WO2021132030A1

WO2021132030A1 - Optical layered body

Info

Publication number: WO2021132030A1
Application number: PCT/JP2020/047235
Authority: WO
Inventors: 博貴木下; 拓己古屋
Original assignee: リンテック株式会社
Priority date: 2019-12-26
Filing date: 2020-12-17
Publication date: 2021-07-01
Also published as: CN114845873A; KR20220121237A; TW202132105A; JPWO2021132030A1

Abstract

Provided is an optical layered body in which it is possible to appropriately form a detachment starting point between a protective film (β) and a resin layer or another layer on the resin layer, without causing any lifting or detachment in the interface between the resin layer and a release sheet (α). This optical layered body includes a release sheet (α), an optical film having a resin layer disposed on one of the outermost surfaces, and a protective film (β). The resin layer has the release sheet (α) stacked directly thereon. The protective film (β) is stacked on the resin layer, directly or via another layer, from the other outermost surface side of the optical film. The resin layer is made of a cured product of a curable composition containing a curable compound. The relation of A1>A2 is satisfied between a detachment force A1 that is required to detach the release sheet (α) from the resin layer at a low-speed detachment condition of 0.3 m/min and an adhesive force A2 that is generated when detaching the protective film (β) from the resin layer, or the other layer, at the low-speed detachment condition of 0.3 m/min.

Description

Optical laminate

The present invention relates to an optical laminate having a release sheet, an optical film, and a protective film.

In recent years, gas barrier films have been widely used as substrate materials and sealing materials. The gas barrier film is required to have a high gas barrier property capable of suppressing the permeation of water vapor, oxygen and the like. In addition, for example, the lightness of the object to be attached can be increased by increasing the translucency so as not to impair the visibility of the object to be attached such as an electronic device to which the gas barrier film is attached. It is also required to prevent it from being damaged.
From the above viewpoint, a curable composition containing a curable compound is applied onto a support, and the curable compound contained in the obtained coating layer is cured to form a thin resin layer, which is directly or directly on the resin layer. It is known to form a gas barrier layer made of an inorganic film or the like via another layer. By such a manufacturing method, a gas barrier film in which a resin layer is located on one surface and a gas barrier layer is located on the other surface can be obtained (Patent Document 1).
Hereinafter, the property of suppressing the permeation of water vapor and oxygen is referred to as "gas barrier property", the film having gas barrier property is referred to as "gas barrier film", and the laminate having gas barrier property is referred to as "gas barrier property laminate". Further, a film used for optical applications is referred to as an "optical film", and a laminate containing an optical film is referred to as an "optical laminate". The above-mentioned translucent gas barrier film is also an optical film, and the gas barrier laminate containing the translucent gas barrier film is also an optical laminate.

Industrially, optical films such as gas barrier films are often manufactured as long films, then rolled into rolls, and stored and transported as wound bodies. For example, in such a roll-shaped gas barrier film, in order to protect the gas barrier layer and improve the handleability of the gas barrier film, a protective film is provided as the outermost layer on one side, and the outermost layer on the other side is provided. As a result, it may take the form of a gas barrier laminated body provided with a release sheet.

For example, Patent Document 2 describes a gas barrier laminate having a base material layer, a gas barrier layer and a protective film, and in Examples, a base material layer / gas barrier layer / protective film made of a protective film 2 / resin. A gas barrier laminate having the configuration of 1 is described.

International Publication No. 2013/018602 International Publication No. 2018/181004

In the case of a gas barrier film in which a resin layer made of a cured product of a curable resin composition is located on one outermost surface and a gas barrier layer is located on the other outermost surface, a release sheet directly laminated on the resin layer (the present inventor). In addition to providing α), we came up with the idea of providing a protective film (β) that is directly laminated on the gas barrier layer to form a gas barrier laminated body.
As a usage pattern of the gas barrier laminate having the above configuration, for example, the following is assumed. First, the protective film (β) is peeled off from the gas barrier layer, an adhesive layer is formed on the surface of the exposed gas barrier layer, and the gas barrier layer is adhesively fixed to the surface of the adherend by this adhesive layer. Then, by peeling the release sheet (α) from the resin layer, the gas barrier film is attached onto the adherend.

However, in the gas barrier laminate having the above structure, when the protective film (β) is peeled from the gas barrier layer, a peeling starting point cannot be formed well between the protective film (β) and the gas barrier layer, and the resin There was a risk of floating or peeling at the interface between the layer and the release sheet (α). Such a problem is not limited to the gas barrier laminate, and the optical film has a resin layer and another layer, and has a structure of a release sheet (α) / resin layer / other layer / protective film (β). This is a common problem for optical laminates and optical laminates in which the optical film is composed of only a resin layer and has a structure of a release sheet (α) / resin layer / protective film (β).
In the gas barrier laminate of Patent Document 2, the protective film 1 is provided on the gas barrier layer as in the gas barrier laminate having the above configuration, and the protective film 1 can be peeled off before the protective film 2. Are listed. However, the base material layer of the gas barrier laminate described in Patent Document 2 is made of a thermoplastic resin, not a cured product of a curable composition, and the protective film has an adhesive. Therefore, there is no problem of preventing peeling at the interface between the resin layer and the release sheet (α), which is present in gas barrier laminates and optical laminates having the above configuration.

In view of the above problems, the present invention relates the protective film (β) to the resin layer or another layer located on the resin layer without causing floating or peeling at the interface between the resin layer and the release sheet (α). An object of the present invention is to provide an optical laminate capable of appropriately forming a peeling starting point between them.

As a result of diligent studies to solve the above problems, the present inventors have a predetermined relationship between the peeling force and the adhesive force when the peeling sheet (α) and the protective film (β) are peeled under predetermined conditions. As a result, it was found that the above problems could be solved, and the present invention was completed.
That is, the present invention provides the following [1] to [9].
[1] The resin includes a release sheet (α), an optical film containing a resin layer located on one of the outermost surfaces, and a protective film (β), and the release sheet (α) is directly laminated on the resin layer. A protective film (β) is laminated on the layer directly or via another layer from the other outermost surface side of the optical film.
The resin layer is a cured product of a curable composition containing a curable compound.
The peeling force A1 when the release sheet (α) is peeled from the resin layer under the low speed peeling condition of 0.3 m / min, and the protective film (β) is the resin layer or the said under the low speed peeling condition of 0.3 m / min. An optical laminate in which the adhesive force A2 when peeling from another layer has a relationship of A1> A2.
[2] The optical laminate according to the above [1], wherein the peeling force A1 is 500 mN / 50 mm or less.
[3] The protective film (β) has a pressure-sensitive adhesive layer, and is detachably adhered to the resin layer or the other layer by the pressure-sensitive adhesive layer, as described in [1] or [2]. The optical laminate according to.
[4] The optical laminate according to the above [3], wherein the pressure-sensitive adhesive layer contains at least one of a polyolefin-based polymer and a polyolefin-based copolymer.
[5] The resin layer is made into any one of the above [1] to [4], which is a cured product of a curable resin composition containing a polymer component (A) and a curable monomer (B). The optical laminate according to the description.
[6] The polymer component (A) is the optical laminate according to the above [5], wherein the glass transition temperature (Tg) is 250 ° C. or higher.
[7] The optical film includes, as the other layer, a functional layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the functional layer contains an inorganic film or a polymer compound. The optical laminate according to any one of the above [1] to [6], which is a layer obtained by subjecting the layer to a modification treatment and in which a protective film (β) is directly laminated on the functional layer. ..
[8] The optical film includes, as the other layer, a gas barrier layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the protective film (β) is directly laminated on the gas barrier layer. The optical laminate according to any one of the above [1] to [6].
[9] The optical film includes, as the other layer, a conductive layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the protective film (β) is directly laminated on the conductive layer. The optical laminate according to any one of the above [1] to [6].

According to the present invention, it is appropriate between the protective film (β) and the resin layer or another layer located on the resin layer without causing floating or peeling at the interface between the resin layer and the release sheet (α). It is possible to provide an optical laminate capable of forming a peeling starting point.

It is sectional drawing which shows an example of the gas barrier laminated body. It is sectional drawing which shows an example of the roll-shaped gas barrier laminated body. It is sectional drawing which shows the other example of the roll-shaped gas barrier laminated body. It is explanatory drawing which shows an example of the manufacturing method of the gas barrier laminated body. It is explanatory drawing which shows an example of the use method of the gas barrier laminated body. It is a figure explaining the method of measuring the peeling force of a gas barrier laminated body and an optical laminated body, and visual inspection.

Hereinafter, an optical laminate according to an embodiment of the present invention (hereinafter, may be referred to as “the present embodiment”) will be described.

1. 1. Optical Laminate The optical laminate according to the embodiment of the present invention includes a release sheet (α), an optical film containing a resin layer located on one of the outermost surfaces, and a protective film (β), and the resin. The release sheet (α) is directly laminated on the layer, and the protective film (β) is laminated directly on the resin layer from the other outermost surface side of the optical film or via another layer, and the resin layer is curable. It is a cured product of a curable composition containing a compound, and has a peeling force A1 when peeling a release sheet (α) from the resin layer under a low speed peeling condition of 0.3 m / min, and a protective film (β) of 0. The adhesive force A2 when peeling from the resin layer or the other layer under the low speed peeling condition of 3 m / min has a relationship of A1> A2.
The peeling force A1 and the adhesive force A2 each have a width of 50 mm, and the protective film (β) or the peeling sheet (α) of the optical laminate is peeled at an angle of 180 ° by the method described in Examples described later. , The peeling force and the adhesive force (mN / 50 mm) when peeled under the condition of the peeling speed of 0.3 m / min. Further, the peeling force B1 and the adhesive force B2, which will be described later, are the peeling force and the adhesive force (mN / 50 mm) measured in the same manner as in the above procedure except that the peeling speed is set to 20 m / min, respectively.
Hereinafter, the peeling speed of 0.3 m / min may be referred to as “low speed peeling condition”, and the peeling speed of 20 m / min may be referred to as “high speed peeling condition”.

The release sheet (α) is directly laminated on the resin layer of the optical film in which the resin layer which is the cured product of the curable composition containing the curable compound is located on one of the outermost surfaces, and the protective film (β) is formed on the resin layer. In a laminate laminated directly from the other outermost surface side of the optical film or via another layer, the protective film (β) is peeled off from the other outermost surface side of the optical film or the other layer above under low-speed peeling conditions. When the adhesive force A2 at the time of peeling and the peeling force A1 at the time of peeling the release sheet (α) from the resin layer under low speed peeling conditions satisfy the above relationship, the release sheet (α) floats at the interface between the resin layer and the release sheet (α). A portion (peeling starting point) that becomes a starting point of peeling can be easily formed between the protective film (β) and the resin layer or the above-mentioned other layer without causing peeling or peeling, and the resin of the peeling sheet (α). It is possible to provide a gas barrier laminate capable of satisfactorily peeling off only the protective film (β) while maintaining the state of close contact with the layer.

If the above relationship is satisfied under the low-speed peeling condition, as long as the protective film (β) is peeled from the resin layer or another layer under the low-speed peeling condition, floating or peeling occurs at the interface between the resin layer and the peeling sheet (α). A peeling starting point can be appropriately formed between the protective film (β) and the resin layer or the above-mentioned other layer without occurring. Therefore, both when the release sheet (α) is peeled from the resin layer and the protective film (β) is peeled from the other outermost surface of the optical film or the above other layer under high-speed peeling conditions. Regardless of the relationship of the peeling force (for example, even if the relationship between the two peeling forces is reversed under the high-speed peeling condition), after forming the peeling starting point of the protective film (β) under the low-speed peeling condition, the protective film (for example) By peeling the release sheet (β) and the release sheet (α) under high-speed release conditions, both can be appropriately peeled off, and the optical film can be attached to the target adherend with high productivity.

FIG. 1 shows an example of a specific configuration of a gas barrier laminate, which is one of the optical laminates according to the embodiment of the present invention.
The gas barrier laminate 10 shown in the schematic cross-sectional view of FIG. 1 includes a gas barrier film 10a, a release sheet 1, and a protective film 4.
The gas barrier film 10a includes a resin layer 2 located on one outermost surface and a gas barrier layer 3 located on the other outermost surface. The release sheet 1 is directly laminated on the surface of the resin layer 2 opposite to the gas barrier layer 3. Further, the protective film 4 is directly laminated on the surface of the gas barrier layer 3 opposite to the resin layer 2. In other words, the protective film 4 is laminated on the resin layer located on one outermost surface of the gas barrier film 10a, which is one of the optical films, from the other outermost surface side of the gas barrier film 10a via the gas barrier layer 3. ing.
The release sheet 1 of FIG. 1 corresponds to the above-mentioned release sheet (α), and the protective film 4 of FIG. 1 corresponds to the above-mentioned protective film (β).
As will be described later, a layer derived from the gas barrier film 10a is finally formed on the adherend in a state where the protective film 4 and the release sheet 1 are peeled off and removed.

The thickness of the optical laminate can be appropriately determined depending on the intended use of the electronic device and the like. From the viewpoint of handleability, the substantial thickness of the optical laminate according to the embodiment of the present invention is preferably 0.3 to 50 μm, more preferably 0.5 to 25 μm, and more preferably 0.7 to 12 μm. Is.
The "substantial thickness" means the thickness in the used state. That is, the above optical laminate has a release sheet (α) and a protective film (β), but the thickness of the partially release sheet (α) and the protective film (β) that are removed during use is “. It is not included in "substantial thickness".

The resin layer can be thinly formed by using a coating method or the like as described later. As the thickness of the optical laminate is reduced, the bending resistance of the optical film after being attached to the adherend can be further improved.

The optical laminate according to the embodiment of the present invention has a resin layer located on one of the outermost surfaces, and the material and thickness of the resin layer and the other layers, the forming method of each layer, and the like are adjusted. Therefore, it is possible to obtain excellent heat resistance and interlayer adhesion, and also have a low birefringence and excellent optical isotropic properties. When a gas barrier layer is provided in addition to the resin layer as in the gas barrier laminate described above, heat resistance, interlayer adhesion, and gas barrier properties can be obtained by adjusting the material and thickness of each layer, the forming method of each layer, and the like. It is excellent, has a low birefringence, and has excellent optical isotropic properties.

1-1. Relationship between the adhesive force of the protective film (β) and the peeling force of the release sheet (α) As described above, the resin layer of the optical film or the resin layer of the protective film (β) under the low speed release condition of 0.3 m / min. The adhesive force A2 when peeling from the other layer located above and the peeling force A1 when peeling the release sheet (α) from the resin layer under the low speed peeling condition of 0.3 m / min are A1> A2. There is a relationship. From the viewpoint of making it easier to form the peeling starting point of the protective film (β), A1 ≧ 1.2 × A2 is preferable, A1 ≧ 1.5 × A2 is more preferable, and A1 ≧ 2.0 × is more preferable. It is A2, and from the viewpoint of preventing the productivity from being lowered too much, it is preferably A1 ≦ 20 × A2, more preferably A1 ≦ 10 × A2, and further preferably A1 ≦ 5 × A2.
The relationship of A1> A2 in the optical laminate is, for example, to appropriately weaken the adhesive force of the pressure-sensitive adhesive layer formed on the other outermost surface side of the optical film of the protective film (β) described later, or In addition to this, by appropriately selecting the material and surface shape of the release sheet (α) and appropriately selecting the material and manufacturing method of the resin layer, the release force of the release sheet (α) with respect to the resin layer can be obtained. It can be realized by increasing it.

The adhesive force B2 when the protective film (β) is peeled from the resin layer or the other layer under the high speed peeling condition of 20 m / min, and the peeling sheet (α) is peeled from the resin layer under the high speed peeling condition of 20 m / min. The relationship with the peeling force B1 is not particularly limited, and B1> B2, B1 = B2, or B1 <B2 may be used.
Since the protective film (β) can be appropriately peeled off from the optical laminate according to the embodiment of the present invention under low-speed peeling conditions, B1> is not always required when the high-speed peeling conditions are adopted in order to increase productivity. It does not have to be related to B2. That is, B1 ≦ B2 may be satisfied. However, from the viewpoint of preventing tearing of the optical laminate during high-speed peeling, preferably 10 × B1 ≧ B2 ≧ B1, more preferably 6.0 × B1 ≧ B2 ≧ B1, and even more preferably 4.5 × B1 ≧ B1. B2 ≧ B1. When the protective film (β) has an adhesive layer, the value of B2 tends to be larger than that of A2, so that B1 ≦ B2 tends to occur. Even in this case, if the relationship of A1> A2 is maintained as described above, the protective film (β) can be appropriately peeled off in both low-speed peeling at the peeling starting point and high-speed peeling thereafter. can do.

1-2. Adhesive strength of the protective film (β) to the resin layer or other layers When the protective film (β) is peeled from the resin layer of the optical film or other layers on the resin layer under low-speed peeling conditions of 0.3 m / min. The adhesive strength A2 of A2 is preferably 100 mN / 50 mm or less, more preferably 85 mN / 50 mm or less, still more preferably 70 mN / 50 mm or less, from the viewpoint of making it easier to form a peeling starting point of the protective film (β). From the viewpoint of making the protective film (β) stable and easily adhere to the resin layer or the other layer even during storage or transportation of the optical laminate, it is preferably 15 mN / 50 mm or more, more preferably 30 mN / 50 mm. That is all.
The adhesive force B2 when peeling the protective film (β) from the resin layer or the other layer under high-speed peeling conditions of 20 m / min is preferable from the viewpoint of preventing tearing of the optical laminate during high-speed peeling. It is 50 to 2000 mN / 50 mm, more preferably 100 to 1000 mN / 50 mm.
In order to keep the values of the adhesive strengths A2 and B2 within the above numerical ranges, for example, the adhesive strength of the pressure-sensitive adhesive layer formed on the surface of the protective film (β) described later on the other outermost surface side of the optical film. Can be achieved by moderately weakening.

1-3. Peeling force of the peeling sheet (α) against the resin layer The peeling force A1 when the peeling sheet (α) is peeled from the resin layer under a low speed peeling condition of 0.3 m / min is applied to the resin layer when the peeling sheet (α) is peeled. When other layers such as a gas barrier layer are present to avoid excessive stress, the other layers are preferably 500 mN / 50 mm or less, more preferably 300 mN / 50 mm or less, from the viewpoint of preventing cracks from occurring in the other layers. It is more preferably 200 mN / 50 mm or less, and from the viewpoint of making the release sheet (α) stable and easily adhere to the resin layer, it is preferably 40 mN / 50 mm or more, more preferably 60 mN / 50 mm or more, still more preferably 80 mN. / 50 mm or more.
Further, the peeling force B1 when peeling the peeling sheet (α) from the resin layer under the high-speed peeling condition of 20 m / min ensures the adhesion of the peeling sheet (α) to the resin layer without excessively reducing the productivity. From the viewpoint of facilitation, it is preferably 40 to 500 mN / 50 mm, more preferably 60 to 300 mN / 50 mm, and further preferably 80 to 200 mN / 50 mm or less.
In order to keep the values of the peeling forces A1 and B1 within the above numerical range, for example, it can be realized by appropriately selecting the material and the surface shape of the peeling sheet (α).

1-4. Optical film The optical film contains at least a resin layer located on one of the outermost surfaces of the optical film. The optical film may be composed of only a resin layer, or may be composed of a resin layer and another layer.
The other layer is located on the outermost surface of the optical film opposite to the outermost surface on which the resin layer is located, and the protective film (β) is directly laminated on the other layer.
Examples of the other layers include (i) a functional layer obtained by modifying a layer containing an inorganic film or a polymer compound, (ii) a gas barrier layer, and (iii) a conductive layer. When the optical film is composed of a resin layer and a gas barrier layer, the optical film becomes a gas barrier film and the optical laminate becomes a gas barrier laminate. When the optical film is composed of a resin layer and a transparent conductive layer, the optical film becomes a transparent conductive film, and the optical laminate becomes a transparent electrode forming laminate.
The other layer and the resin layer may be directly laminated, or may be further laminated between the two layers via another layer.
A plurality of sets of the resin layer and the other layers may be laminated. In this case, another layer may be present between at least one set of the resin layer and the other layer.

When the optical film is a gas barrier film, the water vapor transmittance of the gas barrier film in an atmosphere of 40 ° C. and 90% relative humidity is usually 1.0 × 10 ⁻² g / m ² / day or less, preferably 1.0 × 10 −2 g / m 2 / day or less. It is 8.0 × 10 ^-3 g / m ² / day or less, more preferably 6.0 × 10 ^-3 g / m ² / day or less.

1-5. Resin layer The resin layer of the optical film contained in the optical laminate according to the embodiment of the present invention comprises a cured product of a curable composition containing a curable compound, preferably the polymer component (A) and the polymer component (A). It comprises a cured product of a curable resin composition containing a curable monomer (B). The resin layer may be a single layer, or may include a plurality of laminated layers.

[Polymer component (A)]
The polymer component (A) is not particularly limited, but preferably has a glass transition temperature (Tg) of 250 ° C. or higher, more preferably 290 ° C. or higher, and even more preferably 320 ° C. or higher. By using the polymer component (A) having a Tg of 250 ° C. or higher, it becomes easy to obtain an optical laminate having sufficiently excellent heat resistance.
Here, Tg is the maximum point of tan δ (loss elastic modulus / storage elastic modulus) obtained by viscoelasticity measurement (measurement in the tensile mode in the range of 0 to 250 ° C. at a frequency of 11 Hz and a heating rate of 3 ° C./min). Refers to temperature.

By forming the resin layer of the optical laminate according to the embodiment of the present invention with a cured product of a curable resin composition containing a polymer component (A) having a Tg of 250 ° C. or higher, the resin layer can be formed. Since it exhibits extremely excellent heat resistance, it can be used as an optical laminate having excellent heat resistance.
When the heat resistance of the resin layer is high, the elastic modulus at a high temperature is increased, and the resin layer is less likely to shrink due to heat. As a result, when the optical film has another layer such as a gas barrier layer, it is possible to avoid causing fine cracks in the other layer. Therefore, for example, when the other layer is a gas barrier layer, it is possible to prevent the gas barrier property from being lowered. Further, when the other layer is a conductive layer, it is possible to prevent the conductivity from being lowered. Further, when the peeling force A1 when peeling the peeling sheet (α) from the resin layer or the other layer under the low speed peeling condition of 0.3 m / min is set to 500 mN / 50 mm or less, the heat resistance and the peeling sheet are obtained. From the viewpoint of both preventing the resin layer from being deformed when the (α) is peeled off, it is possible to prevent cracks in the other layers, which is preferable. In addition, when the other layer is a conductive layer, the heat resistance of the resin layer is high, so that when the conductive layer is formed, the resin layer is affected by heating such as annealing treatment and is deformed. It becomes easier to prevent.

The weight average molecular weight (Mw) of the polymer component (A) is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, and more preferably 500,000 to 1,000. It is in the range of 000. The molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 5.0, more preferably 2.0 to 4.5. The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are polystyrene-equivalent values measured by a gel permeation chromatography (GPC) method. By setting Mw to 100,000 or more, it becomes easy to increase the elongation at break of the resin layer.

As the polymer component (A), a thermoplastic resin is preferable, and an amorphous thermoplastic resin is more preferable. By using an amorphous thermoplastic resin, it becomes easy to obtain a resin layer having excellent optical isotropic properties, and it becomes easy to obtain an optical laminate having excellent transparency. Further, since the amorphous thermoplastic resin is generally easily dissolved in an organic solvent, the resin layer can be efficiently formed by using the solution casting method as described later.
Here, the amorphous thermoplastic resin means a thermoplastic resin whose melting point is not observed in the differential scanning calorimetry.

The polymer component (A) is particularly preferably one that is soluble in a general-purpose organic solvent having a low boiling point such as benzene or methyl ethyl ketone (MEK). If it is soluble in a general-purpose organic solvent, it becomes easy to form a resin layer by coating.

A particularly preferable polymer component (A) is an amorphous thermoplastic resin having a Tg of 250 ° C. or higher, which is soluble in a general-purpose organic solvent having a low boiling point such as benzene or MEK.

As the polymer component (A), a thermoplastic resin having a ring structure such as an aromatic ring structure or an alicyclic structure is preferable, and a thermoplastic resin having an aromatic ring structure is more preferable, from the viewpoint of heat resistance.

Specific examples of the polymer component (A) include a polyimide resin and a polyarylate resin having a Tg of 250 ° C. or higher. Since these resins are generally excellent in heat resistance and are amorphous thermoplastic resins, a coating film can be formed by a solution casting method. Among these, a polyimide resin is preferable because it has a high Tg and is excellent in heat resistance, and it is easy to obtain a resin which is soluble in a general-purpose organic solvent while exhibiting good heat resistance.

The polyimide resin is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, an aromatic polyimide resin, an aromatic (carboxylic acid component) -cyclic aliphatic (diamine component) polyimide resin, and a ring-type fat. Group (carboxylic acid component) -aromatic (diamine component) polyimide resin, cyclic aliphatic polyimide resin, fluorinated aromatic polyimide resin and the like can be used. In particular, a polyimide resin having a fluoro group in the molecule is preferable.

The polyimide resin is preferably soluble in a low boiling point organic solvent such as benzene or methyl ethyl ketone. In particular, it is preferably soluble in methyl ethyl ketone. When it is soluble in methyl ethyl ketone, a layer of a curable resin composition can be easily formed by coating and drying.

A polyimide resin containing a fluoro group is particularly preferable from the viewpoint that it is easily dissolved in a general-purpose organic solvent having a low boiling point such as methyl ethyl ketone, and a resin layer is easily formed by a coating method. The polyimide resin containing a fluoro group is preferably an aromatic polyimide resin having a fluoro group.
The aromatic polyimide resin having a fluoro group preferably has a skeleton represented by the following chemical formula in the molecule.

The polyimide resin having a skeleton represented by the above chemical formula has an extremely high Tg exceeding 300 ° C. due to the high rigidity of the skeleton. Therefore, the heat resistance of the resin layer can be greatly improved. Further, the skeleton is linear and has relatively high flexibility, which makes it easy to increase the breaking elongation of the resin layer. Further, the polyimide resin having the above skeleton can be dissolved in a general-purpose organic solvent having a low boiling point such as methyl ethyl ketone by having a fluoro group. Therefore, the coating can be performed by using the solution casting method to form a resin layer as a coating film, and the solvent can be easily removed by drying. The polyimide resins having the skeleton represented by the above chemical formula are 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 4,4'-(1,1,1,3,3,3). It can be obtained by the above-mentioned polymerization and imidization reaction of polyamic acid using -hexafluoropropane-2,2-diyl) diphthalic acid dianhydride.

The polymer component (A) can be used alone or in combination of two or more. Further, the polymer component (A) and the polymer component (A') having a glass transition temperature of less than 250 ° C. may be used in combination. Examples of the polymer component (A') include a polyamide resin and a polyarylate resin having a Tg of less than 250 ° C., and a polyamide resin is preferable.

[Curable monomer (B)]
The curable monomer (B) is a monomer having a polymerizable unsaturated bond, and is a monomer that can participate in a polymerization reaction, a polymerization reaction, and a cross-linking reaction. In addition, in this specification, "curing" means a broad concept including this "monomer polymerization reaction" or "monomer polymerization reaction and subsequent cross-linking reaction of a polymer". By using the curable monomer (B), an optical laminate having excellent solvent resistance can be obtained.
By forming the resin layer into a layer made of a cured product of a curable resin composition containing the above-mentioned polymer component (A) and the above-mentioned curable monomer (B), a thin resin layer having excellent heat resistance is obtained. It becomes easy to form. Further, when such a material is used, optical problems caused by a material having an anisotropic molecular orientation such as a polyester film generally used as a base material of an optical laminate are less likely to occur. ..

The molecular weight of the curable monomer (B) is usually 3000 or less, preferably 200 to 2000, and more preferably 200 to 1000.
The number of polymerizable unsaturated bonds in the curable monomer (B) is not particularly limited. The curable monomer (B) may be a monofunctional monomer having one polymerizable unsaturated bond, but may be a bifunctional type or a trifunctional type having at least a plurality of polymerizable unsaturated bonds. It is preferable to contain one or more of the polyfunctional monomers of the above.

Examples of the monofunctional monomer include a monofunctional (meth) acrylic acid derivative.
The monofunctional (meth) acrylic acid derivative is not particularly limited as long as it is a compound having one (meth) acryloyl group in the molecule, and a known compound can be used.

Examples of the polyfunctional monomer include a polyfunctional (meth) acrylic acid derivative.
The polyfunctional (meth) acrylic acid derivative is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups in the molecule, and known compounds can be used. For example, 2 to 6 functional (meth) acrylic acid derivatives can be mentioned.
Examples of the bifunctional (meth) acrylic acid derivative include compounds represented by the following formulas.

In the formula, R ¹ represents the same meaning as above, and R ² represents a divalent organic group. Examples of the divalent organic group represented by R ² include a group represented by the following formula.

(In the formula, s represents an integer of 1 to 20, t represents an integer of 1 to 30, u and v each independently represent an integer of 1 to 30, and "-" at both ends is. Represents a joiner.)

Specific examples of the bifunctional (meth) acrylic acid derivative represented by the above formula include tricyclodecanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propoxylated ethoxylated bisphenol A di (meth) acrylate. , Ethylated bisphenol A di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) Phenyl] Fluorene and the like can be mentioned. Among these, from the viewpoint of heat resistance and toughness, such as tricyclodecane dimethanol (meth) acrylate, in the above formula, those divalent organic group represented by R ⁷ has a tricyclodecane skeleton, propoxy ethoxylated bisphenol a di (meth) acrylate, such as ethoxylated bisphenol a di (meth) acrylate, in the above formula, those divalent organic group represented by R ⁷ has a bisphenol skeleton, 9,9-bis In the above formula, it is preferable that the divalent organic group represented by ^{R 7} has a 9,9-bisphenylfluorene skeleton, such as [4- (2-acryloyloxyethoxy) phenyl] fluorene.

Other bifunctional (meth) acrylic acid derivatives include neopentyl glycol adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, and caprolactone-modified dicyclopentenyl di (meth) acrylate. Examples thereof include ethylene oxide-modified di (meth) acrylate phosphate, di (acryloxyethyl) isocyanurate, and allylated cyclohexyl di (meth) acrylate.

Examples of the trifunctional (meth) acrylic acid derivative include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate. ) Acrylate, tris (acrylicoxyethyl) isocyanurate and the like.
Examples of the tetrafunctional (meth) acrylic acid derivative include pentaerythritol tetra (meth) acrylate.
Examples of the pentafunctional (meth) acrylic acid derivative include propionic acid-modified dipentaerythritol penta (meth) acrylate.
Examples of the hexafunctional (meth) acrylic acid derivative include dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

A cyclized polymerizable monomer may be used as the curable monomer (B). The cyclization polymerizable monomer is a monomer having a property of radical polymerization while cyclizing. Examples of the cyclization polymerizable monomer include non-conjugated dienes. For example, an α-allyloxymethylacrylic acid-based monomer can be used, and an alkyl ester having 1 to 4 carbon atoms of 2-allyloxymethylacrylic acid can be used. Cyclohexyl 2- (allyloxymethyl) acrylate is preferable, alkyl esters of 2-allyloxymethylacrylic acid having 1 to 4 carbon atoms are more preferable, and methyl 2- (allyloxymethyl) acrylate is even more preferable.
In addition, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-propyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (i-propyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (n-hexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis A cyclized polymerizable monomer such as -2-propenoate can also be used.

The curable monomer (B) can be used alone or in combination of two or more.
Among these, the curable monomer (B) is preferably a polyfunctional monomer because a resin layer having better heat resistance and solvent resistance can be obtained. As the polyfunctional monomer, a bifunctional (meth) acrylic acid derivative is preferable from the viewpoint that it is easily mixed with the polymer component (A), curing shrinkage of the polymer is unlikely to occur, and curling of the cured product can be suppressed. ..
It is more preferable that the curable monomer (B) contains a polyfunctional (meth) acrylate compound and a cyclizationally polymerizable monomer. By using these in combination, it becomes easy to adjust the breaking elongation of the resin layer within the above range while appropriately adjusting the heat resistance of the resin layer.
When the curable monomer (B) contains a polyfunctional monomer, the content thereof is preferably 40% by mass or more, preferably 50 to 100% by mass, based on the total amount of the curable monomer (B). More preferable.

[Curable resin composition]
The curable resin composition used for forming the resin layer according to the embodiment of the present invention includes a polymer component (A), a curable monomer (B), and, if desired, a polymerization initiator and other components described below. It can be prepared by mixing the components and dissolving or dispersing them in a suitable solvent.

The total content of the polymer component (A) and the curable monomer (B) in the curable resin composition is preferably 40 to 99 with respect to the total mass of the curable resin composition excluding the solvent. It is 5.5% by mass, more preferably 60 to 99% by mass, and even more preferably 80 to 98% by mass.

The content of the polymer component (A) and the curable monomer (B) in the curable resin composition is preferably the mass ratio of the polymer component (A) and the curable monomer (B). , Polymer component (A): curable monomer (B) = 30:70 to 90:10, more preferably 35:65 to 80:20.
In the curable resin composition, when the mass ratio of the polymer component (A): the curable monomer (B) is in such a range, the flexibility of the obtained resin layer is more likely to be improved, and the resin layer is easily improved. The solvent resistance of the resin tends to be maintained.

Further, if the content of the curable monomer (B) in the curable resin composition is within the above range, for example, when the resin layer is obtained by a solution casting method or the like, the solvent can be efficiently removed. , The problem of deformation such as curl and swell due to the lengthening of the drying process is solved.

When a plurality of resins having different solvent solubility, such as a combination of the above-mentioned polyimide resin and a polyamide resin or a polyarylate resin, are used in combination as the polymer component (A), first, the resin is added to a solvent suitable for each. After dissolving, it is preferable to add a solution in which another resin is dissolved to a low boiling point organic solvent in which the resin is dissolved.

The curable resin composition can contain a polymerization initiator, if desired. The polymerization initiator can be used without particular limitation as long as it initiates the curing reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.

Examples of the thermal polymerization initiator include organic peroxides and azo compounds. Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, a phosphorus-based photopolymerization initiator, a titanosen-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, and a thioxanthone-based photopolymerization initiator. Etc., and a phosphorus-based photopolymerization initiator is preferable.
When the polymer component (A) is a thermoplastic resin having an aromatic ring, the curing reaction may not easily occur as a result of the polymer component (A) absorbing ultraviolet rays. However, by using the phosphorus-based photopolymerization initiator, the curing reaction can be efficiently advanced by utilizing the light having a wavelength that is not absorbed by the polymer component (A).
The polymerization initiator may be used alone or in combination of two or more.

The content of the polymerization initiator is preferably 0.05 to 15% by mass, more preferably 0.05 to 10% by mass, and 0.05 to 5% by mass with respect to the total mass of the curable resin composition excluding the solvent. Mass% is more preferred.

Further, in the curable resin composition, in addition to the polymer component (A), the curable monomer (B), and the polymerization initiator, photopolymerization of triisopropanolamine, 4,4'-diethylaminobenzophenone, etc. It may contain an initiator.

The solvent used for preparing the curable resin composition is not particularly limited, and for example, an aliphatic hydrocarbon solvent such as n-hexane and n-heptane; an aromatic hydrocarbon solvent such as toluene and xylene; dichloromethane, Halogenated hydrocarbon solvents such as ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, 2- Ketone-based solvents such as pentanone, isophorone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; cellosolve-based solvents such as ethyl cellosolve; ether-based solvents such as 1,3-dioxolane; and the like.

The content of the solvent in the curable resin composition is not particularly limited, but is usually 0.1 to 1000 parts by mass, preferably 1 to 100 parts by mass with respect to 1 part by mass of the polymer component (A). is there. By appropriately adjusting the amount of the solvent, the viscosity of the curable resin composition can be adjusted to an appropriate value.

Further, the curable resin composition may further contain known additives such as a plasticizer, an antioxidant, and an ultraviolet absorber as long as the object and effect of the present invention are not impaired.

The method for curing the curable resin composition can be appropriately determined depending on the type of polymerization initiator and curable monomer used. Details will be described later in the section of the method for manufacturing the optical laminate.

[Properties of resin layer, etc.]
The thickness of the resin layer is not particularly limited, and may be determined according to the purpose of the optical laminate. The thickness of the resin layer is usually 0.1 to 300 μm, preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm, still more preferably 0.1 to 10 μm, and particularly preferably 0.2 to 10 μm. Is.

When the resin layer has a thickness of, for example, about 0.1 to 10 μm, it is possible to prevent the thickness of the optical laminate from increasing, and it is possible to obtain a thin optical laminate. A thin optical laminate is preferable because the optical laminate does not increase the thickness of the entire applicable device in applications such as organic EL displays that are required to be thin. Further, if the thin optical laminate is used, the flexibility and bending resistance of the optical laminate after mounting can be improved.

The resin layer has excellent solvent resistance. Since it has excellent solvent resistance, for example, even when an organic solvent is used when forming another layer on the surface of the resin layer, the surface of the resin layer is hardly dissolved. Therefore, for example, even when another layer such as a gas barrier layer or a conductive layer is formed on the surface of the resin layer by using a resin solution containing an organic solvent, the components of the resin layer are unlikely to be mixed into these layers. , Gas barrier property and conductivity are hard to decrease.

The resin layer has excellent interlayer adhesion with other layers such as a gas barrier layer and a conductive layer. That is, the above-mentioned functional layer, gas barrier layer, or conductive layer can be formed without providing the anchor coat layer on the resin layer.

The resin layer is preferably colorless and transparent. Since the resin layer is colorless and transparent, the optical laminate according to the embodiment of the present invention can be preferably used for optical applications.

As described above, the resin layer can have heat resistance, solvent resistance, interlayer adhesion, and transparency, and further has a low birefringence and excellent optical isotropic properties. it can. Therefore, as will be described later, by forming a gas barrier layer, a conductive layer, or the like on the resin layer having such characteristics by, for example, a solution casting method, the functional layer has excellent gas barrier properties and excellent conductivity. Moreover, it is also possible to prevent the gas barrier property and the conductivity from being impaired by at least one of the heat and the solvent due to at least one of the heat resistance and the solvent resistance of the resin layer. Further, the obtained optical laminate is excellent in heat resistance, interlayer adhesion, and transparency. Further, it is possible to obtain an optical laminate having a low birefringence and excellent optical isotropic properties.

1-6. Gas Barrier Layer The material of the gas barrier layer of the gas barrier laminate according to the embodiment of the present invention is not particularly limited as long as it has gas barrier properties. For example, a gas barrier layer made of an inorganic film, a gas barrier layer containing a gas barrier resin, a gas barrier layer obtained by modifying a layer containing a polymer compound, and the like can be mentioned.
Among these, since a thin layer having excellent gas barrier properties and solvent resistance can be efficiently formed, the gas barrier layer is a gas barrier layer made of an inorganic film and a gas barrier obtained by modifying a layer containing a polymer compound. Layers are preferred.
In other words, the gas barrier layer made of the above-mentioned inorganic film is a functional layer made of an inorganic film having a gas barrier property, and the gas barrier layer obtained by subjecting the layer containing the above-mentioned polymer compound to a modification treatment is In other words, it is also a functional layer obtained by subjecting a layer containing a polymer compound having a gas barrier property to a modification treatment. When the optical laminate is used for applications that do not require or have little need for gas barrier properties, the functional layer made of the above-mentioned inorganic film or the layer containing a polymer compound is modified to obtain a functional layer. It may have a poor gas barrier property.

The inorganic film is not particularly limited, and examples thereof include an inorganic thin-film film.
Examples of the inorganic vapor deposition film include a vapor deposition film of an inorganic compound or a metal.
Inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; inorganic carbides; Examples thereof include inorganic sulfides; inorganic oxidants such as silicon oxide nitrides; inorganic oxidative carbides; inorganic nitriding carbides; and inorganic oxynitride carbides.
Examples of the raw material of the metal vapor deposition film include aluminum, magnesium, zinc, tin and the like.
These can be used alone or in combination of two or more.
Among these, an inorganic vapor deposition film made of an inorganic oxide, an inorganic nitride or a metal as a raw material is preferable from the viewpoint of gas barrier property, and further, an inorganic material made of an inorganic oxide or an inorganic nitride as a raw material is preferable from the viewpoint of transparency. A vapor-deposited film is preferable. Further, the inorganic vapor deposition film may be a single layer or a multilayer.

The thickness of the inorganic thin-film film is preferably in the range of 10 to 2000 nm, more preferably 20 to 1000 nm, more preferably 30 to 500 nm, and further preferably 40 to 200 nm from the viewpoint of gas barrier properties and handleability.

Examples of the method for forming the inorganic vapor deposition film include a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, and an optical CVD method. The CVD method can be mentioned.

Examples of the gas barrier resin used in the gas barrier layer containing the gas barrier resin include polyvinyl alcohol or a partially saponified product thereof, an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene and the like. Examples thereof include resins that do not easily permeate oxygen and the like.

From the viewpoint of gas barrier properties, the thickness of the gas barrier layer containing the gas barrier resin is preferably in the range of 10 to 2000 nm, more preferably 20 to 1000 nm, more preferably 30 to 500 nm, and further preferably 40 to 200 nm.

Examples of the method of forming the gas barrier layer containing the gas barrier resin include a method of applying a solution containing the gas barrier resin on the resin layer and appropriately drying the obtained coating film.

The polymer compound used in the gas barrier layer obtained by modifying a layer containing a polymer compound (hereinafter, may be referred to as “polymer layer”) includes silicon-containing polymer compound, polyimide, polyamide, and polyamide. Examples thereof include imide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer and the like. .. These polymer compounds can be used alone or in combination of two or more.

Among these, the polymer compound is preferably a silicon-containing polymer compound. Examples of the silicon-containing polymer compound include polysilazane compounds (Japanese Patent Laid-Open No. 63-16325, JP-A-62-195024, JP-A-63-81122, JP-A-1-138108, JP-A-2-. 84437, Japanese Patent Application Laid-Open No. 2-175726, Japanese Patent Application Laid-Open No. 4-63833, Japanese Patent Application Laid-Open No. 5-238827, Japanese Patent Application Laid-Open No. 5-345926, Japanese Patent Application Laid-Open No. 2005-36089, Japanese Patent Application Laid-Open No. 6-122852 See JP-A-6-299118, JP-A-6-306329, JP-A-9-313333, JP-A-10-245436, JP-A-2003-514822, International Publication WO2011 / 107018, etc. ), Polycarbosilane compound (Journal of Materials Science, 2569-2576, Vol. 13, 1978, Organometallics, 1336-1344, Vol. 10, 1991, Journal of Organometallic Chemistry, 1-196 See JP-A-51-126300, JP-A-2001-328991, JP-A-2006-117917, JP-A-2009-286891, JP-A-2010-106100, etc.), Polysilane compounds (R. D. Miller, J. Michel; Chemical Review, Vol. 89, p. 1359 (1989), N. Matsumoto; Japanese Journal of Physics, Vol. 37, p. 5425 (1998), JP-A-2008-63586, JP-A. 2009-235358, etc.), polyorganosiloxane-based compounds (see JP-A-2010-229445, JP-A-2010-232569, JP-A-2010-238736, etc.) and the like.

Among these, polysilazane compounds are preferable from the viewpoint of being able to form a gas barrier layer having excellent gas barrier properties. Examples of polysilazane compounds include inorganic polysilazane and organic polysilazane. Examples of the inorganic polysilazane include perhydropolysilazane, and examples of the organic polysilazane include compounds in which part or all of the hydrogen of the perhydropolysilazane is replaced with an organic group such as an alkyl group. Among these, inorganic polysilazane is more preferable from the viewpoint of easy availability and the ability to form a gas barrier layer having excellent gas barrier properties.
Further, as the polysilazane compound, a commercially available product commercially available as a glass coating material or the like can be used as it is.
The polysilazane compound can be used alone or in combination of two or more.

The polymer layer may contain other components in addition to the above-mentioned polymer compound as long as the object of the present invention is not impaired. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, flame retardants and the like.

The content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of being able to form a gas barrier layer having excellent gas barrier properties.

As a method for forming the polymer layer, for example, a layer-forming solution containing at least one polymer compound, optionally other components, a solvent and the like is applied to the resin layer or preferably on the resin layer by a known method. Examples thereof include a method of applying the coating film on the primer layer formed in the above and appropriately drying the obtained coating film to form the coating film.

When applying the layer forming solution, a known device such as a spin coater, a knife coater, or a gravure coater can be used.

It is preferable to dry the obtained coating film or heat the coating film in order to improve the gas barrier property of the gas barrier laminate. As the heating and drying methods, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be adopted. The heating temperature is usually 80 to 150 ° C., and the heating time is usually several tens of seconds to several tens of minutes.

When the above-mentioned polysilazane compound is used when forming the gas barrier layer of the gas barrier laminate, for example, the conversion reaction of polysilazane occurs by heating after coating, and the coating film has excellent gas barrier properties.
On the other hand, when a resin layer having low heat resistance is used, the resin layer may be deformed by heating when forming such a coating film. Deformation of the resin layer may adversely affect the gas barrier property of the gas barrier layer of the gas barrier laminated body. However, since the resin layer according to the embodiment of the present invention has excellent heat resistance, it is unlikely to be deformed by heating during and after coating. Therefore, it is possible to avoid a decrease in the gas barrier property of the gas barrier laminated body due to the deformation of the resin layer.

The thickness of the polymer layer is usually 20 to 1000 nm, preferably 30 to 800 nm, and more preferably 40 to 400 nm.
Even if the thickness of the polymer layer is on the nano-order, a gas-barrier laminate having sufficient gas-barrier performance can be obtained by performing a modification treatment as described later.

Examples of the reforming treatment include ion implantation and vacuum ultraviolet light irradiation. Among these, ion implantation is preferable from the viewpoint of obtaining high gas barrier performance. In ion implantation, the amount of ions implanted into the polymer layer may be appropriately determined according to the purpose of use (required gas barrier property, transparency, etc.) of the gas barrier laminate to be formed.

The injected ions include rare gas ions such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;
Ions of alkane gases such as methane, ethane, propane, butane, pentane, hexane; ions of alkene gases such as ethylene, propylene, butene, and penten; ions of alkaziene gases such as pentadiene and butadiene; acetylene, Ions of alkyne gases such as methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, inden, naphthalene and phenanthrene; ions of cycloalkene gases such as cyclopropane and cyclohexane; cyclopentene, Ions of cycloalkene gases such as cyclohexene;
Ions of conductive metals such as gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten and aluminum;
Ions of silane (SiH ₄ ) or organosilicon compounds; and the like.

Examples of the organosilicon compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and tetrat-butoxysilane;
Alkoxysilanes having substituents or substituents such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane;
Arylalkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane;
Disiloxane such as hexamethyldisiloxane (HMDSO);
Aminosilanes such as bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetrakisdimethylaminosilane, and tris (dimethylamino) silane;
Hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetramethyldisilazane and other silazans;
Cyanatosilanes such as tetraisocyanatesilanes;
Halogenosilanes such as triethoxyfluorosilane;
Alkenylsilanes such as diallyldimethylsilane and allyltrimethylsilane;
Alkylsilane having an unsubstituted or substituent such as di-t-butylsilane, 1,3-disilabtan, bis (trimethylsilyl) methane, tetramethylsilane, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, benzyltrimethylsilane;
Cyril alkynes such as bis (trimethylsilyl) acetylene, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propine;
Cyrilalkenes such as 1,4-bistrimethylsilyl-1,3-butadiyne, cyclopentadienyltrimethylsilane;
Arylalkylsilanes such as phenyldimethylsilane and phenyltrimethylsilane;
Alkynylalkylsilanes such as propargyltrimethylsilane;
Alkenylalkylsilanes such as vinyltrimethylsilane;
Disilane such as hexamethyldisilane;
Siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane;
N, O-bis (trimethylsilyl) acetamide;
Bis (trimethylsilyl) carbodiimide;
And so on.
These ions may be used alone or in combination of two or more.

Among them, at least one selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton because it can be injected more easily and a gas barrier layer having particularly excellent gas barrier properties can be obtained. Seed ions are preferred.

The method of injecting ions is not particularly limited, and examples thereof include a method of irradiating ions (ion beams) accelerated by an electric field, a method of injecting ions in plasma, and the like. Above all, the latter method of injecting plasma ions is preferable because a gas barrier film can be easily obtained.

The plasma ion implantation method includes (I) a method of injecting ions existing in the plasma generated by using an external electric field into the polymer layer, or (II) applying the ions to the layer without using an external electric field. A method of implanting ions existing in the plasma generated only by an electric field due to a negative high voltage pulse into the polymer layer is preferable.

In the method (I) above, the pressure at the time of ion implantation (pressure at the time of plasma ion implantation) is preferably 0.01 to 1 Pa. When the pressure at the time of plasma ion implantation is in such a range, the ions can be implanted easily and efficiently and uniformly, and the target gas barrier layer can be efficiently formed.

The method (II) described above does not require a high degree of decompression, the processing operation is simple, and the processing time can be significantly shortened. In addition, the entire layer can be treated uniformly, and ions in the plasma can be continuously injected into the polymer layer with high energy when a negative high voltage pulse is applied. Furthermore, without the need for special other means such as radio frequency (high frequency, hereinafter abbreviated as "RF") or high frequency power sources such as microwaves, simply applying a negative high voltage pulse to the layer Good quality ions can be uniformly injected into the polymer layer.

In any of the methods (I) and (II), the pulse width when a negative high voltage pulse is applied, that is, when ion is implanted, is preferably 1 to 15 μsec. When the pulse width is in such a range, ions can be injected more easily, efficiently, and uniformly.

The applied voltage when generating plasma is preferably -1 to -50 kV, more preferably -1 to -30 kV, and particularly preferably -5 to -20 kV. If ion implantation is performed when the applied voltage is greater than -1 kV, the ion implantation amount (dose amount) becomes insufficient and the desired performance cannot be obtained. On the other hand, if the ion implantation is performed at a value smaller than -50 kV, the film is charged at the time of ion implantation, and problems such as coloring of the film occur, which is not preferable.

Examples of the ion species to be implanted with plasma ions include the same as those exemplified as the ions to be implanted.

A plasma ion implanter is used to implant the ions in the plasma into the polymer layer.
Specifically, the plasma ion implantation apparatus (i) superimposes high-frequency power on a feed-through that applies a negative high-voltage pulse to a polymer layer (hereinafter, may be referred to as “ion implantation layer”). A device that evenly surrounds the layer for ion implantation with plasma to attract, implant, collide, and deposit ions in the plasma (Japanese Patent Laid-Open No. 2001-26887), (ii) An antenna is provided in the chamber, and high-frequency power is provided. After the plasma reaches the periphery of the ion-implanted layer, positive and negative pulses are alternately applied to the ion-implanted layer to attract and collide the electrons in the plasma with the positive pulse. An apparatus (Japanese Patent Laid-Open No. 2001-156013), (iii), which heats a layer to be ion-implanted, controls the pulse constant to control the temperature, and applies a negative pulse to attract and implant ions in the plasma. A plasma ion implanter that generates plasma using an external electric field such as a high-frequency power source such as a microwave and applies a high voltage pulse to attract and implant ions in the plasma. (Iv) High without using an external electric field. Examples thereof include a plasma ion implanter that implants ions in plasma generated only by an electric field generated by applying a voltage pulse.

Among these, it is preferable to use the plasma ion implantation apparatus of (iii) or (iv) because the processing operation is simple, the processing time can be significantly shortened, and it is suitable for continuous use.
Examples of the method using the plasma ion implantation apparatus of (iii) and (iv) are those described in International Publication WO2010 / 021326.

In the plasma ion injection devices of (iii) and (iv), since the plasma generating means for generating plasma is also used by the high voltage pulse power supply, special other means such as a high frequency power source such as RF or microwave is used. By simply applying a negative high voltage pulse, plasma is generated, the ions in the plasma are continuously injected into the polymer layer, and the surface portion has a portion modified by ion injection. A gas barrier laminate having a molecular layer, that is, a gas barrier layer formed can be mass-produced.

The thickness of the portion where the ions are injected can be controlled by the injection conditions such as the type of ions, the applied voltage, and the processing time, and is determined according to the thickness of the polymer layer, the purpose of use of the gas barrier laminate, and the like. However, it is usually 5 to 1000 nm.

The injection of ions can be confirmed by performing elemental analysis measurement near 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).

It can be confirmed that the gas barrier layer has a gas barrier property because the water vapor permeability of the gas barrier layer is small.
The water vapor transmittance of the gas barrier layer in an atmosphere of 40 ° C. and 90% relative humidity is usually 1.0 g / m ² / day or less, preferably 0.8 g / m ² / day or less, and more preferably 0. .5g ^/ m is in 2 / day, more preferably not more than 0.1 g ^/ m 2 / day. The water vapor permeability can be measured by a known method.

1-7. Conductive layer The conductive layer provided in the optical laminate according to the embodiment of the present invention is not particularly limited in material as long as it has conductivity, but it is preferably a transparent conductive layer. Here, "transparent" means that the light transmittance at a wavelength of 450 nm is 80% or more.
Examples of the conductive material constituting the transparent conductive layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, antimonated tin oxide (ATO); fluorine-doped tin oxide (FTO); tin oxide, germanium-doped zinc oxide (GZO), zinc oxide, indium oxide, indium tin oxide (ITO). , Semi-conductive metal oxides such as zinc indium oxide (IZO); metals such as gold, silver, chromium and nickel; mixtures of these metals with conductive metal oxides; inorganic conductivity such as copper iodide and copper sulfide Substances; organic conductive materials such as polyaniline, polythiophene, polypyrrole; and the like. A metal such as silver may form a transparent conductive layer by aggregating particles such as nanofillers, nanorods, and nanofibers.

There are no particular restrictions on the method of forming the transparent conductive layer. For example, a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method and the like can be mentioned. Further, for example, a transparent conductive layer may be obtained from the coating film by applying a coating material containing a particulate metal to the laminate for a transparent conductive film.

The thickness of the transparent conductive layer may be appropriately selected according to the application and the like. It is usually 10 nm to 50 μm, preferably 20 nm to 20 μm.

1-8. Release sheet (α)
The release sheet (α) has a role of protecting the resin layer when the optical laminate is stored, transported, etc., and is peeled off in a predetermined step.

The release sheet (α) is preferably in the form of a sheet or a film. The sheet-like or film-like shape is not limited to a long one, but also includes a short flat plate-like one.

The release sheet (α) is a paper base material such as glassin paper, coated paper, or high-quality paper; a laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene on these paper base materials; Those that have been sealed with starch, polyvinyl alcohol, acrylic-styrene resin, etc .; or polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and plastic films such as polyolefin films such as polyethylene and polypropylene; glass, etc. Can be mentioned.

Further, the release sheet (α) may have a release agent layer provided on a paper base material or a plastic film from the viewpoint of ease of handling, but has a curable composition on the release sheet (α). When an object is applied to form a resin layer, the curable composition does not spread on the release sheet (α), resulting in a non-uniform coating film or an unapplied portion. From the viewpoint of this, it is preferable that the release agent layer does not exist. That is, it is preferable that the release sheet (α) does not have a release agent layer and the resin layer is directly formed on the release sheet (α).
When the release agent layer is provided, the release layer can be formed by using a conventionally known release agent such as a silicone type release agent, a fluorine type release agent, an alkyd type release agent, and an olefin type release agent.
The thickness of the release agent layer is not particularly limited, but is usually 0.02 to 2.0 μm, more preferably 0.05 to 1.5 μm.
Further, the resin layer is usually flexible, and when the release sheet (α) has the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer and the resin layer may adhere to each other. , It is preferable not to have an adhesive layer.

The thickness of the peeling sheet (α) is preferably 25 to 150 μm from the viewpoint of maintaining heat resistance, avoiding an increase in peeling force due to an increase in peeling area, and reducing strain generated in the optical laminate during winding. More preferably, it is 40 to 125 μm.

The surface roughness Ra (arithmetic mean roughness) of the release sheet (α) is preferably 10.0 nm or less, more preferably 8.0 nm or less. The surface roughness Rt (maximum cross-sectional height) is preferably 100 nm or less, more preferably 50 nm or less.
When the surface roughness Ra and Rt are 10.0 nm or less and 100 nm or less, respectively, it is possible to prevent the surface roughness of the layer in contact with the process film from becoming excessively large. Therefore, when the optical laminate has the above-mentioned functional layer, gas barrier layer, conductive layer, and the like, it becomes easy for those layers to exert the desired functions.
The surface roughness Ra and Rt are values obtained by the optical interferometry in a measurement area of 100 μm × 100 μm.

1-9. Protective film (β)
The protective film (β) has a role of protecting functional layers such as a gas barrier layer and a transparent conductive layer when the optical laminate is stored, transported, etc., and is peeled off in a predetermined step.
The protective film (β) is preferably in the form of a sheet or a film. The sheet-like or film-like shape is not limited to a long one, but also includes a short flat plate-like one.
The protective film (β) is usually attached to the surface of the resin layer or the other layer after the resin layer contained in the optical film or the other layer on the resin layer is formed. Alternatively, from the viewpoint of preventing the protective film (β) from unintentionally falling off from another layer, it is preferable that the adhesive layer is provided on the base material. In this case, an adhesive layer is provided on the surface of the protective film (β) on the optical film side. Since the protective film (β) has an adhesive layer, the protective film (β) is detachably adhered to the resin layer or another layer. As the base material of the protective film (β), a material having the same material and thickness as the release sheet (α) can be used.

The adhesive strength of the pressure-sensitive adhesive layer can be determined by selecting the material, thickness, etc. of the protective film (β) under low-speed peeling conditions of 0.3 m / min to the resin layer of the optical film or another resin layer on the resin layer. The adhesive force A2 when peeling from the layer has a relationship of A1> A2 with respect to the peeling force A1 when the peeling sheet (α) is peeled from the resin layer under a low speed peeling condition of 0.3 m / min. It has been adjusted.
As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a pressure-sensitive adhesive containing a polyolefin-based polymer, and a pressure-sensitive adhesive containing a polyolefin-based copolymer are used. Examples thereof include adhesives and the like. Of these, it is more preferable that the pressure-sensitive adhesive layer contains at least one of a polyolefin-based polymer and a polyolefin-based copolymer from the viewpoint of facilitating the acquisition of the adhesive strength A2 that facilitates the relationship of A1> A2. Examples of the polyolefin-based polymer include polyethylene and polypropylene, and examples of the polyolefin-based copolymer include an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid copolymer.
Examples of the protective film containing a commercially available polyolefin-based adhesive that can be used as the protective film (β) include San-A Kaken Co., Ltd. Sanitect PAC-3-50THK and Sanitect PAC-2-70.

1-10. Other Configuration Examples of Optical Laminates The optical laminates according to the embodiment of the present invention are not limited to those shown in FIG. 1, and a plurality of sets are laminated with the resin layer and the above other layers as one set. It may be a thing. Further, one layer or two or more layers may be contained between the resin layer and the other layer as long as the object of the present invention is not impaired. When a plurality of sets of the resin layer and the gas barrier layer are laminated, at least one of the adjacent sets may include one layer or two or more other layers.
Examples of the other layer include a conductor layer, a shock absorbing layer, an adhesive layer, a bonding layer, a process sheet, and the like. Further, the arrangement position of the other layer is not particularly limited.

Examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, antimonated tin oxide (ATO); fluorine-doped tin oxide (FTO); tin oxide, germanium-doped zinc oxide (GZO), zinc oxide, indium oxide, indium tin oxide (ITO). , Semi-conductive metal oxides such as zinc indium oxide (IZO); metals such as gold, silver, chromium and nickel; mixtures of these metals with conductive metal oxides; inorganic conductivity such as copper iodide and copper sulfide Substances; organic conductive materials such as polyaniline, polythiophene, polypyrrole; and the like.

There are no particular restrictions on the method of forming the conductor layer. For example, a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method and the like can be mentioned.

The thickness of the conductor layer may be appropriately selected according to the application and the like. It is usually 10 nm to 50 μm, preferably 20 nm to 20 μm.

The shock absorbing layer is for protecting the above-mentioned functional layer, gas barrier layer, conductive layer, etc. when a shock is applied to these layers. The material forming the shock absorbing layer is not particularly limited, and examples thereof include an acrylic resin, a urethane resin, a silicone resin, an olefin resin, and a rubber material.

The method for forming the shock absorbing layer is not particularly limited. For example, a material for forming the shock absorbing layer and, if desired, a shock absorbing layer forming solution containing other components such as a solvent are placed on the layer to be laminated. Examples thereof include a method of coating, drying the obtained coating film, and heating or the like as necessary to form the coating film.
Alternatively, a shock absorbing layer may be separately formed on the release base material, and the obtained film may be transferred onto the layer to be laminated and laminated.
The thickness of the shock absorbing layer is usually 1 to 100 μm, preferably 5 to 50 μm.

The adhesive layer is a layer used when the optical laminate is attached to the adherend. The material for forming the adhesive layer is not particularly limited, and known adhesives such as acrylic, silicone, and rubber, adhesives, heat sealants, and the like can also be used.

The bonding layer is a layer used when a resin layer and the above other layers are combined as one set and a plurality of sets are bonded together to manufacture an optical laminate. The bonding layer is a layer for bonding the resin layer contained in each adjacent set and the other layer to maintain the laminated structure. The bonding layer may be a single layer or a plurality of layers. Examples of the bonding layer include a layer having a single-layer structure formed by using an adhesive and a layer having a layer formed by using an adhesive on both sides of a support layer.

The material used for forming the bonding layer is not particularly limited as long as it can bond the resin layer and the other layers to each other and maintain the laminated structure, and a known adhesive can be used. The adhesive is preferable because the resin layer and the other layers can be bonded to each other at room temperature.
Examples of the pressure-sensitive adhesive used for the bonding layer include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive. Among these, acrylic adhesives and urethane adhesives are preferable from the viewpoint of adhesive strength, transparency and handleability. Further, an adhesive capable of forming a crosslinked structure as described later is preferable.
The pressure-sensitive adhesive may be in any form such as a solvent-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, and a hot-melt type pressure-sensitive adhesive.

1-11. Roll-shaped optical laminate FIG. 2 is a schematic cross-sectional view showing an example of a roll-shaped gas barrier laminate which is a roll-shaped optical laminate.
The roll-shaped gas barrier laminate 10A shown in FIG. 2 has a roll-shaped portion 10A ₁ wound around a tubular or rod-shaped core material 11. _{Then, the drawer portion 10A 2} is formed by pulling out the tip portion of the roll-shaped portion 10A _1.
In the roll-shaped gas barrier laminate 10A shown in FIG. 2, the roll-shaped portion 10A ₁ is formed so that the protective film 4 is located outside the release sheet 1. Therefore, it is possible to make it difficult to apply stress to the protective film 4 in the roll-shaped portion 10A _1.
The optical laminate of the present invention can appropriately peel off the protective film (β) in both low-speed peeling at the peeling starting point and high-speed peeling thereafter. Therefore, when the protective film (β) is continuously peeled from the roll-shaped optical laminate, if the protective film (β) can be appropriately peeled off at a low speed at the peeling starting point, then roll-to-roll. The protective film (β) can be appropriately peeled off in the high-speed peeling in the above process.

FIG. 3 is a schematic cross-sectional view showing another example of the roll-shaped gas barrier laminate, which is a roll-shaped optical laminate.
The roll-shaped gas barrier laminate 10B shown in FIG. 3 has a roll-shaped portion 10B ₁ wound around the core material 11. _{Then, the drawer portion 10B 2} is formed by pulling out the tip portion of the roll-shaped portion 10B _1.
In the roll-shaped gas barrier laminate 10B shown in FIG. 3, the roll-shaped portion 10B ₁ is formed so that the protective film 4 is located inside the release sheet 1. Therefore, it becomes easy to prevent the protective film 4 from being peeled off due to contact with an external object or the like during storage or transportation of the gas barrier laminate 10B.

1-12. How to use the optical laminate When using the optical laminate, the protective film (β) and release sheet (α) are peeled from the optical laminate. Then, it is used in a state of being attached to a target adherend such as a display or an electronic device.
FIG. 5 is a diagram showing an example of how to use the gas barrier laminate having the configuration shown in FIG.
In the usage method of this example, first, as shown in FIGS. 5A to 5B, the protective film 4 is peeled off from the gas barrier layer 3. Here, when the protective film 4 is peeled off, the peeling sheet 1 is required to be kept in close contact with the resin layer 2 without floating or peeling off from the resin layer 2. Since the release sheet 1 continues to adhere to the resin layer 2 even after the protective film 4 is peeled off, the protection of the gas barrier layer can be continued even in the subsequent steps.

Next, as shown in FIG. 5 (c), an adhesive layer 5 is formed on the surface of the exposed gas barrier layer 3, and as shown in FIG. 5 (d), the protective film 4 is peeled off by the adhesive layer 5. The gas barrier layer 3 of the gas barrier laminated body 10 after being formed is adhesively fixed to the surface of the adherend 20. As the material forming the adhesive layer 5, a material that can be used for the adhesive layer described above can be used. When the adherend has an adhesive layer, the step of forming the adhesive layer 5 can be omitted.

After that, as shown in FIG. 5 (e), the gas barrier film 10a is attached onto the adherend 20 by peeling the release sheet 1 from the resin layer 3.

1-13. Method for Manufacturing Optical Laminate The optical laminate according to the embodiment of the present invention is manufactured by using a release sheet (α). By using the release sheet (α), the optical laminate can be efficiently and easily manufactured. In particular, a method having the following steps 1 to 4 is preferable.

Step 1: Forming a curable resin layer on a release sheet (α) using a curable resin composition containing a polymer component (A) and a curable monomer (B) Step 2: Step 1 Step 3: Forming a resin layer composed of a cured resin layer by curing the curable resin layer obtained in Step 3: Others such as a functional layer, a gas barrier layer, a conductive layer, etc. on the resin layer obtained in Step 2. Step of forming a layer Step 4: A step of laminating a protective film (β) on other layers such as a functional layer, a gas barrier layer, and a conductive layer obtained in step 3.

FIG. 4 shows an example of a manufacturing process of a gas barrier laminate, which is one of the optical laminates according to the embodiment of the present invention. 4 (a) to 4 (b) are in the above step 1, FIGS. 4 (c) to 4 (d) are in the above step 2, and FIG. 4 (e) is in the above step 3, FIG. 4 (f). Corresponds to each of the above steps 4.

(Step 1)
First, a curable resin composition containing the polymer component (A) and the curable monomer (B) is cured on the release sheet (α) (corresponding to reference numeral 1 in FIG. 4 (a)). A curable resin layer (corresponding to reference numeral 2a in FIG. 4B), which is the previous resin layer, is formed.

The method of applying the curable resin composition onto the release sheet (α) is not particularly limited, and is a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, and a die coating method. , A known coating method such as a gravure coating method can be used.

The method for drying the obtained coating film is not particularly limited, and conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. Even if the curable resin composition used for forming the resin layer contains the polymer component (A) having a very high Tg, the solution casting method is performed by containing the curable monomer (B). When the coating film obtained by using the above is dried, the solvent can be efficiently removed.

The drying temperature of the coating film is usually 30 to 150 ° C., preferably 50 to 120 ° C. The drying time is usually 1 to 10 minutes, more preferably 2 to 7 minutes.
The thickness of the dry coating film (curable resin layer) is not particularly limited, but it may be the same as the thickness of the resin layer described above because there is almost no difference from the thickness after curing.

(Step 2)
Next, the curable resin layer obtained in step 1 is cured to form a cured resin layer. This cured resin layer becomes a resin layer (symbol 2 in FIG. 4C).
The method for curing the curable resin layer is not particularly limited, and a known method can be adopted. For example, when the curable resin layer is formed by using a curable resin composition containing a thermosetting initiator, the curable resin layer can be cured by heating the curable resin layer. .. The heating temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C.

When the curable resin layer is formed by using a curable resin composition containing a photopolymerization initiator, the curable resin layer is irradiated with an electromagnetic wave as an active energy ray to obtain a curable resin. The layer can be cured. Electromagnetic waves can be irradiated using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.

The wavelength of the electromagnetic wave is preferably in the ultraviolet light region of 200 to 400 nm, more preferably 350 to 400 nm. Irradiation dose is usually illuminance 50 ~ 1000mW / cm ^2, light amount 50 ~ 5000mJ / cm ^2, preferably in the range of 200 ~ 5000mJ / cm ^2. The irradiation time is usually 0.1 to 1000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds. In order to satisfy the above-mentioned amount of light in consideration of the heat load in the light irradiation step, irradiation may be performed a plurality of times.

In this case, in order to prevent deterioration of the polymer component (A) due to electromagnetic waves and coloring of the resin layer, the curable resin composition is irradiated with electromagnetic waves through a filter that absorbs light having a wavelength unnecessary for the curing reaction. You may. According to this method, light having a wavelength that is unnecessary for the curing reaction and deteriorates the polymer component (A) is absorbed by the filter, so that the deterioration of the polymer component (A) is suppressed and the colorless and transparent resin is used. Layers are easier to obtain.
As the filter, a resin film such as a polyethylene terephthalate film can be used. When a resin film is used, it is preferable to provide a step of laminating a resin film such as a polyethylene terephthalate film on the curable resin layer between

steps

1 and 2. The resin film is usually peeled off after the step 2.

Further, the curable resin layer can be cured by irradiating the curable resin layer with an electron beam as an active energy ray. When irradiating an electron beam, an electron beam accelerator or the like can be used. The irradiation dose is usually in the range of 10 to 1000 grad. The irradiation time is usually 0.1 to 1000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds.

The curable resin layer may be cured in an inert gas atmosphere such as nitrogen gas, if necessary. By performing curing in an inert gas atmosphere, it becomes easier to prevent oxygen, moisture, and the like from interfering with curing.

As described above, the resin film formed by the procedures of coating, drying, and curing can be formed thin, so that it is highly flexible and can have optical isotropic properties. Further, since it is a curable resin, it can be made excellent in heat resistance and solvent resistance.

(Step 3)
Then, on the resin layer obtained in step 2, a layer of a composition for forming a gas barrier layer by using the above-mentioned solution containing the gas barrier resin or the like, in other words, a gas barrier layer before curing (FIG. 4). The gas barrier layer (reference numeral 3 in FIG. 4 (e)) is formed by forming the reference numeral 3a) of (d) and curing the layer of this composition. When the gas barrier layer made of an inorganic film is formed by vapor deposition or the like, the state shown in FIG. 4 (c) is directly transferred to the state shown in FIG. 4 (e).
As a method for forming the gas barrier layer, the method described above can be appropriately adopted.
For example, when the gas barrier layer is a layer obtained by modifying a layer containing a silicon-containing polymer compound, a step of forming a layer containing the silicon-containing polymer compound on a resin layer and a silicon-containing high content thereof. A gas barrier layer can be formed by a step of subjecting a layer containing a molecular compound to a modification treatment.

The gas barrier layer contained in the gas barrier laminate can be formed by various methods such as an extrusion molding method and a coating method, but the gas barrier performance of the gas barrier laminate may deteriorate depending on the method of forming the gas barrier layer. In particular, when a gas barrier layer is formed by a forming method involving heating, for example, coating / drying, the resin layer may be physically or chemically affected, and properties such as gas barrier properties may be deteriorated.

As a method for forming a layer containing a silicon-containing polymer compound and a method for performing a modification treatment, the methods described above can be adopted.
Further, as a method of performing the modification treatment, the silicon is carried while transporting a long film in which a layer containing a silicon-containing polymer compound is formed on the resin layer obtained in step 2 in a certain direction. It is preferable that the layer containing the contained polymer compound is subjected to a modification treatment to produce a gas barrier laminate.
According to this manufacturing method, for example, a long gas barrier laminate can be continuously manufactured.

(Step 4)
By attaching the protective film (β) on the gas barrier layer obtained in step 3, a gas barrier laminate can be obtained. This step is performed, for example, by arranging the forming surface of the pressure-sensitive adhesive layer of the protective film (β) toward the gas barrier layer and sequentially pressing the protective film (β) so as not to take in bubbles.

As described above, the manufacturing method having the above steps 1 to 4 forms a curable resin layer by using the release sheet (α), and efficiently obtains the gas barrier laminate according to the embodiment of the present invention. , Can be manufactured continuously and easily.

Next, specific examples of the present invention will be described, but the present invention is not limited to these examples. Measurement of peeling forces A1, B1 and adhesive strengths A2 and B2 in the gas barrier laminates and optical laminates produced in Examples and Comparative Examples described later, appearance evaluation when the protective film (β) is peeled off, and , The water vapor permeability of the gas barrier film used for each gas barrier laminate was measured and calculated by the following procedure.
[Measurement of peeling force and adhesive force]
The protective film or release sheet of the gas barrier laminate and the optical laminate (both 50 mm wide) is peeled under the conditions of a peel angle of 180 ° and a peel speed of 0.3 m / min or 20 m / min, and the peeling force at that time. And the adhesive strength (mN / 50 mm) was measured. The test environment is 23 ° C and 50% relative humidity, and a low-speed peeling tester (manufactured by A & D Co., Ltd., product name: Tensilon universal testing machine RTG) is used for peeling at a peeling speed of 0.3 m / min. -1225) was used, and a high-speed peeling tensile tester (manufactured by Tester Sangyo Co., Ltd., product name: high-speed peeling tester TE-701) was used for peeling at a peeling speed of 20 m / min.
In measuring the peeling force A1, for the gas barrier laminate, as shown in FIG. 6A, both sides of the gas barrier layer 3 are in the state of the gas barrier film before the protective film (β) is attached to the gas barrier layer 3. A sample adhered to the glass plate 30 with the adhesive film 5 was prepared as a measurement sample. As for the optical laminate, a resin layer before the protective film (β) was attached to the glass plate with a double-sided adhesive film was prepared as a measurement sample. Then, the release sheet (α) was peeled off from these measurement samples, and the release force A1 was measured.
In measuring the adhesive strength A2, the gas barrier laminate was a polyethylene terephthalate (PET) film group having a thickness of 50 μm, as shown in FIG. 6B, instead of the gas barrier films of Examples and Comparative Examples. A gas barrier layer 3 was formed on the material 40 in the same procedure as in Examples and Comparative Examples, a protective film (β) was attached onto the gas barrier layer, and the material was stored in the above test environment for 24 hours. After that, a sample in which the surface of the PET film base material 40 opposite to the one provided with the gas barrier layer 3 was fixed to the glass plate 30 with the double-sided adhesive film 5 was prepared as a measurement sample. As for the optical laminate, a resin layer before the protective film (β) was attached to the glass plate with a double-sided adhesive film was prepared as a measurement sample. Then, the adhesive strength A2 was measured by peeling the protective film (β) from these measurement samples. The calculation of the measured value was based on JIS Z0237: 2000, and the average value of the two measurements was taken as each peeling force and adhesive force.
Regarding the final gas barrier laminates and optical laminates obtained in Examples and Comparative Examples, the protective film (β) was removed when the peeling force A1 was measured, and the protective film (β) was removed when the adhesive force A2 was measured. Even if the surface opposite to the peeling sheet (α) or protective film (β) to be peeled off is fixed to the glass plate 30 after the sheet (α) is removed, the peeling force A1 measured in the above procedure, It has the same value as the adhesive strength A2.
[Appearance evaluation]
The exposed surface of the release sheet 1 of the gas barrier laminate produced in Examples and Comparative Examples was fixed to the glass plate 30 with the double-sided adhesive film 5 to prepare a sample for evaluation. Then, when the protective film 4 was peeled off under the condition of a peeling speed of 0.3 m / min or 20 m / min, the appearance of the remaining laminated body was visually observed. When there was no abnormality in the appearance and no floating or peeling occurred in the resin layer, it was evaluated as "G", and when at least one of the floating and peeling occurred in the resin layer, it was evaluated as "F". The appearance of the optical laminate produced in the examples was also evaluated in the same manner as in the above procedure.

<Example 1>
(1) Preparation of Resin Layer As a polymer component, 100 parts by mass of a polyimide resin (PI) pellet (KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., Tg = 354 ° C., weight average molecular weight 280,000) contains methyl ethyl ketone. A 15% by weight solution of PI was prepared by dissolving in a solvent. Next, in this solution, 122 parts by mass of tricyclodecanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP) as a curable compound, and bis (2,4,6-trimethyl) as a polymerization initiator. Benzoyl) -phenylphosphine oxide (Omnirad TPO, manufactured by BASF) was added and mixed in an amount of 5 parts to prepare a curable composition 1. The curable compound and the polymerization initiator used in this example and other experimental examples do not contain a solvent and are all raw materials having a solid content of 100%.
Next, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., Cosmoshine PET100A4100, thickness 100 μm) was prepared as a release sheet (α), and a curable resin composition was prepared on the surface opposite to the easy-adhesion layer surface. Was applied by hand coating, and the obtained coating film was heated at 100 ° C. for 3 minutes to dry the coating film.
Further, on this dried coating film, a PET film (manufactured by Toyo Boseki Co., Ltd., Cosmo Shine PET50A4100, thickness 50 μm) having the same easy-adhesive layer on one side as described above is placed so that the surface opposite to the easy-adhesive surface faces. Using a belt conveyor type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., product name: ECS-401GX), and using a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd., product name: H04-L41) The curing reaction was carried out under the conditions of a height of 100 mm, an ultraviolet lamp output of 3 kW, an illuminance of a light wavelength of 365 nm of 150 mW / cm ² , and a light amount of 400 mJ / cm ² (measured by an ultraviolet photometer UV-351 manufactured by ORC Manufacturing Co., Ltd.). A resin layer having a thickness of 5 μm was formed.

(2) Lamination of Gas Barrier Layer Next, the PET film laminated on the coating film is peeled off to expose the resin layer, and a coating agent containing a polysilazane compound (perhydropolysilazane (PHPS)) as a main component on the resin layer () A 200 nm thick polymer containing perhydropolysilazane by applying Amiacca NL-110-20, solvent: xylene) manufactured by Merck Performance Materials Co., Ltd. by the spin coating method and heating and drying at 100 ° C. for 2 minutes. A compound layer (polysilazane layer) was formed.
Next, using a plasma ion injection device (manufactured by Nippon Denshi Co., Ltd., RF power supply: "RF"56000; manufactured by Kurita Seisakusho Co., Ltd., high voltage pulse power supply: PV-3-HSHV-0835), the gas flow rate is 100 sccm, Duty. Under the conditions of ratio 0.5%, applied DC voltage -6 kV, frequency 1000 Hz, applied RF power 1000 W, chamber internal pressure 0.2 Pa, DC pulse width 5 μsec, and processing time 200 seconds, ions derived from argon gas were added to the polymer compound layer ( It was injected into the surface of the polysilazane layer) to form a gas barrier layer. By laminating the gas barrier layer on the resin layer in this way, a gas barrier film was produced on the release sheet (α). The same treatment was repeated to obtain a gas barrier film with a release sheet having two gas barrier layers.

(3) Adhesion of protective film A polyolefin-based protective film (manufactured by Sanei Kaken Co., Ltd., Sanitect PAC-3-50THK) (low density polyethylene group) was used as a protective film (β-1) on the gas barrier layer side of the obtained gas barrier film. A gas barrier laminate was obtained by attaching a material, an olefin adhesive, and a thickness of 50 μm)).

<Example 2>
In Example 1, instead of the protective film (β-1), an ethylene-vinyl acetate copolymer (EVA) -based protective film (manufactured by Sanei Kaken Co., Ltd., Sanitect PAC-2-70 (low density polyethylene base material, EVA) A gas barrier laminate was obtained in the same manner as in Example 1 except that the adhesive (thickness 70 μm)) was used as the protective film (β-2).

<Comparative example 1>
100 parts by mass of an acrylate resin (Cybinol LT-57 manufactured by Saiden Chemical Co., Ltd.) and 4 parts by mass of an isocyanate-based cross-linking agent (Kokazai K-315 manufactured by Saiden Chemical Co., Ltd.) are mixed to form an adhesive composition (1). ) Was obtained. A protective film (β-3) is prepared by forming an adhesive layer having a thickness of 5 μm on a polyester film (PET38-600E, manufactured by Nissin Kasei Co., Ltd.) using the adhesive composition (1). did. Then, a gas barrier laminate was produced in the same procedure as in Example 1 except that the protective film (β-3) was used instead of the protective film (β-1).

<Comparative example 2>
100 parts by mass of acrylate resin (Cyvinol LT-55 manufactured by Saiden Chemical Co., Ltd.), 1.6 parts by mass of isocyanate-based cross-linking agent (Kokazai K-200 manufactured by Saiden Chemical Co., Ltd.), and isocyanate-based cross-linking agent (Saiden Chemical Co., Ltd.) 2 parts by mass of Koukazai M-2) manufactured by Koukazai Co., Ltd. was mixed to obtain a pressure-sensitive adhesive composition (2). A protective film (β-4) is prepared by forming an adhesive layer having a thickness of 5 μm on a polyester film (PET38-T100G manufactured by Nissin Kasei Co., Ltd.) using the adhesive composition (2). did. Then, a gas barrier laminate was produced in the same procedure as in Example 1 except that the protective film (β-4) was used instead of the protective film (β-1).

<Example 3>
In Example 1, an optical laminate was obtained in the same procedure as in Example 1 except that the gas barrier layer was not laminated and the protective film was directly attached to the resin layer.

<Example 4>
In Example 2, an optical laminate was obtained in the same procedure as in Example 2 except that the gas barrier layer was not laminated and the protective film was directly attached to the resin layer.

Table 1 shows the measurement results of the gas barrier laminate and the optical laminate of each Example and Comparative Example.

As is clear from the results in Table 1, the gas barrier laminates of Examples 1 and 2 and the optical laminates of Examples 3 and 4 both peel the release sheet (α) from the resin layer under low-speed release conditions. The peeling force A1 and the adhesive force A2 when peeling the protective film (β) from the gas barrier layer under low-speed peeling conditions have a relationship of A1> A2, and the protective film (β) may be peeled off. It can be seen that it shows a nice appearance. The gas barrier laminates of Examples 1 and 2 and the optical laminates of Examples 3 and 4 have a peeling force B1 when the high-speed peeling condition peeling sheet (α) is peeled from the resin layer under low-speed peeling conditions. The adhesive force B2 when the protective film (β) is peeled from the gas barrier layer under low-speed peeling conditions has a relationship of B2> B1, but the gas barrier laminates of Examples 1 and 2 and Examples 3 and 4 The peeling starting point can be easily formed in the optical laminate by satisfying the relationship of A1> A2. Therefore, it can be seen that the protective film (β) can be peeled even under high-speed peeling conditions.

On the other hand, in the gas barrier laminates of Comparative Examples 1 and 2, since the release sheet (α) and the protective film (β) have an A1 <A2 relationship, the release starting point is easily formed under low speed release conditions. As a result, it can be understood that when the protective film (β) is peeled off, the resin layer formed on the peeling sheet (α) is lifted or peeled off.

According to the optical laminate of the present invention, the protective film (β) is appropriately peeled between the resin layer or another layer without causing floating or peeling at the interface between the resin layer and the release sheet (α). Since the starting point can be formed, peeling can be performed satisfactorily under a wide range of peeling conditions from low speed to high speed. Therefore, the members for elements constituting various electronic devices such as organic EL elements and thermoelectric conversion elements can be made into an optical laminate capable of corresponding to various manufacturing conditions.

1: Release sheet (α)
2: Resin layer 2a: Curable resin layer 3: Gas barrier layer (other layers)
3a: Gas barrier layer before curing 4: Protective film (β)
5:

Adhesive layers

10, 10A, 10B: Gas barrier laminate (optical laminate)
10A ₁ , 10B ₁ : Roll-shaped

part

10A ₂ , 10B ₂ : Drawer part 10a: Gas barrier film 11: Core material 20: Adhesive body 30: Glass plate 40: PET film base material

Claims

An optical film containing a release sheet (α), a resin layer located on one of the outermost surfaces, and a protective film (β) are included, and the release sheet (α) is directly laminated on the resin layer, and optical is applied to the resin layer. A protective film (β) is laminated directly or via another layer from the other outermost surface side of the film.
The resin layer is a cured product of a curable composition containing a curable compound.
The peeling force A1 when the release sheet (α) is peeled from the resin layer under the low speed peeling condition of 0.3 m / min, and the protective film (β) is the resin layer or the said under the low speed peeling condition of 0.3 m / min. An optical laminate in which the adhesive force A2 when peeling from another layer has a relationship of A1> A2.
The optical laminate according to claim 1, wherein the peeling force A1 is 500 mN / 50 mm or less.
The optical laminate according to claim 1 or 2, wherein the protective film (β) has an adhesive layer and is detachably adhered to the resin layer or the other layer by the adhesive layer. body.
The optical laminate according to claim 3, wherein the pressure-sensitive adhesive layer contains at least one of a polyolefin-based polymer and a polyolefin-based copolymer.
The optical laminate according to any one of claims 1 to 4, wherein the resin layer is a cured product of a curable resin composition containing a polymer component (A) and a curable monomer (B). ..
The optical laminate according to claim 5, wherein the polymer component (A) has a glass transition temperature (Tg) of 250 ° C. or higher.
The optical film includes, as the other layer, a functional layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the functional layer is changed to a layer containing an inorganic film or a polymer compound. The optical laminate according to any one of claims 1 to 6, which is a layer obtained by performing a quality treatment and in which a protective film (β) is directly laminated on the functional layer.
The optical film includes, as the other layer, a gas barrier layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the protective film (β) is directly laminated on the gas barrier layer. The optical laminate according to any one of claims 1 to 6.
The optical film includes, as the other layer, a conductive layer located on the outermost surface opposite to the outermost surface on which the resin layer is located, and the protective film (β) is directly laminated on the conductive layer. The optical laminate according to any one of claims 1 to 6.