JP2017033624A - Organic electroluminescent laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for organic electroluminescence having excellent hardness, transparency and folding endurance.SOLUTION: In a laminate for organic electroluminescence, an optical laminate is laminated on one surface of an organic electroluminescent layer. The laminate for organic electroluminescence is characterized in that cracking or breaking does not occur even if a test, in which the whole surface of the laminate for organic electroluminescence is folded at 180° at intervals of 20 mm, is repeated 100,000 times.SELECTED DRAWING: None

Description

The present invention relates to an organic electroluminescence laminate.

In recent years, an optical film used for organic electroluminescence has an excellent hardness and sometimes has an excellent durability folding performance that does not cause cracks even when the optical film is repeatedly folded.

However, since hardness and folding performance are usually in a trade-off relationship, with conventional optical films, when the hardness is improved, the durable folding performance is lowered, and when the durable folding performance is improved, the hardness is lowered. Therefore, these performances could not be improved at the same time.

In organic electroluminescence, a glass substrate is often used. However, although glass has high hardness, it cannot be given folding performance because it is broken when folded, and glass is a material with a large specific gravity. When the glass is thinned, 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 provided on one surface of a base film such as a cellulose acylate film or a polyester film. An optical film provided is disclosed.
However, such an optical film has excellent hardness, but the base film may be cut off or fold marks may be caused by repeated folding, and it does not satisfy the durable folding performance required in recent years. There wasn't.

In addition, since it has excellent mechanical strength, it has been studied to use a polyimide film as a substrate film in an optical film. Generally, a polyimide film has low transparency and is used for an optical film. There was a problem that was not suitable.
Furthermore, even if a polyimide film is used as the base material film, it has been difficult to achieve both excellent durability folding performance and hardness required in recent years.

JP 2014-186210 A

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

The present invention is an organic electroluminescence laminate in which an optical laminate is laminated on one surface of an organic electroluminescence layer, and a test is performed in which the entire surface of the organic electroluminescence laminate is folded by 180 ° at intervals of 20 mm. It is a laminate for organic electroluminescence characterized in that it is not cracked or broken when repeated 100,000 times.

In the laminate for organic electroluminescence of the present invention, it is preferable that the base material film of the optical laminate is a polyimide film or an aramid film.
Moreover, it is preferable that the thickness of a base film is 10-55 micrometers in an optical laminated body.
Moreover, the optical laminated body was provided on the side opposite to the base film side of the first hard coat layer, and the first hard coat layer provided on the side opposite to the organic electroluminescence layer of the base film. It is preferable to have a second 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, It is preferable to contain silica fine particles dispersed in the resin component, and the silica fine particles are preferably reactive silica fine particles.
Moreover, it is preferable that an optical laminated body further has the cured layer of a monofunctional monomer.

In the organic electroluminescence 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 base film is preferably a polyimide film or an aramid film.
Here, since the polyimide film and the aramid film have an aromatic ring in the molecule, they are generally colored (yellow), but when used for optical film applications, the skeleton in the molecule is changed. It is a film called “transparent polyimide” or “transparent aramid” with improved transparency. On the other hand, a colored conventional polyimide film or the like is preferably used for an electronic material such as a printer or an electronic circuit in terms of heat resistance and flexibility.
The laminate for organic EL using the base film made of these materials does not generate cracks or breaks in the durability folding test described later, and has not only excellent durability folding performance required in recent years, but also excellent hardness. And also has transparency.
Moreover, a polyimide film and an aramid film are excellent also in heat resistance, and can also provide further excellent hardness and transparency by baking.

Here, in the organic EL laminate of the present invention, the excellent hardness is a pencil hardness test (load of 750 g) defined in JIS K5600-5-4 (1999) of a hard coat layer in an optical laminate described later. It means that the hardness measured under the conditions is 5H or more, preferably 6H or more, and more preferably 7H or more.
Moreover, in the laminate for 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 a concavo-convex 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 base film side, it means that the total light transmittance is 80% or more, and the total light transmittance is 85% or more. Preferably there is.

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

The aramid film generally has a skeleton represented by the following formulas (18) and (19). Examples of the aramid film include a compound represented by the following formula (20). Is mentioned.
In the following formula, n is a repeating unit and represents an integer of 2 or more.

Commercially available polyimide films or aramid films represented by the above formulas (1) to (17) and (20) may be used.
Examples of commercially available products of the transparent polyimide film include Neoprim produced by Mitsubishi Gas Chemical Company, and examples of commercially available products of the transparent aramid film include Mikutron manufactured by Toray Industries, Inc.
Moreover, what was synthesize | combined by the well-known method may be used for the polyimide film or aramid film represented by said Formula (1)-(17) and (20).
For example, a method for synthesizing a polyimide film represented by the above formula (1) is described in Japanese Patent Application Laid-Open No. 2009-132091. Specifically, the following formula (21)

And 4,4′-hexafluoropropylidenebisphthalic dianhydride (6FPA) represented by the following reaction with 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFDB) Can be obtained.

The weight average molecular weight of the polyimide film or the aramid film is preferably in the range of 3000 to 500,000, more preferably in the range of 5000 to 300,000, and still more preferably in the range of 10,000 to 200,000. . If the weight average molecular weight is less than 3000, sufficient strength may not be obtained. If the weight average molecular weight exceeds 500,000, the viscosity increases and the solubility decreases, so that a film having a smooth surface and a uniform film thickness is obtained. It may not be possible.
In addition, in this specification, a weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC).

Among the polyimide films or aramid films, a polyimide film or aramid film having a structure in which charge transfer within a molecule or between molecules hardly occurs is preferable because it has excellent transparency. Specifically, the above formula (1 ) To (8), polyimide films having an alicyclic structure such as the above formulas (9) to (12), and aramid films having a halogen group such as the above formula (20).
Moreover, in the fluorinated polyimide films such as the above formulas (1) to (8), since they have a fluorinated structure, they have high heat resistance and are not colored by heat during the production of the polyimide film. So it has excellent transparency.
Since the base film can have a hardness measured under the pencil hardness test (750 g load) defined in JIS K5600-5-4 (1999) of the hard coat layer described later, the above formula (1 It is preferable to use a fluorinated polyimide film such as) to (8) or an aramid film having a halogen group such as the above formula (20). Especially, since the said pencil hardness can provide the very outstanding hardness of 7H or more, it is more preferable to use the polyimide film represented by the said Formula (1).

The substrate film preferably has a thickness of 10 to 55 μm. When the thickness of the base film is less than 10 μm, the curl of the organic EL laminate of the present invention is increased, the hardness is insufficient, and the pencil hardness described later may not be 4H or more. When the organic EL laminate of the present invention is produced by Roll to Roll, wrinkles are likely to occur, and the appearance may be deteriorated. On the other hand, if the thickness of the substrate film exceeds 55 μm, the folding performance of the organic EL laminate of the present invention may be insufficient, and may fail to satisfy the requirements for the durability folding test described later. The laminate for EL becomes heavy, which is not preferable in terms of weight reduction.

The organic EL laminate of the present invention does not crack or break when the test for folding the entire surface of the organic EL laminate at 180 ° at a distance of 20 mm is repeated 100,000 times.
The organic EL laminate of the present invention is preferably free from cracking or breaking when the test of folding the entire surface of the organic EL laminate at 180 ° at a spacing of 15 mm is repeated 100,000 times. It is more preferable that no cracks or breaks occur when the test for folding the entire surface of the laminate for organic EL 180 ° is repeated 100,000 times.
FIG. 1 is a cross-sectional view schematically showing a test for folding the entire surface of the organic EL laminate of the present invention by 180 ° at an interval of 520 mm (hereinafter also referred to as a durable folding test). In the present invention, the interval of 520 mm means that the distance between the opposed organic EL laminates is 520 mm.
As shown in FIG. 1A, in the durability folding test, first, one side of the organic EL laminate 10 of the present invention and another side facing the one side are parallel to each other. It fixes to the arrange | positioned upper fixing | fixed part 11 and the lower fixing | fixed part 12, 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 of this invention in the said durable folding test is a rectangle.
Further, as shown in FIG. 1, the upper fixing portion 11 is fixed, and the lower fixing portion 12 is movable to the left and right while maintaining parallel to the upper fixing portion 11.

Next, as shown in FIG. 1 (b), the bent portion of the test piece 10 is moved to the vicinity of the other side fixed to the lower fixing portion 12 by moving the lower fixing portion 12 to the left. Further, as shown in FIG. 1C, 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 to the right.
By moving the lower fixing portion 12 as shown in FIGS. 1A to 1C, the entire surface of the organic EL laminate of the present invention can be folded 180 °.
The laminate for organic EL of the present invention is cracked or broken when the folding test shown in FIGS. 1A to 1C is performed 100,000 times on the laminate for organic EL 10 times. Does not occur. When the organic EL laminate 10 of the present invention is cracked or broken within 100,000 times, the durable folding performance of the organic EL laminate of the present invention becomes insufficient. In this invention, when the said durable folding test is performed 150,000 times to the laminated body 10 for organic EL of this invention, it is preferable that a crack or a fracture | rupture does not arise.
Further, the organic EL laminate 10 of the present invention may be one that does not crack or break when the above durability folding test is performed on one side, but the above durability folding test is performed on both sides. When done, it is preferred that no cracks or breaks occur.
In the present invention, even when the above-mentioned laminate 10 for organic EL of the present invention is rotated by 90 ° and the same durability folding test is performed, the same cracking or breakage does not occur.

The organic EL laminate of the present invention preferably has interference fringe prevention performance.
This is because the organic EL laminate of the present invention has folding performance, and thus has a new problem of interference fringes such that the interference fringes are conspicuous in the folded portion or the interference fringes move when folded.
The organic EL laminate of the present invention obtains the spectral reflectance of the organic EL laminate in a wavelength range of 400 nm to 700 nm, and the standard deviation of the spectral reflectance in an arbitrary range of 50 nm is less than 0.045. It is preferable.
The standard deviation of the spectral reflectance can be obtained by the following procedure.
First, the reflectance in the wavelength range of 380 nm to 780 nm of the laminate for organic EL of the present invention is measured by a 5-degree reflection measurement method using a spectrophotometer. Specifically, the surface on which the hard coat layer of the organic EL laminate of the present invention is formed is irradiated with light having an incident angle of 5 degrees, and the positive light reflected by the organic EL laminate of the present invention is reflected. The reflected light in the reflection direction is received, and the reflectance in the wavelength range of 380 nm to 780 nm is measured.
Subsequently, an approximate value is calculated | required with a quadratic polynomial about the wavelength range of 400-700 nm of the said measurement data.
Finally, the standard deviation is calculated from the difference between the measured value and the approximate value by the second order polynomial for an arbitrary range of 50 nm.
In addition, the said spectral reflectance used the spectral reflectance measured with the spectrophotometer (MPC3100, Shimadzu Corp. make).

In the organic EL laminate of the present invention, in the visible light region having a wavelength of 400 nm to 700 nm, the standard deviation of the spectral reflectance in an arbitrary range of 50 nm is less than 0.045.
The laminate for organic EL of the present invention that satisfies the requirement of the standard deviation of the spectral reflectance has an extremely excellent interference fringe prevention performance, and no interference fringes are generated in the folded portion, and the movement caused by folding is performed. No interference fringes are observed.
In the organic EL laminate of the present invention, in the visible light region having a wavelength of 400 nm to 700 nm, the standard deviation of the spectral reflectance in an arbitrary 50 nm range is preferably less than 0.035, and less than 0.025. It is more preferable.
In the organic EL laminate of the present invention, the standard deviation in the range of 50 nm having the largest standard deviation in the wavelength range of 400 to 700 nm is more preferably less than 0.045, and less than 0.035. It is particularly preferred that it is less than 0.025 and most preferred.

In the organic EL laminate of the present invention, it is preferable that the optical laminate further has a cured layer of a monofunctional monomer.
It is preferable to have the cured layer of the monofunctional monomer on the side surface opposite to the organic EL layer of the substrate film.
Moreover, the cured layer of the monofunctional monomer may have between the base film and a first hard coat layer described later, and a first hard coat layer and a second hard coat layer described later. Although it may have in between, it is more preferable to have between the said base film and the 1st hard-coat layer mentioned later from a viewpoint which provides the extremely outstanding interference fringe prevention property.
The cured layer of the monofunctional monomer is a layer for imparting the above-described interference fringe prevention performance.
In the laminated body for organic EL of the present invention, when the optical laminated body forms the cured layer of the monofunctional monomer, the monofunctional monomer component in the cured layer composition of the monofunctional monomer described later is By dissolving the material film or the like, the refractive index of the dissolved part 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. When the thickness is less than 0.5 μm, the above-described interference fringe prevention performance may not be sufficiently imparted, and when it exceeds 8 μm, sufficient pencil hardness may not be imparted.
The 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.
In addition, the thickness of the said hard-coat layer can be measured by cross-sectional microscope observation.

Examples of the monofunctional monomer used in the cured layer of the monofunctional monomer include an ionizing radiation curable resin, and among them, a monofunctional acrylic monomer is preferably used.
The monofunctional acrylic monomer is at least one selected from the group consisting of acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate. In particular, even when a polyimide film or the like having excellent solvent resistance is used as a resin substrate, the film can be suitably dissolved, and extremely excellent interference fringe prevention performance is imparted. Since it can do, it is preferable that it is acryloyl morpholine.

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

The composition for a cured layer of the monofunctional monomer is similar to the composition for a hard coat layer described later, a photopolymerization initiator, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, and coloring. An inhibitor, a colorant (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, an adhesion promoter, a polymerization inhibitor, an antioxidant, a surface modifier, and the like may be added.

In the laminate for organic EL of the present invention, the optical laminate is 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 a second hard coat layer provided on the opposite side surface.
Hereinafter, both the first hard coat layer and the second hard coat layer are also simply referred to as “hard coat layers” unless it is necessary to distinguish between 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 the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) of the hard coat layer is 4H or more. In addition, sufficient durable folding performance can be imparted to the organic EL laminate of the present invention. The more preferable lower limit of the Martens hardness at the cross-sectional center 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-mentioned durable foldability 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 within the above range, the surface of the hard coat layer has sufficient durability folding performance and a load of 1 kg / cm ² with # 0000 steel wool. It is possible to impart extremely excellent scratch resistance such that no scratches are generated in a steel wool test in which the steel is reciprocated 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, it is preferable that the Martens hardness of the first hard coat layer is larger than the Martens hardness of the second hard coat layer. By having such a Martens hardness relationship, the pencil hardness of the organic EL laminate of the present invention is particularly good. This is because when the organic EL laminate of the present invention is subjected to a pencil hardness test and a pencil is loaded with a load, deformation of the organic EL laminate of the present invention is suppressed, and scratches and dent deformation are prevented. This is because it decreases. In addition, it has sufficient durability folding performance, and scratches do not occur in the steel wool test in which the surface of the hard coat layer is rubbed back and forth 3500 times while applying a load of 1 kg / cm ² with # 0000 steel wool. Extremely excellent scratch resistance can be imparted.
As a method for 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 made so that the content of silica fine particles described later is contained more on the first hard coat layer side. And the like.
In the organic EL laminate of the present invention, the hard coat layer may have a single structure, and in this case, the silica fine particles described later are unevenly distributed on the base film side in the hard coat layer, that is, the above-mentioned It is preferable that the proportion of silica fine particles in the hard coat layer is inclined so as to be larger on the base film side and smaller as it goes to the side opposite to the base film side.
In the present specification, “Martens hardness” is the hardness when the indenter is pushed in by 500 nm by the hardness measurement by the nanoindentation method.
In addition, in this specification, the measurement of the Martens hardness by the said nanoindentation method was performed using "TI950 TriboIndenter" made from HYSITRON (Heiditron). That is, a Berkovich indenter (triangular pyramid) as the above indenter was pushed in by 500 nm from the surface of the hard coat layer of the organic EL laminate of the present invention and held constant to relieve the residual stress. The max load is measured, and the Martens hardness is calculated by P _max / A using the max load (P _max (μN) and a recessed area (A (nm ² ) having 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 also contains silica fine particles dispersed in the resin component.
Examples of the polyfunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and pentaerythritol tris. (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 (meta 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, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and PO , EO, caprolactone and the like.
Among these, since the above-mentioned Martens hardness can be satisfactorily satisfied, those having 3 to 6 functionalities are preferable, for example, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA). ), Dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, and the like are preferable.
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 that can form a crosslinked structure with the polyfunctional (meth) acrylate monomer. By containing the reactive silica fine particles, the first hard coat layer Can be sufficiently increased in hardness.

The 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 preferably used, and more preferably a photocurable unsaturated group. Particularly preferred are ionizing radiation-curable unsaturated groups. Specific examples of the reactive functional group include an ethylenically unsaturated bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

The reactive silica fine particles are not particularly limited and conventionally known fine particles 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 microparticles | fine-particles, the product made from Nissan Chemical Industries; MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, the product made by JGC Catalysts &Chemicals; V8802, V8803 etc. are mentioned, for example. .

The silica fine particles may be spherical silica fine particles, but are preferably atypical silica fine particles. Spherical silica fine particles and atypical silica fine particles may be mixed.
In the present specification, the atypical silica fine particles mean silica fine particles having a shape having potato-like random irregularities on the surface.
Since the atypical silica fine particles have a larger surface area than the spherical silica fine particles, the inclusion of such atypical silica fine particles increases the contact area with the polyfunctional (meth) acrylate, etc. The layer hardness (pencil hardness) can be made more excellent.
Whether or not the atypical silica fine particles are present can be confirmed by observing a cross section of the first hard coat layer with an electron microscope.

When the silica fine particles are irregular-shaped silica fine particles, the average particle diameter of the irregular-shaped silica fine particles is preferably 5 to 200 nm. When the thickness is less than 5 nm, it is difficult to produce the fine particles themselves, the fine particles may be aggregated, and it may be extremely difficult to make an irregular shape. The dispersibility of atypical silica fine particles may be poor and agglomerate in stages. On the other hand, when the average particle diameter of the irregular-shaped silica fine particles exceeds 200 nm, large irregularities may be formed on the hard coat layer, or a problem such as an increase in haze may occur.
The average particle size of the irregular-shaped silica fine particles is the average of the maximum value (major axis) and the minimum value (minor axis) of the distance between the two points on the outer periphery of the irregular-shaped silica fine particles appearing by cross-sectional microscope observation of the hard coat layer. Value.

The hardness (Martens hardness) of the first hard coat layer can be controlled by controlling the size and blending 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 first hard coat layer, the silica fine particles have a diameter of 5 to 200 nm, and preferably 25 to 60 parts by mass with respect to 100 parts by mass of the resin component.

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.
In addition to the polyfunctional (meth) acrylate, the second hard coat layer may contain polyfunctional urethane (meth) acrylate and / or polyfunctional epoxy (meth) acrylate as a resin component.
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 fine particle in said 2nd hard-coat layer, For example, it is preferable that it is 0-20 mass% in said 2nd hard-coat layer.

The hard coat layer may contain a material other than the above-described materials as long as it satisfies the above-described Martens hardness in any case of the first hard coat layer and the second hard coat layer. For example, as a resin component material, a polymerizable monomer or a polymerizable oligomer that forms a cured product upon irradiation with ionizing radiation may be included.
Examples of the polymerizable monomer or polymerizable oligomer include 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. It is done.
Examples of the (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule or the (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule include urethane (meth) acrylate and polyester (meth) ) Acrylates, epoxy (meth) acrylates, melamine (meth) acrylates, polyfluoroalkyl (meth) acrylates, and silicone (meth) acrylate monomers or oligomers. These polymerizable monomers or polymerizable oligomers may be used alone or in combination of two or more. Of these, urethane (meth) acrylate having a polyfunctionality (6 functionalities or more) and a weight average molecular weight of 1000 to 10,000 is preferable.

In addition, in order to adjust the hardness, the viscosity of the composition, improve the adhesion, etc., the material constituting the hard coat may further contain a monofunctional (meth) acrylate monomer.
Examples of the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxypolyethylene glycol (meth) acrylate, isostearyl (meth) acrylate, 2-acryloyloxyethyl succinate, acryloylmorpholine, 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.
Moreover, the weight average molecular weight of the polymerizable oligomer is preferably 1000 to 20,000, more preferably 1000 to 10,000, and still more preferably 2000 to 7000.
In addition, in this specification, the weight average molecular weight of the said polymerizable monomer and polymerizable oligomer is the weight average molecular weight of polystyrene conversion measured by GPC method.

The hard coat layer may contain an ultraviolet absorber (UVA).
As described later, the organic EL laminate of the present invention is particularly preferably used for a mobile terminal such as a foldable smartphone or tablet terminal, but such a mobile terminal is often used outdoors, Therefore, there exists a problem that the polarizer arrange | positioned under the organic electroluminescent laminated body of this invention is exposed to an ultraviolet-ray, and deteriorates easily.
However, since the hard coat layer is disposed on the display screen side of the polarizer, if the hard coat layer contains an ultraviolet absorber, the polarizer is preferably deteriorated by exposure to ultraviolet rays. 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.

As said ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, etc. are mentioned, for example.

Examples of the triazine ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. 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.
Examples of commercially available triazine ultraviolet absorbers include TINUVIN460, TINUVIN477 (both manufactured by BASF), LA-46 (manufactured by ADEKA), and the like.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy. Examples include benzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate, and hydroxymethoxybenzophenone sodium sulfonate.
Moreover, as a commercially available benzophenone type ultraviolet absorber, CHMASSORB81 / FL (made by BASF) etc. are mentioned, for example.

Examples of the benzotriazole ultraviolet absorber include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2 -(2H-benzotriazol-2-yl) -6- (linear and side chain 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 Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole Can be mentioned.
Moreover, as a commercially available benzotriazole type ultraviolet absorber, for example, KEMISORB 71D, KEMISORB 79 (all manufactured by Chemipro Kasei Co., Ltd.), JF-80, JAST-500 (all manufactured by Johoku Chemical Co., Ltd.), ULS-1933D (Manufactured by one company), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) and the like.

Among these ultraviolet absorbers, triazine ultraviolet absorbers and benzotriazole ultraviolet absorbers are preferably used.
The ultraviolet absorber preferably has higher solubility with the resin component constituting the hard coat layer, and preferably has less bleed-out after the above-described durability folding test.
The UV absorber is preferably polymerized or oligomerized.
As the ultraviolet absorber, a polymer or oligomer having a benzotriazole, triazine, or benzophenone skeleton is preferable, and specifically, (meth) acrylate having a benzotriazole or benzophenone skeleton and methyl methacrylate (MMA) in an arbitrary ratio. It is preferable that it is what was heat-copolymerized with.
The UVA can also serve to protect the organic EL layer from ultraviolet rays.

Although it does not specifically limit as content of the said ultraviolet absorber, It is preferable that it is 1-6 mass parts with respect to 100 mass parts of resin solid content of the said hard-coat layer. If the amount is less than 1 part by mass, the effect of containing the above-described ultraviolet absorber in the hard coat layer may not be sufficiently obtained. If the amount exceeds 6 parts by mass, the hard coat layer may be markedly colored or deteriorated in strength. May occur. The minimum with more preferable content of the said ultraviolet absorber is 2 mass parts, and a more preferable upper limit is 5 mass parts.

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. It is preferable that If it is less than the lower limit of each layer thickness, the hardness of the hard coat layer may be significantly reduced, and if it exceeds the upper limit of each layer thickness, coating of the coating liquid to form the hard coat layer becomes difficult, Moreover, the workability (especially chipping resistance) resulting from the thickness being too thick may deteriorate.
The more preferred lower limit of the layer thickness of the first hard coat layer is 2.5 μm, the more preferred upper limit is 4.5 μm, the more preferred lower limit of the layer thickness of the second hard coat layer is 1.0 μm, and the more preferred upper limit is 3.5 μm.
In addition, the layer thickness of the said hard-coat layer is an average value of the thickness of arbitrary 10 places obtained by measuring by the electron microscope (SEM, TEM, STEM) observation of a cross section.

In the above optical laminate, the organic EL laminate of the present invention having a hard coat layer preferably has a light transmittance of 380 nm of 10% or less, more preferably 8% or less. If the transmittance exceeds 10%, when the organic EL laminate of the present invention is used for a mobile terminal, the polarizer may be easily exposed to ultraviolet rays and deteriorate. A more preferable upper limit of the transmittance of light having a wavelength of 380 nm of the hard coat layer is 5%.
The hard coat layer preferably has a haze of 2.5% or less. If it exceeds 2.5%, when the organic EL laminate of the present invention is used in a mobile terminal, whitening of the display screen may be a problem. A more preferable upper limit of the haze is 1.5%, and a more preferable upper limit is 1.0%.
The transmittance and haze can be measured according to JIS K-7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).
The haze of the entire organic EL laminate of the present invention is the sum of the haze of the hard coat layer and the haze of the substrate film. When the haze of the substrate film is higher than 1%, The overall haze of the laminate for EL is higher than 1%.

If necessary, the hard coat layer may be, 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. These components may be contained.

In addition, the optical layered body is provided with another hard coat layer (hereinafter referred to as a back hard disk) on the opposite side surface of the base film on which the above-described hard coat layers (first hard coat layer and second hard coat layer) are provided. (Also referred to as a coat layer) may be formed. As said back surface hard-coat layer, the layer similar to the hard-coat layer mentioned above is mentioned, for example.
The back hard coat layer preferably has a back hard coat layer (1) and / or a back hard coat layer (2).
Examples of the back hard coat layer (1) and the back hard coat layer (2) include layers having the same composition and thickness as the first hard coat layer or the second hard coat layer described above.
That is, when the optical laminate has the back hard coat layer, the back hard coat layer has a structure having the back hard coat layer (1) similar to the first hard coat layer described above, and the second hard coat described above. A structure having a back hard coat layer (1) similar to the coat layer, a back hard coat layer (1) similar to the first hard coat layer described above, and a back hard coat layer (2 similar to the second hard coat layer described above) ) Are laminated in this order from the base film side, the back hard coat layer (1) similar to the second hard coat layer described above, and the back hard coat layer (2 similar to the first hard coat layer described above) ) Are laminated in this order from the base film side.
In addition, since the said back surface hard-coat layer is arrange | positioned on the side surface opposite to the outermost surface 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 adding an antifouling agent to the hard coat layer in the optical laminate.
The hard coat layer containing the antifouling agent preferably has a surface contact angle with water of 100 ° or more, and in the laminate for organic EL of the present invention immediately after production, the water on the surface of the hard coat layer. More preferably, the contact angle with respect to the surface of the second hard coat layer is reciprocated 3500 times while applying a load of 1 kg / cm ² with # 0000 steel wool. The contact angle of water on the surface of the hard coat layer after the treatment is preferably 90 ° or more, and more preferably 103 ° or more.

It is preferable that the antifouling agent is contained unevenly on the outermost surface side of the hard coat layer. When the antifouling agent is uniformly contained in the hard coat layer, it is necessary to increase the amount of addition in order to impart sufficient antifouling performance, which may lead to a decrease in the film strength of the hard coat layer. When the hard coat layer has the first hard coat layer and the second hard coat layer described above, the antifouling agent is unevenly distributed on the outermost surface side of the second hard coat layer disposed on the outermost surface side. It is preferably 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, a coating film formed using a composition for a hard coat layer described later is dried and cured. Before the coating, heat is applied to the coating film to lower the viscosity of the resin component contained in the coating film to increase fluidity, and the antifouling agent is unevenly distributed on the outermost surface side. Select and use a stain, float the antifouling agent on the surface of the coating without applying heat when drying the coating, and then cure the coating to bring the antifouling agent to the outermost surface. The method of making it unevenly distributed is mentioned.

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. The antifouling agent may be an acrylic antifouling agent.
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 resin material described above. If the amount is less than 0.01 part by weight, the hard coat layer may not be provided with sufficient antifouling performance, and the slipperiness is poor, so that scratches may occur even in the steel wool resistance test. On the other hand, if it exceeds 3.0 parts by weight, the hardness of the hard coat layer may decrease, and the antifouling agent itself becomes a ball (micelle) state, and the resin component and the antifouling agent of the hard coat layer However, there is a possibility of fine phase separation (sea-island state) and whitening.
The antifouling agent preferably has a weight average molecular weight of 20,000 or less, and preferably has 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.
In addition, when the said antifouling agent does not have a reactive functional group, the antifouling agent is transferred to the back surface when it is stacked, whether it is a roll or a sheet, according to the present invention. Therefore, if another member is pasted or applied to the back surface, the other member may be peeled 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 antifouling performance durability (durability), and in particular, the hard coat layer containing the above-mentioned fluorine-containing antifouling agent has a fingerprint. Difficult (not conspicuous) and good wiping property. Furthermore, since the surface tension at the time of application | coating of the said composition for hard-coat layer formation can be lowered | hung, leveling property is good and the external appearance of the hard-coat layer to form becomes a favorable thing.
In addition, the hard coat layer containing the silicone-containing antifouling agent has good sliding properties and good steel wool resistance.
Since the laminate for organic EL of the present invention containing such a silicone-containing antifouling agent in the hard coat layer has a good sliding feeling when brought into contact with a finger or a pen, the tactile sensation is improved. In addition, fingerprints are hardly attached to the hard coat layer (not easily noticeable), and the wiping property is good. Furthermore, since the surface tension at the time of coating of the composition (hard coat layer composition) at the time of forming the hard coat layer can be lowered, the leveling property is good and the appearance of the hard coat layer to be formed is good. It will be a thing.
Moreover, as said antifouling agent which has the said reactive functional group, it can obtain as a commercial item, As a commercial item other than the above, as a silicone-containing antifouling agent, for example, SUA1900L10 (Shin Nakamura Chemical Co., Ltd.) ), SUA1900L6 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel Cytec Co., Ltd.), UT3971 (manufactured by Nihon Gosei Co., Ltd.), BYKUV3500 (manufactured by BYK Chemie), BYKUV3510 (manufactured by BYK Chemie), BYKUV3570 (manufactured by BYK Chemie), X22 -164E, X22-174BX, X22-2426, KBM503. KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), TEGO-RAD2250, TEGO-RAD2300. TEGO-RAD2200N, TEGO-RAD2010, TEGO-RAD2500, TEGO-RAD2600, TEGO-RAD2700 (manufactured by Evonik Japan), Megafax RS854 (manufactured by DIC) and the like can be mentioned.
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.), 650A, tangent 601AD, tangent 602, and the like.
Examples of the antifouling agent having a fluorine-containing and silicone-containing reactive functional group include, for example, MegaFac RS851, MegaFac RS852, MegaFac RS853, MegaFac RS854 (manufactured by DIC), Opstar TU2225, Opstar TU2224. (Manufactured by JSR), X71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the optical layered body, the first hard coat layer contains a surfactant (leveling agent) as necessary in order to improve the coating property of the composition when forming the first hard coat layer. It may be.
When the leveling agent is added in an excessive amount, bubbles are generated in the coating film when the first hard coat layer is formed, resulting in defects or when the second hard coat layer is laminated. The coat layer may repel or adhesion may deteriorate.
Moreover, when the coating film at the time of forming a 1st hard-coat layer is also non-uniform | heterogenous, there are unevenness | corrugation, a defect, etc., a crack and a fracture | rupture may arise in the durable folding test mentioned above.

The hard coat layer can be formed using, for example, a hard coat layer composition to which the resin component and reactive silica fine particles, an ultraviolet absorber, and other components are added.
The said composition for hard-coat layers may contain a solvent as needed.

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), Amide (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 two or more of them may be used in combination.
Among them, as the solvent, the resin component such as the polymerizable monomer and / or polymerizable oligomer described above, and other additives can be dissolved or dispersed to suitably apply the hard coat layer composition. And methyl isobutyl ketone and methyl ethyl ketone are preferred.

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

As a method for producing the optical laminate using the hard coat layer composition, for example, on one surface of the base film, the hard coat layer composition is applied to form a coating layer, Examples include a method of curing the coating layer after drying.

Examples of the method for forming the coating layer by applying the hard coat layer composition on one surface of the substrate film include spin coating, dipping, spraying, die coating, bar coating, and rolls. Various known methods such as a coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a bead coater method can be used.

Although it does not specifically limit as a drying method of the said coating film, Generally it is good to dry for 10 to 120 second at 30-120 degreeC.
Moreover, what is necessary is just to select a well-known method suitably according to the composition etc. of the said composition for hard-coat layers as a hardening method of the said coating film. For example, if the hard coat layer composition is of an ultraviolet curable type, the coating layer may be cured by irradiating with ultraviolet rays.

In the case where the hard coat layer has the first hard coat layer and the second hard coat layer described above, the composition for the first hard coat layer prepared for forming the first hard coat layer is the above group. The coating film formed on the material film is dried and then half cured. By forming a second hard coat layer to be described later in a state where the coating film is not completely cured but half cured, the adhesion between the first hard coat layer and the second hard coat layer becomes extremely excellent. . Examples of the method of half-curing the coating film include a method of irradiating the dried coating film with ultraviolet rays at 100 mJ / cm ² or less.
The second hard coat layer composition prepared for forming the second hard coat layer was applied onto the half-cured first hard coat layer and the formed coating film was dried. By completely curing, the 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) will be excellent by fully hardening the coating film using the said composition for 2nd hard-coat layers. As a method for completely curing the coating film of the second hard coat layer composition, for example, the coating film is in a nitrogen atmosphere (oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, and further preferably 100 ppm or less). And the method of hardening by ultraviolet irradiation is mentioned. The steel wool resistance can also be improved by increasing the degree of cross-linking (reaction rate) on 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 fully hardened | cured (a 1st hard-coat layer and a 2nd hard-coat layer), ultraviolet irradiation The total amount is preferably 150 mJ / cm ² or more.

In the present invention, the hard coat layer may be formed using a conventionally known thermosetting sol-gel method.
The thermosetting sol-gel method is generally a method in which an alkoxysilane compound having an epoxy group is hydrolyzed to a gel that loses fluidity by a polycondensation reaction. The method of obtaining is generally known, but in addition, for example, the alkoxysilane compound is hydrolyzed and subjected to a polycondensation reaction to obtain an oxide, or the alkoxysilane compound having an isocyanate group is heated to polycondensate. Alternatively, an oxide may be obtained, or an alkoxysilane compound and an isocyanate group-containing compound may be mixed at an arbitrary ratio, followed by 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 hydrolyzable silicon group in the molecule. For example, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

The hydrolyzate of the alkoxysilane compound having the epoxy group can be obtained by performing hydrolysis by dissolving the alkoxysilane compound having the epoxy group in an appropriate solvent. Examples of the solvent used include 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, Alternatively, a mixture thereof can be mentioned. Of these, methyl ethyl ketone is preferred because it has a drying rate suitable for forming a film.

When performing the said hydrolysis, you may use a catalyst as needed. It does not specifically limit as a catalyst to be used, A well-known acid catalyst or a base catalyst 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, and oxalic acid. And inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol-like fillers such as acidic colloidal silica and oxidized thania sol; These may be used alone or in combination of two or more.
Examples of the base catalyst include aqueous solutions of alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide, aqueous ammonia, and aqueous solutions of amines. Of these, the use of hydrochloric acid or acetic acid, which has high catalytic reaction efficiency, is preferred.

Further, the alkoxysilane compound is not particularly limited, and for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrimethoxysilane. Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldi 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-isocyanatopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 2-isocyanatoethyltri n-propoxysilane etc. are mentioned.

The compound having an isocyanate group is not particularly limited, and examples thereof include tolylene diisocyanate (TDI), 3,3′-tolylene-4,4′-isocyanate, diphenylmethane 4,4′-diisocyanate (MDI), and 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-carbamate, polymethylene polyphenyl isocyanate, 3,3′-dimethoxy 4,4′-diphenyl diisocyanate, diphenyl ether 2,4,1′-triisocyanate, m-xylylene diisocyanate (MXDI) ), Polymethylene polyphenyl isocyanate (PAPI) and the like.

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 such as preventing reflection by external light and screen glare. From the viewpoint of improving, it is preferable to have a concavo-convex shape on the surface opposite to the base film side.
The hard coat layer having the concavo-convex shape may be one in which the first hard coat layer has a concavo-convex shape on the surface opposite to the base film, or the side opposite to the base film of the second hard coat layer. It may have an uneven shape on the surface.
The concave and convex shape of the hard coat layer is defined as Sm as the average interval between the concave and convex portions on the surface opposite to the base film side of the hard coat layer, θa as the average inclination angle of the concave and convex portions, and Ra as the arithmetic average roughness It is preferable that the following formula is satisfied.
30 μm <Sm <90 μm,
2 <θa <15,
0.5 μm <Ra <1.5 μm
Said Sm, (theta) a, and Ra are the values obtained by the method based on JISB0601-1994, For example, it can measure and obtain | require by the surface roughness measuring device: SE-3400 / made by Kosaka Laboratory.

The concave and convex shape of the hard coat layer is defined as Sm as the average interval between the concave and convex portions on the surface opposite to the base film side of the hard coat layer, θa as the average inclination angle of the concave and convex portions, and Ra as the arithmetic average roughness It is preferable that the following formula is 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
Said Sm, (theta) a, and Ra are the values obtained by the method based on JISB0601-1994, For example, it can measure and obtain | require by the surface roughness measuring device: SE-3400 / made by Kosaka Laboratory.

The uneven shape on the surface opposite to the base film side of the hard coat layer may be formed by a composition containing an antiglare agent, formed by phase separation of a 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 true sphere, an ellipse, or an indefinite shape. As the antiglare agent, inorganic or organic fine particles can be used, and transparent fine particles are preferable.
Specific examples of the organic fine particles include plastic beads. Examples of plastic beads include 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), and the like. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include polystyrene beads.
Examples of the inorganic fine particles include inorganic silica beads having a specific shape such as amorphous silica and spherical shape.
Among them, it is preferable to use acrylic-styrene copolymer beads and / or amorphous silica as the antiglare agent.

The average particle size of the antiglare agent is preferably 1 to 10 μm, and more preferably 3 to 8 μm. The average particle diameter is a value obtained by measuring with a laser diffraction / scattering particle size distribution measuring apparatus in the state of 5 mass% toluene dispersion.
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 contains an internal scattering particle further. The internal scattering particles impart internal haze and can suppress surface glare (scintillation) and the like.
Examples of the internal scattering particles include organic particles having a relatively large refractive index difference from the binder resin constituting the hard coat layer. For example, acrylic-styrene copolymer beads (refractive index of 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 have the properties as the antiglare agent and the properties as internal scattering particles.

The average particle diameter of the internal scattering particles is preferably 0.5 to 10 μm, and more preferably 1 to 8 μm. The average particle diameter is a value obtained by measuring with a laser diffraction / scattering particle size distribution measuring apparatus in the state of 5 mass% toluene dispersion.
The amount of the internal scattering particles added is preferably 0.1 to 40% by mass and more preferably 1 to 30% by mass with respect to 100 parts by mass of the binder resin solid content.

Examples of the binder resin of the hard coat layer having a concavo-convex shape on the surface opposite to the base film side include the same binder resins that can be used for the hard coat layer described above.

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 effects of the present invention are 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 a concavo-convex 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 can be mixed and dispersed with a solvent to prepare a hard coat layer composition, which can be formed by a known method. The method for preparing the hard coat layer composition and the method for forming the hard coat layer using the same are the same as the method for preparing the hard coat layer composition described above and the method for 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 it is less than 1 μm, the antiglare property may not be suitably imparted. If it exceeds 10 μm, curling or cracking may occur.
The layer thickness is a value obtained by measuring the cross section of the optical layered body with an electron microscope (SEM, TEM, STEM).

The optical layered body preferably further has a conductive layer.
As said electroconductive layer, it is preferable that a conductive fibrous filler is included as a electrically conductive agent, for example.

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 increase 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 conductive fibrous filler is less than 1 μm, a conductive layer having sufficient conductive performance may not be formed, and aggregation may occur, resulting in an increase in haze value or a decrease in light transmission performance. Therefore, 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 further preferable range is 10 to 30 μm.
The fiber diameter and fiber length of the conductive fibrous filler are, for example, the fiber diameter and fiber length of the conductive fibrous filler at 1000 to 500,000 times using an electron microscope such as SEM, STEM, or TEM. It can obtain | require as an average value of 10 places measured.

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, and wire wall. These conductive carbon fibers can use 1 type (s) or 2 or more types.

As said metal fiber, the fiber produced by the wire-drawing method or the cutting method which extends stainless steel, iron, gold | metal | money, silver, aluminum, nickel, titanium etc. thinly and long can be used, for example. Such metal fiber can use 1 type (s) or 2 or more types. 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. One or more kinds of such metal-coated synthetic fibers can be used. Among these metal-coated synthetic fibers, a metal-coated synthetic fiber using silver is preferable because of its excellent conductivity.

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

Examples of other conductive agents other than the conductive fibrous filler include various cationic compounds having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups, and sulfonic acid. Anionic compounds having anionic groups such as bases, sulfate ester bases, phosphate ester bases, phosphonate bases, amphoteric compounds such as amino acids and aminosulfuric acid esters, nonions such as amino alcohols, glycerols and polyethylene glycols Compounds, organometallic compounds such as tin and titanium alkoxides, and metal chelate compounds such as acetylacetonate salts thereof, compounds obtained by increasing the molecular weight of the compounds listed above, and tertiary amino groups , A quaternary ammonium group or a metal chelate moiety, and ionization 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.
As content of the said other electrically conductive agent, it is preferable that it is 1-50 mass parts with respect to 100 mass parts of resin components which comprise the said electroconductive layer. When the amount is less than 1 part by mass, a conductive layer having sufficient conductivity may not be formed. When the amount exceeds 50 parts by mass, the haze of the conductive laminate of the present invention increases or the light transmission performance is insufficient. It may become.

Furthermore, as the conductive agent, for example, conductive fine particles can also be used.
Specific examples of the conductive fine particles include those made of a metal oxide. As such a metal oxide, for example, ZnO (refractive index 1.90, the numerical value in parenthesis represents a refractive index), CeO ₂ (1.95), Sb ₂ O ₃ (1.71). , SnO ₂ (1.997), indium tin oxide (1.95) often referred to 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), and the like can be given. The average particle size of the conductive fine particles is preferably 0.1 nm to 0.1 μm. By being within 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 almost no haze and good total light transmittance. A thing is obtained.
As content of the said electroconductive fine particles, it is preferable that it is 10-400 mass parts with respect to 100 mass parts of resin components which comprise the said electroconductive layer. If the amount is less than 10 parts by mass, a conductive layer having sufficient conductivity may not be formed. If the amount exceeds 400 parts by mass, the haze of the conductive laminate of the present invention is increased or the light transmission performance is insufficient. It may become.

Examples of the conductive agent include aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, and mixed conjugated poly. (Phenylene vinylene), a double-chain conjugated system which is a conjugated system having a plurality of conjugated chains in the molecule, a conductive complex which is a polymer obtained by grafting or block co-polymerizing the above-mentioned conjugated polymer chain onto a saturated polymer, etc. It is also possible to use a high molecular weight conductive agent.

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 high refractive index fine particles are not particularly limited, and for example, aromatic ring resin or sulfur resin such as aromatic polyimide resin, epoxy resin, (meth) acrylic resin (acrylate, methacrylate compound), polyester resin and urethane resin. Examples thereof include fine particles made of a material having a high refractive index such as a resin having a high refractive index containing atoms and bromine atoms and precursors thereof, or metal oxide fine particles and metal alkoxide fine particles.
The low refractive index fine particles are not particularly limited. For example, a resin having a low refractive index containing a fluorine atom in a resin material such as an epoxy resin, a (meth) acrylic resin, a polyester resin, and a urethane resin, and a precursor thereof. Examples include fine particles made of a material having a low refractive index, magnesium fluoride fine particles, hollow or porous fine particles (organic or inorganic), and the like.

A conventionally well-known thing can be used as said organic EL layer.
In the organic EL laminate 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 organic EL laminate 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.

Since the laminate for organic EL of the present invention has the above-described configuration and does not cause cracking or breaking in the durability folding test, it has extremely excellent foldability, and further has excellent hardness and transparency. Have.
Such a laminate for organic EL of the present invention can be used not only as a surface protective film for an image display device such as a liquid crystal display device, but also for a curved display, a surface protective film for a product having a curved surface, and the surface of a foldable member. Can be used as a protective film.
Especially, since the laminated body for organic EL of this invention has the extremely outstanding foldability, it is used suitably as a surface protection film of a foldable member.
Moreover, since the laminated body for organic EL of this invention is a member used as uses, such as a foldable smart phone and a foldable tablet, it is preferable that it is what has antimicrobial property. The method for imparting antibacterial properties is not particularly limited, and conventionally known methods can be mentioned.
Moreover, it is preferable that the laminated body for organic EL of this invention has the blue light cut property by a conventionally well-known method. The blue light means light having a wavelength of 385 to 495 nm.

The foldable member is not particularly limited as long as it is a member having a structure that can be folded, and examples thereof include a foldable smartphone, a foldable touch panel, a tablet, and a foldable (electronic) album.
The member provided with the structure to be folded may be folded at one place or plural places. The direction of folding can also be arbitrarily determined as necessary.

Since the laminated body for organic EL of this invention consists of the structure mentioned above, it has the outstanding hardness, transparency, and durable folding performance.
For this reason, the laminated body for organic EL of this invention can be used conveniently as a curved surface display, the surface protection film of the product which has a curved surface, and the surface protection film of a foldable member.

It is sectional drawing which shows a durable folding test typically.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1
A polyimide film represented by the above formula (1) having a thickness of 30 μm was prepared as a base film, and a hard coat layer composition 1 having the following composition was applied to one surface of the base film, A film was formed.
Next, the solvent in the coating film is evaporated by heating the formed coating film at 70 ° C. for 1 minute, and ultraviolet rays are radiated in the air using an ultraviolet irradiation device (light source H bulb manufactured by Fusion UV System Japan). The film was half-cured by irradiation so that the integrated light amount was 100 mJ / cm ² to form a first hard coat layer having a thickness of 3 μm.
Subsequently, the hard coat layer composition A having the following composition was applied onto the first hard coat layer to form a coating film. Next, the solvent in the coating film is evaporated by heating the formed coating film at 70 ° C. for 1 minute, and the ultraviolet ray is converted into an oxygen concentration using an ultraviolet irradiation device (light source H bulb manufactured by Fusion UV System Japan). Was applied under the condition of 200 ppm or less so that the integrated light amount was 200 mJ / cm ² to completely cure the coating film, thereby forming a second hard coat layer having a thickness of 2 μm to produce an optical laminate. .

(Composition 1 for hard coat layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei 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 & Chemicals) 50 parts by mass (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the obtained first hard coat layer 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 Toa Gosei Co., Ltd.) 50 parts by mass polyfunctional acrylate polymer (Acryt 8KX-012C, Taisei Fine Chemical) 25 parts by mass (solid conversion)
Antifouling agent (BYKUV3500, manufactured by Big Chemie) 1.5 parts by mass (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained second hard coat layer 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 changed to 0.75 μm.

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

(Example 6)
Implemented except that the hard coat layer composition 2 having the following composition was used instead of the hard coat layer composition 1 and the hard coat layer composition B having the following composition was used instead of the hard coat layer composition A. 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 2 for hard coat layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass Hexafunctional acrylate (MF001, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25 parts by mass atypical silica fine particles (average particle size 25 nm, JGC 50 parts by mass (solid conversion)
Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained first hard coat layer was 890 MPa.

(Composition B for hard coat layer)
Urethane acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.) 50 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 50 parts by mass of an antifouling agent (BYKUV3500, manufactured by BYK Chemie) 5 parts by weight (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained second hard coat layer was 600 MPa.

(Example 7)
Implemented except that the hard coat layer composition 3 having the following composition was used instead of the hard coat layer composition 1 and the hard coat layer composition C having the following composition was used instead of the hard coat layer composition A. 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 3 for hard coat layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 35 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass atypical silica fine particles (Average particle diameter 25 nm, manufactured by JGC Catalysts & Chemicals) 30 parts by mass (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the obtained first hard coat layer was 620 MPa.

(Composition C for hard coat layer)
Urethane acrylate (KRM8452, manufactured by Daicel Ornex) 100 parts by mass antifouling agent (TEGO-RAD2600, manufactured by Evonik Japan)
1.5 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the obtained second hard coat layer was 420 MPa.

(Example 8)
Implemented except that the hard coat layer composition 4 having the following composition was used instead of the hard coat layer composition 1 and the hard coat layer composition D having the following composition was used instead of the hard coat layer composition A. 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 4 for hard coat layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass hexafunctional acrylate (MF001, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts by mass polyfunctional acrylate polymer (PVEEA, AX-4) -HC, manufactured by Nippon Shokubai Co., Ltd.)
15 parts by weight (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight atypical silica fine particles (average particle size 25 nm, manufactured by JGC Catalysts & Chemicals) 50 parts by weight (solid conversion)
Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Solvent (MIBK) 150 parts by mass The Martens hardness of the obtained first hard coat layer was 800 MPa.

(Composition D for hard coat layer)
Urethane acrylate (UV7600B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 50 parts by mass Pentaerythritol triacrylate (M306, manufactured by Toagosei Co., Ltd.) 50 parts by mass of antifouling agent (X71-1203M) (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass (solid) Conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained second hard coat layer was 600 MPa.

Example 9
Implemented except that the hard coat layer composition 5 having the following composition was used instead of the hard coat layer composition 1 and the hard coat layer composition E having the following composition was used instead of the hard coat layer composition A. 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 5 for hard coat layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass solid silica Fine particles (average particle size 12 nm, MIBKSD, manufactured by Nissan Chemical Industries)
50 parts by weight (solid conversion)
Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained first hard coat layer was 730 MPa.
Further, the solid silica fine particles were spherical solid silica fine particles.

(Composition E for hard coat layer)
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 size 12 nm, MIBKSD, manufactured by Nissan Chemical Co., Ltd.) 10 parts by mass antifouling Agent (OPTOOL DAC, manufactured by Daikin Industries, Ltd.) 0.5 parts by mass (solid conversion)
Photopolymerization initiator (Irg184) 4 parts by weight solvent (MIBK) 150 parts by weight The Martens hardness of the obtained second hard coat layer 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 produced in the same manner as in 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 base film was 20 μm.

(Example 13)
As a base film, it replaced with the polyimide film represented by said Formula (1) with a thickness of 30 micrometers, and was the same as Example 1 except having used the polyimide film represented by the said Formula (2) with a thickness of 30 micrometers. Thus, an optical laminate was produced.

(Example 14)
As a base film, it replaced with the polyimide film represented by said Formula (1) with a thickness of 30 micrometers, and was the same as Example 1 except having used the polyimide film represented by the said Formula (3) with a thickness of 30 micrometers. Thus, an optical laminate was produced.

(Example 15)
As a base film, it replaced with the polyimide film represented by said Formula (1) with a thickness of 30 micrometers, and it was the same as Example 1 except having used the polyimide film represented by said Formula (8) with a thickness of 30 micrometers. Thus, an optical laminate was produced.

(Example 16)
As a base film, it replaced with the polyimide film represented by said Formula (1) with a thickness of 30 micrometers, and was the same as Example 1 except having used the polyimide film represented by the said Formula (9) with a thickness of 30 micrometers. Thus, an optical laminate was produced.

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

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

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

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

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

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

(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 produced in the same manner as in 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 an organic EL laminate in which the optical laminate is laminated on one surface of the organic EL layer is prepared. Was evaluated. The results are shown in Table 2.

(Durable folding test)
Samples prepared by cutting organic EL laminates according to Examples and Comparative Examples (hereinafter, the surface on which the hard coat layer is formed as the front surface and the opposite side surface as the back surface) into a 30 mm × 100 mm rectangle. , Attached to an endurance tester (DLDMMLH-FU, manufactured by Yuasa System Equipment Co., Ltd.) with a bending inner diameter of 10 mm (distance between opposing samples is 20 mm), and the entire surface on the side where the hard coat layer of the sample is formed The test for folding 180 ° (test to fold the back side to the outside) was performed 100,000 times.
Thereafter, the sample is replaced with a new sample, and the test of folding the entire surface of the sample opposite to the surface on which the hard coat layer is formed by 180 ° (the test of folding the surface so that the surface is on the outside) is performed 100,000 times. Evaluation based on the criteria.
○: Even if the above test is performed on both sides, the sample is not cracked. Δ: When the above test is performed so that the back surface is outside, the sample is not cracked. When the test was performed on the outside, the sample was cracked. X: The sample was cracked regardless of whether the test was performed on the front surface or the back surface.

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

(Steel wool (SW) resistance)
Using the # 0000 steel wool (trade name: BON STAR, manufactured by Nippon Steel Wool Co., Ltd.), the outermost surface of the hard coat layer of the organic EL laminates according to the examples and comparative examples was subjected to a load of 1 kg / cm ² . While applying, it was rubbed back and forth 3500 times at a speed of 50 mm / sec, and then the presence or absence of scratches on the surface of the hard coat layer 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 (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 durable folding performance, scratch resistance and transparency, and the pencil hardness was very excellent at 5H or more.
On the other hand, the organic EL 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 was bad, it was inferior to durable foldability.
Also, 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, Reference in which the base film was too thick In the organic EL laminate according to Example 4, cracks did not occur when the endurance folding test was performed so that the back surface was on the outside, but cracks occurred when the front surface was on the outside. Oops.
Further, in Reference Example 2 in which the second hard coat layer was not formed, the scratch resistance was also inferior.
Moreover, in Reference Example 5 in which the first hard coat layer was not formed, the pencil hardness was inferior.

The organic electroluminescent laminated body of this invention can be used conveniently as a surface material of a foldable image display apparatus.

10 Laminated body 11 for organic EL of the present invention 11 Upper fixing portion 12 Lower fixing portion

Claims (8)

A laminate for organic electroluminescence in which an optical laminate is laminated on one surface of an organic electroluminescence layer,
A laminate for organic electroluminescence which does not break or break when a test of folding the entire surface of the organic electroluminescence laminate by 180 ° at an interval of 20 mm is repeated 100,000 times. The laminate for organic electroluminescence according to claim 1, wherein the optical laminate is a polyimide film or an aramid film. The organic electroluminescent laminate according to claim 1 or 2, wherein the optical laminate has a base film thickness of 10 to 55 µm. The optical laminate includes a first hard coat layer provided on the side opposite to the organic electroluminescence layer of the base film, and a second hard coat layer provided on the side opposite to the base film side of the first hard coat layer. The laminate for organic electroluminescence according to claim 1, 2 or 3, further comprising 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 laminated body for organic electroluminescence of Claim 4 containing the silica fine particle disperse | distributed in the component. The laminated body for organic electroluminescence according to claim 5, wherein the silica fine particles are reactive silica fine particles. The organic electroluminescence laminate according to claim 1, 2, 3, 4, 5, or 6, wherein the optical laminate further comprises a cured layer of a monofunctional monomer. 8. The organic electroluminescence layer according to claim 1, wherein the substrate of the organic electroluminescence layer is a polyimide film, an aramid film, a polyester film, a polyethylene naphthalate film, a cycloolefin film, or an acrylic film. Laminated body.

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