness of the second hard coat layer was 10 μm.

(Reference Example 4)
An optical laminate was produced in the same manner as in Example 11 except that the thickness of the base film was 100 μm.

(Reference Example 5)
An optical laminate was produced in the same manner as in Example 1 except that the first hard coat layer was not provided and the thickness of the second hard coat layer was 3 μm.

The optical laminates obtained in Examples and Comparative Examples are laminated on a commercially available organic EL layer, and a laminate for an organic EL in which the optical laminate is laminated on one side of the organic EL layer is produced, The evaluation of The results are shown in Table 2.

(Durable folding test)
A sample produced by cutting the organic EL laminates according to the Examples and Comparative Examples (hereinafter, the side on which the hard coat layer is formed is the front and the opposite side is the back) into a rectangle of 30 mm x 100 mm , Attached to a durability tester (DLDMLH-FU, manufactured by Yuasa System Instruments Co., Ltd.) so that the bending inner diameter is 10 mm (the distance between opposing samples is 20 mm), and the entire surface of the side on which the hard coat layer is formed Was subjected to a test of folding 180 ° (test of folding so that the back surface is on the outside) 100,000 times.
Thereafter, the sample is replaced with a new sample, and the entire surface on the opposite side of the surface on which the hard coat layer is formed of the sample is folded 180 ° (test for folding so that the surface is on the outside) 100,000 times It was evaluated on the basis of
:: No cracking occurred in the sample even if the above test was performed on both sides :: No cracking occurred in the sample when the above test was performed with the back side facing outside, but the surface was In the case of the outer side, the sample was cracked x: The sample was cracked regardless of whether the above test was performed on the surface or the back surface

(Pencil hardness)
The pencil hardness of the organic EL laminate according to the example and the comparative example was measured based on JIS K5600-5-4 (1999).

(Steel wool (SW) resistance)
The outermost surface of the hard coat layer of the organic EL laminate according to the example and the comparative example was treated with a load of 1 kg / cm ² using # 0000 steel wool (trade name: BON STAR, manufactured by Nippon Steel Wool). Reciprocal friction was performed at a speed of 50 mm / sec 3500 times while being applied, and the presence or absence of scratches on the surface of the hard coat layer thereafter was visually observed and evaluated according to the following criteria.
○: no scratch ×: there was a scratch

(Total light transmittance)
The total light transmittance (%) was measured according to JIS K-7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number; HM-150).

As shown in Table 2, the organic EL laminates according to Examples 1 to 17 were excellent in endurance folding performance, abrasion resistance and transparency, and also very excellent in pencil hardness of 5H or more.
On the other hand, the organic electroluminescent laminated body which concerns on Comparative Examples 1-4 which did not use a polyimide film or an aramid film as a base film was inferior to pencil hardness.
Moreover, in the organic electroluminescent laminated body which concerns on the comparative example 5, since the adhesiveness of a 1st hard-coat layer and a 2nd hard-coat layer is bad, it was inferior to durable foldability.
In addition, Reference Example 1 in which the first hard coat layer was too thick, Reference Example 2 in which the second hard coat layer was not formed, Reference Example 3 in which the second hard coat layer was too thick, and reference in which the base film was too thick. In the organic EL laminate according to Example 4, no cracking occurred when the above-mentioned endurance folding test was performed so that the back surface was on the outside, but cracking occurred when it was performed such that the surface was on the outside. Oops.
Moreover, in the reference example 2 which did not form a 2nd hard-coat layer, abrasion resistance was also inferior.
Moreover, in the reference example 5 which did not form a 1st hard-coat layer, pencil hardness was inferior.

The organic EL laminate of the present invention can be suitably used as a surface material of a foldable image display device.

10 laminate for organic EL 11 of the present invention upper fixed part 12 lower fixed part

Claims (8)

It is a laminate for organic electroluminescence in which an optical laminate is laminated on one side of the organic electroluminescence layer,
A laminate for organic electroluminescence, which is characterized in that no cracking or breakage occurs when the test of folding the entire surface of the organic electroluminescent laminate at an interval of 20 mm by 180 ° is repeated 100,000 times. The laminate for organic electroluminescence according to claim 1, wherein the base film of the optical laminate is a polyimide film or an aramid film. The laminate for organic electroluminescence according to claim 1 or 2, wherein the thickness of the base film of the optical laminate is 10 to 55 μm. The optical laminate comprises a first hard coat layer provided on the side opposite to the organic electroluminescent layer of the base film, and a second hard coat layer provided on the side opposite to the base film on the first hard coat layer. The laminate for organic electroluminescence according to any one of claims 1 to 3, which has a hard coat layer. The second hard coat layer contains a cured product of a polyfunctional (meth) acrylate monomer as a resin component, and the first hard coat layer contains a cured product of a polyfunctional (meth) acrylate as a resin component, and the resin The laminate for organic electroluminescence according to claim 4, which contains a silica fine particle dispersed in the component. 6. The laminate for organic electroluminescence according to claim 5, wherein the silica fine particles are reactive silica fine particles. 7. The organic electroluminescent laminate according to claim 1, wherein the optical laminate further comprises a cured layer of a monofunctional monomer. 8. The organic electroluminescent layer according to claim 1, wherein the substrate is a polyimide film, an aramid film, a polyester film, a polyethylene naphthalate film, a cycloolefin film or an acrylic film. Laminates.

Images